Review Article Bioactive Micronutrients in Coffee - downloads
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Review Article Bioactive Micronutrients in Coffee: Recent Analytical Approaches for Characterization and Quantification Abdulmumin A. Nuhu Department of Chemistry, Ahmadu Bello University, PMB 1069, Zaria, Kaduna 2222, Nigeria Correspondence should be addressed to Abdulmumin A. Nuhu; [email protected] Received 22 September 2013; Accepted 7 November 2013; Published 22 January 2014 Academic Editors: D. Koya, T. Nurmi, and S. van Hemert Copyright © 2014 Abdulmumin A. Nuhu. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Production of coffee beans is an important lifeline for the economy of several countries in Latin America, Africa, and Asia. e brew from this well sought for cash crop is readily consumed due to its good sensory qualities owing to the presence of many micronutrients. Some of these chemical compounds possess biological activities, including antiproliferative, antioxidant, and antimicrobial effects. Four representative groups of these micronutrients, namely, caffeine, chlorogenic acid, diterpenes, and trigonelline, play key roles in these bioactive effects of coffee. In order to guarantee the quality of coffee products and to protect consumer interest and safeguard their well-being, it is extremely important to employ sensitive and accurate analytical methods in the characterization and quantitative determination of these bioactive constituents. is review aims to present recent applications in this regard. 1. Introduction Coffee is a popular beverage that is widely consumed around the world [1, 2]. Since its introduction into Arabia from Ethiopia many centuries ago [3], its cultivation has continued to blossom in three regions of our globe, namely, Africa, Latin America and Asia, [4–6]. Coffee is oſten produced from the roasted beans of a great variety of coffee crops [7]. However, Coffea canephora and Coffea arabica are the two most eco- nomically important species [8, 9]. It can now be found in both organic and conventional types [10]. Presently, the largest coffee bean producing region is Latin America [11], leading to an immense boost in the economy of the respective countries by bringing in the much needed foreign exchange. Unfortunately, market shocks, extreme weather conditions, and pests are an enormous challenge to this reality [12, 13]. World prices of coffee beans vary reasonably with their geographical source, as this affects the physical presentation of these beans and their nutritive components, two factors that are important in determination of coffee quality [14–17]. ere are many nutritive substances in coffee brews which vary with the types of techniques employed in brewing pro- cesses [18]. Coffee contains mineral ingredients such as Ca, K, Fe, P, Ni, Mg, and Cr [19], polyphenols, caffeine, melanoidins, and carbohydrates [20, 21] among others. Since the vari- ability of these chemical constituents affects price of coffee commodities by determining their qualities, there must be sensitive, precise, and accurate analytical means for their determination. It is, therefore, the aim of this paper to present a review on the recent analytical methods that have been applied to the characterization and quantification of four important bioactive constituents in coffee: caffeine, chloro- genic acid, diterpenes, and trigonelline. 2. Bioactive Compounds of Coffee Coffee is rich in many bioactive substances and its consump- tion has been associated with many beneficial effects [22]. ese include, but not limited to, reduced risk of hepato- cellular carcinoma [23], antiproliferative effect against some human cancer cell lines [24], therapeutic potential against Alzheimer’s disease [25], and antioxidant capacity through modulation of Nrf2 nuclear translocation [26]. 2.1. Caffeine. Caffeine (C 8 H 10 N 4 O 2 ), an alkaloid that is chemically known as 1,3,7-trimethylxanthine (or 1,3,7-tri- methyl-1H-purine-2, 6(3H, 7H)-dione), is among the most commonly consumed stimulants worldwide [27, 28]. It Hindawi Publishing Corporation ISRN Nutrition Volume 2014, Article ID 384230, 13 pages http://dx.doi.org/10.1155/2014/384230
Transcript of Review Article Bioactive Micronutrients in Coffee - downloads
Review ArticleBioactive Micronutrients in Coffee Recent AnalyticalApproaches for Characterization and Quantification
Abdulmumin A Nuhu
Department of Chemistry Ahmadu Bello University PMB 1069 Zaria Kaduna 2222 Nigeria
Correspondence should be addressed to Abdulmumin A Nuhu aanuhuyahoocom
Received 22 September 2013 Accepted 7 November 2013 Published 22 January 2014
Academic Editors D Koya T Nurmi and S van Hemert
Copyright copy 2014 Abdulmumin A Nuhu This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited
Production of coffee beans is an important lifeline for the economy of several countries in Latin America Africa and AsiaThe brew from this well sought for cash crop is readily consumed due to its good sensory qualities owing to the presence ofmany micronutrients Some of these chemical compounds possess biological activities including antiproliferative antioxidantand antimicrobial effects Four representative groups of these micronutrients namely caffeine chlorogenic acid diterpenes andtrigonelline play key roles in these bioactive effects of coffee In order to guarantee the quality of coffee products and to protectconsumer interest and safeguard their well-being it is extremely important to employ sensitive and accurate analytical methods inthe characterization and quantitative determination of these bioactive constituents This review aims to present recent applicationsin this regard
1 Introduction
Coffee is a popular beverage that is widely consumed aroundthe world [1 2] Since its introduction into Arabia fromEthiopiamany centuries ago [3] its cultivation has continuedto blossom in three regions of our globe namely Africa LatinAmerica and Asia [4ndash6] Coffee is often produced from theroasted beans of a great variety of coffee crops [7] HoweverCoffea canephora and Coffea arabica are the two most eco-nomically important species [8 9] It can now be found inboth organic and conventional types [10] Presently thelargest coffee bean producing region is Latin America [11]leading to an immense boost in the economy of the respectivecountries by bringing in the much needed foreign exchangeUnfortunately market shocks extreme weather conditionsand pests are an enormous challenge to this reality [12 13]World prices of coffee beans vary reasonably with theirgeographical source as this affects the physical presentationof these beans and their nutritive components two factorsthat are important in determination of coffee quality [14ndash17]
There aremany nutritive substances in coffee brewswhichvary with the types of techniques employed in brewing pro-cesses [18] Coffee containsmineral ingredients such as Ca KFe P Ni Mg and Cr [19] polyphenols caffeine melanoidins
and carbohydrates [20 21] among others Since the vari-ability of these chemical constituents affects price of coffeecommodities by determining their qualities there must besensitive precise and accurate analytical means for theirdetermination It is therefore the aim of this paper to presenta review on the recent analytical methods that have beenapplied to the characterization and quantification of fourimportant bioactive constituents in coffee caffeine chloro-genic acid diterpenes and trigonelline
2 Bioactive Compounds of Coffee
Coffee is rich in many bioactive substances and its consump-tion has been associated with many beneficial effects [22]These include but not limited to reduced risk of hepato-cellular carcinoma [23] antiproliferative effect against somehuman cancer cell lines [24] therapeutic potential againstAlzheimerrsquos disease [25] and antioxidant capacity throughmodulation of Nrf2 nuclear translocation [26]
21 Caffeine Caffeine (C8H10N4O2) an alkaloid that is
chemically known as 137-trimethylxanthine (or 137-tri-methyl-1H-purine-2 6(3H 7H)-dione) is among the mostcommonly consumed stimulants worldwide [27 28] It
Hindawi Publishing CorporationISRN NutritionVolume 2014 Article ID 384230 13 pageshttpdxdoiorg1011552014384230
2 ISRN Nutrition
N
NNO
N
O
Figure 1 Chemical structure of caffeine
contains two fused rings (Figure 1) that are related to purines[29] Caffeine is found in many natural and processedproducts Examples of these sources include green tea [30 31]mate tea [32 33] chocolate [34] and caffeinated beveragesand energy drinks [35ndash37] C arabica [38] and Robustacoffee (C canephora var Robusta) [39] also contain thismicronutrient
Consumption of caffeine has shownmany positive effectsin various human and animal experimentations At a dose of6mgKgminus1 bodymass it was found to exhibit ergogenic effectthe ability to increase physical exercise without a concomitantincrease in effort sensation in sedentary men [40] Its stimu-latory activity was also tested with some promising results inpersonswith Parkinsonrsquos disease where it can be used toman-age both motor and nonmotor symptoms [41] In a mousemodel crude caffeine was found to reduce the accumulationof 120573-amyloid peptides a characteristic feature in patientssuffering from Parkinsonrsquos disease [42] Investigations haverevealed that crude caffeine did possess hydrophilic antiox-idant activity (145 120583mol Trolox equivalent (TE)g) and lipo-philic antioxidant activity (66 120583mol TEg) and its adminis-tration has led to the inhibition of cyclooxygenase-2 enzymebetter than aspirin [43]
Some of the adverse effects of high doses of caffeineinclude decrease tonus of the lower esophageal sphinctermuscle overstimulation of central nervous system intrauter-ine growth retardation and higher risk of miscarriage [44]Withdrawal from caffeine ingestion may present with lowermental alertness diminished performance and over sleepi-ness [45]
22 Chlorogenic Acid Chlorogenic acid (CGA) (Figure 2)which has nothing to do with chlorine is an ester that isformed from the reaction of caffeic acid with L-quinic acidhence the name 5-caffeoylquinic acid (5-CQA) [46 47] It isa polyphenolic compound that is abundant in many plants[48] It is present in tobacco leaves [49] mulberry tree [50]and coffee beans [51] It is found to be responsible for theastringent taste of coffee brews [52 53] Many positive effectshave been attributed to CGA For instance its hypolipidemiceffect has led to weight reduction in experimental mice [5455] The antioxidant activities of this phytochemical wereexhibited against ischemia-reperfusion injury [56] and inthe protection against oxidative damage of macromoleculessuch as DNA lipids and proteins [57] When administeredto mice under scopolamine-induced amnesia CGA hasshown neuroprotective function via the inhibition of acetylcholinesterase [58]
Different microbial entities are susceptible to CGArsquos anti-microbial activities With respect to viruses CGA has shown
OOH
OHOH
OHHO
HO
O
O
Figure 2 Chemical structure of chlorogenic acid
O H
lt OHOH
H
H
CH3
Figure 3 Chemical structure of the diterpene cafestol
antihepatitis B virus potency in a duckling model [59] andpotential anti-H1N1 influenza virus [60] CGA analogs thatshowed appreciable anti-HIV activities have been synthesized[61] CGA is not only active against viral particles but ithas also antibacterial and antifungal functions At minimuminhibitory concentrations (MIC) of 20ndash80120583gmL the growthof all bacterial pathogens tested was inhibited by CGA [62]It is argued that the high resistance of immature peach fruitsto the brown rot fungus Monilinia laxa is due to their highcontents of CGA [63]
23 Diterpenes Diterpenes are a group of terpenoids com-monly found as secondary metabolites in terrestrial andmarine organisms [64]They often occur in a C-20 backbonewhere isoprene units combine in different forms to give anarray of diterpenes such as abietane [65] cembrane [66]guanacastepene A [67] quinonoid [68] jatropha [69] andcafestol and kahweol [70] typesThese and several othersmaybe found in coffee [71] tea [72] and Salvia spp [73] Sometypes have been isolated from the fungus Trichoderma longi-brachiatum [74] and from sponge family [75]
Diterpenes have displayed several types of bioactivitiesvia different mechanisms A diterpene alkaloid isolated fromthe Caribbean sponge Agelas citrina has shown antifungalfunction [76] Experiment with oridonin type has demon-strated its antiproliferative effect against leukemia-derivedJurkat cells [77] Abietane type was cytotoxic to human pan-creatic cancer cell line MIA PaCa-2 [78] Antioxidant func-tion is found in Salvia officinalis [79] and an isolate of theBrazilian alga Dictyota menstrualis has indicated anti-HIVpotential of this phytochemical [80] Antimicrobial activitiesare found in a recent review [81] Some diterpenes are toxicto insects [82] and to embryos of medaka Japanese rice fish[83] Structure of cafestol is given in Figure 3
24 Trigonelline Trigonelline (TRG) (Figure 4) is a nitroge-nous compound a pyridine alkaloid that is derived from themethylation of the nitrogen atom of nicotinic acid (niacin)
ISRN Nutrition 3
N+
O
O
minus
Figure 4 Chemical structure of trigonelline
hence the name N-methyl nicotinic acid [84ndash86] TRG isfound in pumpkin seeds [87] mangrove legumes [88] Mor-inga oleifera tree [89] and coffee [90 91] It is used as roastinglevel discriminator in both Arabica and Robusta coffees [92]
TRG has a proven antidiabetic effect its administrationto model rats suffering from diabetes mellitus has resultedin reduced blood glucose levels in oral glucose tolerance test[93] It has also shown beneficial effects in rats displayingperipheral neuropathy a condition forwhich there is no effec-tive drug for its treatment [94] Its function as an inhibitor ofNrf2 gene transcription has caused pancreatic cancer cells tobe more susceptible to cell death through apoptosis [95] Atan MIC of 08mgmL TRG content of C canephora extractshas correlated positively with reduction in biofilm formationvia bacteriostatic action on Streptococcus mutans [96]
3 Extraction Methods forBioactive Micronutrients of Coffee
Extraction and preconcentration procedures may be neces-sary for any good and sensitive characterization and deter-mination of analytes especially when these are present invery low concentrations Many traditional and conventionalmethods have been employed in the extraction of bioactivemicronutrients of coffee preparatory to their analysis
31 Solid-Liquid Extraction Different types of coffee brew-ing techniques have profound influence on the types andamounts of chemical compounds in coffee [18] These tech-niques all of which are based on solid-liquid extraction(SLE) include Boiled Morcha Pot French press TurkishPlunger and Espresso types [97 98] On comparison Turkishstyle and French press provided the highest amounts of kah-weol and cafestol compared to others [71] In SLE water isoften the solvent for extraction which is beneficial to polarand water-soluble analytes [70] For analytical determina-tions extraction can be carried out in other solvents but maybe reconstituted in water before further analysis [89] Bi et al[99] however found that a mixture of ethanol and water(5050 vv) was most effective for removal of caffeine fromcoffeewasteDuring a 90min extraction 60methanol and asolventsolid ratio of 40mLg spent coffee grounds providedthe best conditions for obtaining extract with high phe-nolic compounds including CGA [100] Because the maindiscriminator in these SLE methods is polarity it leads tolimited selectivity in extraction when caffeine was analyzedin roasted coffee ground not only caffeine was extractedwith the SLE procedure [101]This method of extraction maytherefore present interference problems during instrumentalanalysis
Other conditions that define the performance of SLE pro-cedures are the effect of temperature and duration of extrac-tion [92 102] As a result of different temperature sensitivitiesof the complex mixture of constituents in coffee it is difficultto satisfy the temperature needs of individual analytes ina single-extraction system In an attempt to eliminate thischallenge a double-extraction method was described whichaccommodated the extraction of both thermolabile CGA andthermostable caffeine with high recoveries [20] In this sys-tem one batch is fed into selected stages at mild temperatureand pressure while another is fed into remaining stages athigher temperature and pressure and 50 of extracts fromeach stream are mixed and lyophilized Apart from beingcumbersome multistep SLE may lead to loss of some ana-lytes It was recently found that proprietary ethanol single-step extraction resulted in higher content of caffeine thanmultistep procedures [103]
32 Liquid-Liquid Extraction and Solid-Phase ExtractionLiquid-liquid extraction (LLE) is one of the most widely usedtraditional sample preparation techniques [104] The dispar-ity in solubility of an analyte in two immiscible solvents is har-nessed for its extraction For the extraction of the four bioac-tive constituents of coffee LLE can be practiced by extractingthese analytes fromaqueousmedium to an organic oneHow-ever because each of these constituents has at least a mod-erate solubility in water application of LLE in this regard islimited In one example caffeine was extracted from waterinto dichloromethane while CGA remained in the residualaqueous solution [105] To solubilize a polar analyte in anorganic solvent during an LLE procedure especially whengas chromatographic analysis is intended it is sometimesnecessary to add ionic surfactants in the extraction medium[106 107]
Solid-phase extraction (SPE) utilizes the sorptive capacityof a stationary sorbent in SPE cartridge in order to extractanalytes It starts by conditioning the cartridge after whichthe sample is run through then dried and finally eluted usinga suitable solvent [108 109] Recently Caprioli et al [110] haveexplained the application of SPE for the extraction of CGAin Arabica and Robusta coffees using Strata-X cartridge Lowtemperatures and methanol as extraction solvent resulted inthe most efficient extraction of CGA
Both LLE and SPE applications are dwarfed by beingmul-tistep and environmentally unfriendly due to large solventvolumes involved especially with regard to LLE
33 Microwave-Assisted and Ultrasound-Assisted ExtractionsMicrowave-assisted extraction (MAE) is a solvent reductionextraction method that uses electromagnetic energy to assist(enhance) extraction of analytes Microwave interacts withmatter in a special way that causes instantaneous heatingthus facilitating desorption of analytes from their matricesand improving mass transfer rate [111 112] Compared toconventional solvent extraction MAE is faster and involvesminimal use of solvent In just under 40 smaximumphenoliccontent was obtained from spent filter coffee under theinfluence of low concentrated ethanol [113] Hongcheng et al
4 ISRN Nutrition
[114] have developed a fastMAEmethod for the simultaneousextraction of TRG caffeine and nicotinic acid from coffeeusing a pressure of 200 psi Other conditions that can affectthis procedure include temperature and wattage At thetemperature of 50∘Candwattage of 800wCGA- and caffeine-rich extracts were prepared from coffee beans [115]
Another assisted extraction procedure is ultrasound-assisted extraction (UAE) a procedure that uses sound fre-quency to agitate extraction medium and speed up contactbetween solvent and matrix It has found a number of appli-cations in the extraction of phytochemicals [50 116] Theenergy burst from UAE equipment causes thermal heatingthat reduces extraction timeWang et al [117] have found thatquantity of caffeine extracted from coffee reached saturationin only 15 s and augmented positivelywith increase in temper-ature at an operating frequency of 28 kHz UAE was success-fully applied to the determination of TRG in coffee powderand instant coffee with excellent recoveries [118]
Some of the demerits of MAE and UAE include the diffi-culty in selecting appropriate extraction conditions (includ-ing type of solvent pressure and frequency) that would notcause excessive heating and lead to degradation of some ana-lytes necessity of clean-up after extraction and relative highcost of equipment
34 Other Extraction Methods The combination of gas-likemass transfer and liquid-like solvating abilities of supercrit-ical fluids is exploited in the extraction method known assupercritical fluid extraction (SFE) In this method a solventat its supercritical state is used to speed up extraction byan increased matrix-penetrating ability and enhanced masstransfer potential Although large industrial application ofSFE is often hindered by the trade-off between selectivityand recovery efficiency this method is still found in routinelaboratory applications [79 119] Among the numerous fac-tors that affect performance of this approach temperatureand pressure are key considerations in recovery and selec-tivity calculations Machmudah et al [120] have found thatrecovery of caffeine and the separation factor of CGA fromcaffeine were positively correlated with increasing height(pressure) of nonpolar recovery section in the separationsystem using supercritical carbon dioxide (SCCO
2) in water
They also found that recovery of caffeine in the SCCO2phase
increased with decreased temperature This could only betrue at pressures below the crossover pressure Above thecrossover pressure (sim200 bar) however an increase in tem-perature resulted in an increased recovery as observed in theextraction of caffeine from Robusta coffee husks [39]
Solid-phase microextraction (SPME) was introduced inthe 1990s in response to the challenges posed by SPE It basi-cally involves sorption of an analyte to a commercial fibercoated with polymeric substance followed by a desorptionstep using a thermal process or suitable solvent SPME allowsfor solvent minimization and provides for higher sampleenrichment Different forms of SPME techniques are prac-ticed but the headspace type (HS-SPME) is very suitablein the analysis of volatile compounds [121 122] Affinity ofan analyte towards the fiber can be enhanced by carefully
selecting the right polymer coating material [123] Lopez-Darias et al [124] found that poly-(ViHIm+Clminus) gave excel-lent performance for aromatic alcohols while polyacrylamidecoating performed better for heterocyclic aromatics Tem-perature and extraction time also influence the performanceof this method as noticed in a different experiment wherepoly-dimethyl-siloxane in combination with divinylbenzene(PDMSDVB) SPME fiber with a 65 120583m thick film coatingwas used for the extraction of caffeine and CGA in coffee[125] Some of the shortcomings of SPME include leaching ofcoatingmaterial breaking of fiber and bending of the syringesupport
4 Methods for Characterizationand Quantification of BioactiveMicronutrients of Coffee
Due to the economic importance of coffee and its constit-uent bioactive substances consumer interest and safetyshould remain paramount Therefore there is an increasingdemand for proper quality control for certification of contentsand reducing counterfeits and substandard products Toachieve these noble goals sensitive and accurate analyticalmethods for both qualitative and quantitative determinationsand characterization of chemical substances in coffee arerequired There are many analytical procedures (Table 1)including chromatographic photometric spectral and elec-trochemical methods that are geared toward this end [126127]
41 Separation-Based Methods To reduce interference andincrease sensitivity an extract is commonly run througha separation system followed by detection of separatedcontents using a suitable detector Among themany analyticaltechniques that have been applied in the determination ofcoffee constituents high performance liquid chromatogra-phy (HPLC) gas chromatography (GC) and capillary elec-trophoresis (CE) in combinationwith various detectors suchas ultravioletvisible (UVVis) detector diode array detector(DAD) refractive index (RI) detector and chemilumines-cence detector are often applied for the determination ofnonvolatile volatile polar and nonpolar classes of analytes
411 HPLC Methods This is one of the most powerful toolsavailable for analytical applications inmany fields Because ofits versatility low limits of detection (LOD) and accessibilityits applications can now be found in numerous methods forthe analyses of industrial chemicals agroallied chemicalsand constituents of foods and beverages It is the singlemost applied separation-based method of quantification forbioactive constituents in coffee and coffee products AHPLC-based method for TRG determination and for the qualitycontrol of coffee products was explained by Liu et al [118]After its separation TRG was detected at 260 nm 120582 The totalcontents of CGA and its isomers in a cup of certified ItalianEspresso coffee were between 15225 and 22234mgKgminus1 asdetermined by HPLC-DAD [110] Results of HPLC-UVRIanalysis of 17 Brazilian Arabica cultivars have revealed that
ISRN Nutrition 5
Table 1 Analytical methods for characterization and quantification of bioactive micronutrients in coffee
Micronutrient Method Figure of merit ReferenceCGA SWV LOD (0049 120583gmLminus1) Yardim 2012 [141]CGA caffeine UV-Vis Ra (91ndash9843) CVb (280ndash545) Belay and Gholap 2009 [105]TRG HPLC R (gt90) RSD (lt3) Liu et al 2011 [118]Caffeine NIRchemometrics RSD (1707) RMSEP (0378mgg) Zhang et al 2013 [152]TRG caffeine HPLC LOD (002mgL) LOQ (0005) Hongcheng et al 2012 [114]Caffeine DART-TOFMS R (97ndash107) RSD (lt5) Danhelova et al 2012 [101]TRG caffeine 1H-NMR CV (24 42) LOD (058 132mgg) del Campo et al 2010 [156]CGA DPP SWV LOD (0236 120583molLminus1 134 nmolLminus1) Araujo et al 2009 [144]CGA isomers 2D-NMR R (75ndash80) R2 (09960ndash09994) Wei et al 2010 [155]Caffeine CE HPLC LOD (087 0021mg100 g) RSD (lt2) Bizzotto et al 2013 [137]Caffeine CVc LOD (0348 120583molLminus1) R2 (0999) Mersal 2012 [142]Caffeine CE RSD (lt2) Li et al 2009 [139]CGA DPV LOD (0148 120583molLminus1) Santos et al 2011 [146]CGA isomers HPLC R (67ndash99) R2 (gt099) Caprioli et al 2013 [110]CGA BiosensorSWV LOD (0915 120583molLminus1) R (932ndash1057) Fernandes et al 2009 [147]Cafestol kahweol HPLC RSD (lt5) Sridevi et al 2011 [71]Caffeine CVSWV LOD (0137 120583molLminus1) R (gt90) Amare and Admassie 2012 [145]aPercent recovery bcoefficient of variation ccyclic voltammetry
semidry processing method showed lower levels of CGAand TRG than coffee processed by wet method which goesto confirm the effect of different processing methods onconstituents of coffee [128] In another experiment HPLC-UVVis analysis revealed that coffee contains 006ndash255caffeine and this value decreases with roasting intensity [129]
HPLC can be performed in either reverse or normalphasemode A caffeine assessment tool (CAT) was developedwith results obtained from a reverse-phase- (RP-) HPLC-UVanalysis of several coffee and coffee-based beverages [130]Moreira and Scarminio [131] have applied RP-HPLC-DADfor the determination of caffeine at 275 nm 120582 using a binaryethanol-dichloromethane solution (1 1) as mobile phaseMobile phase in gradient flow mode is often employed toresolve complex mixtures When different coffee extractionmethods were tested using a mixture of 01 formic acid inwater and 01 formic acid in acetonitrile in this type of flowmode CGA and caffeine contents of the different extractswere different confirming that contents may vary accordingto method of extraction [125]
Two-dimensional HPLC (2D-HPLC) may provide forbetter resolution than in ordinary practiceThe application ofthis system in combination with chemiluminescence detec-tor allowed for increased sensitivity and better selectivityin the determination of antioxidant constituents of threeEspresso coffees (ldquoRistrettordquo ldquoDecaffeinatordquo and ldquoVollutordquo)[132] Elsewhere a C-18 and Bondapak NH
2columns in
series were used for the simultaneous determination of TRGcaffeine and nicotinic acid [114] This method selected con-ditions optimal at 120∘C and 200 psi and good separationwas achieved in just 3min driven by 002Mphosphoric acid-methanol (70 30 vv) mobile phase at 08mLmin
Apart from the common detection systems (UVVisDAD and RI) often employed in liquid chromatographic
applications for the characterization of these coffee con-tents applications of MS detection are also found in the lit-erature By a careful selection of parameters molecularmarkers for distinguishing between different coffee samplesor between constituents can be assigned [133] In a methodof liquid chromatographymultistage spectrometry (LCMS119899) (119899 = 2ndash4) described by Jaiswal and Kuhnert [134]hitherto unreported isomers of CGA (triacyl CGAs) weredetected in Robusta coffee bean extracts and their struc-tures assigned using LCMS119899 fragmentation patterns Incombination with similar fragmentation patterns (LCMS119899119899 = 2-3) relative hydrophobicity and fragmentation analogywere also harnessed to distinguish between two isomericclasses of CGA (CGA lactones and cinnamoylshikimate)which are formed from CGA by loss of water at high pro-cessing temperatures [135] Interestingly a high temperaturereverse phase liquid chromatography coupled with isotoperatio mass spectrometry (HT-RPLCIRMS) was employed todistinguish between natural and synthetic caffeine in coffeedrinks without the painful need for extraction by using 12057513 Cvalues (between 25 and 32permilfor natural caffeine and between33 and 38permilfor synthetic caffeine) as distinguishable groups[136] This method will be a special aid in the fight againstcounterfeiting and adulteration of coffee products
412 CE and Other Methods CE uses a very small diameterbore capillary to effect separation of charged analytes dis-solved in a suitable buffer The driving force for this separa-tion system is the use of high voltage that influences electroki-netic migration of analytes to either of the positive and neg-ative poles Hence a candidate analyte for CE must possess anet negative or positive charge for effective separation In thelast five years CE has been applied in many fields includingthe analysis of plant materials [86] While HPLC did provide
6 ISRN Nutrition
lower values of LOD for the determination of caffeine indecaffeinated coffee than CE the latter was 30 faster hadlower cost of reagents and generated smaller volumes ofresidues [137] In a similar experiment a fast hydrodynamicinjection (50mBar 7 s) was applied in the analysis of caffeinein commercial decaffeinated coffee using a 48 cm times 50 120583mfused-silica capillary [138] Other optimized conditions forthis method include a mixture of sodium carbonate (10mmolLminus1) and sodium dodecyl sulfate (50mmolLminus1) asbuffer 15 kV voltage and 206 nm 120582 Elsewhere Li et al [139]have explained a CEmethod for the determination of caffeinein roasted coffee This method is characterized by extremelyhigh precision percent relative standard deviation (RSD)was less than 08 for retention time and 17 for peak areas
GC determination can be extremely important especiallyin the analysis of volatile components of coffee [108 121]For semivolatile and nonvolatile portions however alter-native methods will be more desirable and effective Oneof such methods is based countercurrent chromatography(CCC) which differs significantly from the preceding typesof separation systems by not involving any solid supportInstead two immiscible solvents are used one solvent apiecefor the stationary and mobile phases This is exemplified inthe method of Machmudah et al [120] where SCCO
2and
water were used in countercurrent flow mode to effect theseparation of CGA from caffeine Recently a method basedon the high-speed mode (HSCCC) which could be used forthe preparative isolation of milligram amount of CGA fromcoffee was explained [140]
42 Separation-Less Methods In many instances determi-nation of analytes is performed without the need to gothrough a separation step Molecular behaviors such as massfragmentation patterns magnetic resonance electrical prop-erties and UVVis or IR absorbance are used for their directcharacterization andor quantificationThesemethods can bedefined by extremely low LODs high throughput and goodselectivity and sensitivity in their applications to the analysisof coffee micronutrients
421 Spectroscopic Methods These methods are based onlight-absorbing or light-emitting properties of molecules asthey interact with electromagnetic radiation As a moleculeabsorbs light energy of defined wavelength electronic tran-sition characteristic of that molecule is elicited and thiscan be used for the characterization and quantification ofsuch molecule At 324 nm CGA has a strong 120587-120587lowast transitionresulting from the delocalized electrons on benzene ringand this was used for its characterization and quantificationin coffee bean extract [105] Null hypothesis was obeyedbetween the results obtained by this method and results ofHPLC analysis
Many determinations of antioxidant activities in coffee bydifferent mechanisms are based on UVVis absorption spec-troscopy [113] CGA and caffeine are among the main antiox-idant micronutrients in coffee Their antioxidant capaci-ties were measured using 221015840-azino-bis(3-ethylbenzothiazo-line-6-sulphonic acid (ABTS) 22-diphenyl-1-picrylhydrazyl
(DPPH) and Folin-Ciocalteau [102] In a similar inves-tigation antioxidant capacities of these hydrophilic com-poundswere also investigated using disodiumnitrosodisulfo-nate (Fremyrsquos salt) and 2266-tetramethyl-1-piperidinyloxy(TEMPO) and results for different coffee brewing techniqueswere obtained as 460ndash1023 (Filter) lt42 (Plunger) and856 (Espresso) [98] DPPH-radical scavenging activitygreater than 75 was recorded in the extract of green coffeebeans containing 22ndash40 caffeine and 31ndash62 CGA [115]
422 Electrochemical Methods Oxidation-reduction behav-iors of analytes at electrode surfaces may be used for thecharacterization of such analytes based on their specificrelationships with potential and current or other electricalquantities Different types of voltammetry and coulometryhave been applied in the determination of coffee constituentswith high sensitivity selectivity and speed For instanceoxidation of CGA at the surface of boron-doped diamondelectrode using adsorptive transfer stripping voltammetricconditions was applied for the electrochemical estimationof antioxidant properties of coffee samples with very lowLOD (49 ngmL) and good linearity within the concentrationrange of 025ndash400120583gmL [141] Direct determination ofcaffeine was achieved by square-wave voltammetry (SWV)using a highly selective pseudo carbon paste electrode versusSCE [142]
Different additives may influence the performance ofthese methods in several ways While milk proteins (caseinand bovine serum albumin) formed complexes with polyphe-nolic constituents in coffee thereby significantly reduc-ing their available OH groups and thus their antioxidantcapacities as revealed by coulometric titration with hexa-cyanoferrate (III) ions [143] addition of cationic surfactant(cetyltrimethylammonium bromide) in the supporting elec-trolyte (004mol Lminus1 phosphate buffer pH 60) significantlyenhanced the reduction of caffeine at hanging mercury dropelectrode determined by both differential-pulse polarogra-phy (DPP) and SWV [144] When the surface of a glassycarbon electrode was modified by the deposition of thin filmof 4-amino-3-hydroxynaphthalene sulfonic acid (AHNSA)highly selective electrocatalyzed oxidation of caffeine wasachieved leading to its high recoveries in coffee extracts [145]
Recently an electrochemical sensor for the selectivedetermination of CGA in coffee samples by differential pulsevoltammetry (DPV) was constructed from the deposition ofa thin film of molecularly imprinted siloxane (MIS) on goldsurface [146] In a similar application by Fernandes et al[147] CGA was selectively determined by SWV at +025V(versus AgAgCl) using a biosensor constructed from 1-n-butyl-3-methylimidazoliumhexafluorophosphate containingdispersed iridium nanoparticles (Ir-BMIPF
6) and polyphe-
nol oxidase
423 Spectral Methods Analytical characterization andquantification can also be achieved through stand-alonespectral revelations MS fragmentation patterns under dif-ferent ionization modes have been employed in chemicalanalysis including analysis of components of coffee [148]
ISRN Nutrition 7
Direct analysis in real time (DART) coupled to time-of-flightmass spectrometry (TOFMS) yielded a high throughput(lt1min per run) analysis of caffeine in coffee samples [101]Without the need for sample preparation or chromatographicseparation the molecular ion (M +H)+ resulting from themethod of DART-MS was used for the identification ofcaffeine in commercial instant coffee samples [149] Caffeinehas a mass to charge ratio (119898119911) of 194 and its characteriza-tion alongside kahweol (119898119911 296) and cafestol (119898119911 298)two marker compounds for C arabica and C canephorawas achieved in the method of single photon ionizationcoupled with TOFMS (SPI-TOFMS) developed by Hertz-Schunemann et al [150] for the recognition of roasting gasprofiles of coffee
Characterization of bioactive components of coffee canalso be achieved by using their near-IR (NIR) (2500ndash4000 cmminus1) absorption spectra Methods based on thisapproach are nondestructive and can offer reliable speed ofdetermination In addition to qualitative analysis chemomet-ric models can assist in quantitative interpretation of NIRspectral data In one example caffeine TRG and CGA weredetermined as components of sensory quality in Arabicaroasted coffee samples using ordered prediction selection(OPS) algorithm partial least squares (PLS) andNIR spectra[151] Recently Zhang et al [152] developed an improvedregression model for NIR determination of caffeine Thismethod is characterized by root mean square error of crossvalidation (RMSECV) of 0375mgg RSD of 1707 andcorrelation coefficient of 0918 at PLS factor of 7
For some time now nuclear magnetic resonance (NMR)spectrometry has been offering good information for theidentification and structural elucidation of compounds andthis has now been extended to coffee constituents Using 1H-NMR and partial least squares discriminant analysis (OPLS-DA) models TRG and CGA were found among the mainmetabolites that can characterize and separate C ara-bica samples according to their geographical origin [153]Recently structures of CGA lactones which hitherto werenot available in the literature were established from NMRdata [140] Self-association and complexation of coffee con-stituents both in coffee brews and in aqueousmedia can poseserious challenge for their analytical resolutions DrsquoAmelioet al [154] have investigated structural features of CGA-caffeine complexation using high resolution 1H-NMR NMRcan also offer quantitative information on chemical com-ponents in coffee Without a nuclear Overhauser effectthree isomers of CGA were identified and quantified ingreen coffee bean extract through integration of 2D NMRcarbon signals by use of relaxation reagent and inverse-gateddecouplingmethod [155] According to del Campo et al [156]caffeine and TRG among other constituents of coffee canbe quantitatively analyzed by use of their singlet 1H-NMRsignals within 76ndash95 ppm and the use of 3-(trimethylsilyl)-2233-tetradeuteropropionic acid both as internal standardand as reference for 120575 = 000 ppm
5 Conclusions
Coffee is a popular beverage that is obtained from differentvarieties of coffee beansThis important drink contains many
micronutrients some of which have proven bioactivitiessuch as anticancer antimicrobial antioxidant and host ofother effects Four important groups of these biologicallyimportant micronutrients namely caffeine CGA diter-penes and TRG have been discussed in this review Becauseof their importance in biological systems recent analyticalmethods for their characterization and quantitative determi-nation have also been reviewed It is envisaged that properapplications of these methods will go a long way in aidingquality assurance and safeguarding consumer safety andsatisfaction
Conflict of Interests
The author declares that there is no conflict of interestsregarding the publication of this paper
References
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[2] A L Oliveira F A CabralM N Eberlin andHM A B Cord-ello ldquoSensory evaluation of black instant coffee beverage withsome volatile compounds present in aromatic oil from roastedcoffeerdquo Ciencia e Tecnologia de Alimentos vol 29 no 1 pp 76ndash80 2009
[3] JMiran ldquoSpace mobility and translocal connections across theRed Sea area since 1500rdquo Northeast African Studies vol 12 no1 pp 9ndash26 2012
[4] K Hundera R Aerts M de Beenhouwer et al ldquoBoth forestfragmentation and coffee cultivation negatively affect epiphyticorchid diversity in Ethiopian moist evergreen Afromontaneforestsrdquo Biological Conservation vol 159 pp 285ndash291 2013
[5] F Serra C G Guillou F Reniero et al ldquoDetermination ofthe geographical origin of green coffee by principal componentanalysis of carbon nitrogen and boron stable isotope ratiosrdquoRapid Communications in Mass Spectrometry vol 19 no 15 pp2111ndash2115 2005
[6] P Moguel and V M Toledo ldquoBiodiversity conservation in tra-ditional coffee systems ofMexicordquoConservation Biology vol 13no 1 pp 11ndash21 1999
[7] F Anthony B Bertrand O Quiros et al ldquoGenetic diversity ofwild coffee (Coffea arabica L) using molecular markersrdquoEuphytica vol 118 no 1 pp 53ndash65 2001
[8] A-M Klein I Steffan-Dewenter and T Tscharntke ldquoBee polli-nation and fruit set of Coffea arabica and C canephora (Rubia-ceae)rdquoTheAmerican Journal of Botany vol 90 no 1 pp 153ndash1572003
[9] A Lecolier P Besse A Charrier T-N Tchakaloff and MNoirot ldquoUnraveling the origin of Coffea arabica ldquoBourbonpointurdquo from la Reunion a historical and scientific perspectiverdquoEuphytica vol 168 no 1 pp 1ndash10 2009
[10] D C Carvalho M R P L Brigagao M H S Santos F B Ade Paula A Giusti-Paiva and L Azevedo ldquoOrganic and Con-ventional Coffea arabica L a comparative study of the chemicalcomposition and physiological biochemical and toxicologicaleffects inWistar ratsrdquo Plant Foods for Human Nutrition vol 66no 2 pp 114ndash121 2011
8 ISRN Nutrition
[11] S Topik J M Talbot and M Samper ldquoIntroduction global-ization neoliberalism and the latin American coffee societiesrdquoLatin American Perspectives vol 37 no 2 pp 5ndash20 2010
[12] C M Tucker H Eakin and E J Castellanos ldquoPerceptions ofrisk and adaptation coffee producers market shocks andextreme weather in Central America and Mexicordquo GlobalEnvironmental Change vol 20 no 1 pp 23ndash32 2010
[13] E G Burbano M G Wright N E Gillette et al ldquoEfficacy oftraps lures and repellents for Xylosandrus compactus (Cole-optera Curculionidae) and other ambrosia beetles on Coffeaarabica plantations and Acacia koa nurseries in Hawaiirdquo Envi-ronmental Entomology vol 41 no 1 pp 133ndash140 2012
[14] C W Kathurima B M Gichimu G M Kenji S M Muhohoand R Boulanger ldquoEvaluation of beverage quality and greenbean physical characteristics of selected Arabica coffee geno-types in Kenyardquo African Journal of Food Science vol 3 no 11pp 365ndash371 2009
[15] W J Rogers S Michaux M Bastin and P Bucheli ldquoChanges tothe content of sugars sugar alcohols myo-inositol carboxylicacids and inorganic anions in developing grains from differentvarieties of Robusta (Coffea canephora) andArabica (C arabica)coffeesrdquo Plant Science vol 149 no 2 pp 115ndash123 1999
[16] R Teuber ldquoGeographical indications of origin as a tool of prod-uct differentiation the case of coffeerdquo Journal of InternationalFood and Agribusiness Marketing vol 22 no 3-4 pp 277ndash2982010
[17] H C Liu C F You C Y Chen Y C Liu and M T ChungldquoGeographic determination of coffee beans usingmulti-elementanalysis and isotope ratios of boron and strontiumrdquo FoodChemistry vol 142 pp 439ndash445 2013
[18] T Niseteo D Komes A Belscak-Cvitanovic D Horzic andM Bude ldquoBioactive composition and antioxidant potential ofdifferent commonly consumed coffee brews affected by theirpreparation technique and milk additionrdquo Food Chemistry vol134 no 4 pp 1870ndash1877 2012
[19] M Oliveira S Casal S Morais et al ldquoIntra- and interspecificmineral composition variability of commercial instant coffeesand coffee substitutes contribution to mineral intakerdquo FoodChemistry vol 130 no 3 pp 702ndash709 2012
[20] J A Vignoli D G Bassoli and M T Benassi ldquoAntioxidantactivity polyphenols caffeine andmelanoidins in soluble coffeethe influence of processing conditions and raw materialrdquo FoodChemistry vol 124 no 3 pp 863ndash868 2011
[21] S I Mussatto L M Carneiro J P A Silva I C Roberto and JA Teixeira ldquoA study on chemical constituents and sugarsextraction from spent coffee groundsrdquo Carbohydrate Polymersvol 83 no 2 pp 368ndash374 2011
[22] Y F Chu P H Brown B J Lyle et al ldquoRoasted coffees high inlipophilic antioxidants and chlorogenic acid lactones are moreneuroprotective than green coffeesrdquo Journal of Agricultural andFood Chemistry vol 57 no 20 pp 9801ndash9808 2009
[23] S Johnson W P Koh R Wang S Govindarajan M C Yu andJ M Yuan ldquoCoffee consumption and reduced risk of hepatocel-lular carcinoma findings from the Singapore Chinese HealthStudyrdquo Cancer Causes and Control vol 22 no 3 pp 503ndash5102011
[24] J Tai S Cheung E Chan and D Hasman ldquoAntiproliferationeffect of commercially brewed coffees on human ovarian cancercells in vitrordquoNutrition and Cancer vol 62 no 8 pp 1044ndash10572010
[25] GWArendash andC Cao ldquoCaffeine and coffee as therapeuticsagainst Alzheimerrsquos diseaserdquo Journal of Alzheimerrsquos Disease vol20 no 1 pp 117ndash126 2010
[26] U Boettler K Sommerfeld N Volz et al ldquoCoffee constituentsas modulators of Nrf2 nuclear translocation and ARE (EpRE)-dependent gene expressionrdquo Journal of Nutritional Biochem-istry vol 22 no 5 pp 426ndash440 2011
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xanthines XAC and caffeinerdquo Structure vol 19 no 9 pp 1283ndash1293 2011
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[29] N Amaresh A R Mullaicharam andM A El-Khider ldquoChem-istry and pharmacology of caffeine in different types of tealeavesrdquo International Journal of Nutrition Pharmacology Neu-rological Diseases vol 1 no 2 pp 110ndash115 2011
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[33] V Olmos N Bardoni A S Ridolfi and E C Villaamil LeporildquoCaffeine levels in beverages from Argentinarsquos market applica-tion to caffeine dietary intake assessmentrdquo Food Additives andContaminants A vol 26 no 3 pp 275ndash281 2009
[34] S Oba C Nagata K Nakamura et al ldquoConsumption of coffeegreen tea oolong tea black tea chocolate snacks and thecaffeine content in relation to risk of diabetes in Japanese menandwomenrdquoBritish Journal of Nutrition vol 103 no 3 pp 453ndash459 2010
[35] S N Bhupathiraju A Pan V S Malik et al ldquoCaffeinated andcaffeine-free beverages and risk of type 2 diabetesrdquoThe Ameri-can Journal of Clinical Nutrition vol 97 pp 155ndash166 2013
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[37] R S J Keast D Sayompark G Sacks B A Swinburn and L JRiddell ldquoThe influence of caffeine on energy content of sugar-sweetened beverages lsquothe caffeine-calorie effectrsquordquo EuropeanJournal of Clinical Nutrition vol 65 no 12 pp 1338ndash1344 2011
[38] P Mazzafera andM B Silvarolla ldquoCaffeine content variation insingle greenArabica coffee seedsrdquo Seed Science Research vol 20no 3 pp 163ndash167 2010
[39] J Tello M Viguera and L Calvo ldquoExtraction of caffeine fromRobusta coffee (Coffea canephora var Robusta) husks usingsupercritical carbon dioxiderdquo Journal of Supercritical Fluids vol59 pp 53ndash60 2011
[40] G Laurence K Wallman and K Guelfi ldquoEffects of caffeine ontime trial performance in sedentary menrdquo Journal of Sports Sci-ences vol 30 no 12 pp 1235ndash1240 2012
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Disease Markers
BioMed Research International
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Oxidative Medicine and Cellular Longevity
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Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
2 ISRN Nutrition
N
NNO
N
O
Figure 1 Chemical structure of caffeine
contains two fused rings (Figure 1) that are related to purines[29] Caffeine is found in many natural and processedproducts Examples of these sources include green tea [30 31]mate tea [32 33] chocolate [34] and caffeinated beveragesand energy drinks [35ndash37] C arabica [38] and Robustacoffee (C canephora var Robusta) [39] also contain thismicronutrient
Consumption of caffeine has shownmany positive effectsin various human and animal experimentations At a dose of6mgKgminus1 bodymass it was found to exhibit ergogenic effectthe ability to increase physical exercise without a concomitantincrease in effort sensation in sedentary men [40] Its stimu-latory activity was also tested with some promising results inpersonswith Parkinsonrsquos disease where it can be used toman-age both motor and nonmotor symptoms [41] In a mousemodel crude caffeine was found to reduce the accumulationof 120573-amyloid peptides a characteristic feature in patientssuffering from Parkinsonrsquos disease [42] Investigations haverevealed that crude caffeine did possess hydrophilic antiox-idant activity (145 120583mol Trolox equivalent (TE)g) and lipo-philic antioxidant activity (66 120583mol TEg) and its adminis-tration has led to the inhibition of cyclooxygenase-2 enzymebetter than aspirin [43]
Some of the adverse effects of high doses of caffeineinclude decrease tonus of the lower esophageal sphinctermuscle overstimulation of central nervous system intrauter-ine growth retardation and higher risk of miscarriage [44]Withdrawal from caffeine ingestion may present with lowermental alertness diminished performance and over sleepi-ness [45]
22 Chlorogenic Acid Chlorogenic acid (CGA) (Figure 2)which has nothing to do with chlorine is an ester that isformed from the reaction of caffeic acid with L-quinic acidhence the name 5-caffeoylquinic acid (5-CQA) [46 47] It isa polyphenolic compound that is abundant in many plants[48] It is present in tobacco leaves [49] mulberry tree [50]and coffee beans [51] It is found to be responsible for theastringent taste of coffee brews [52 53] Many positive effectshave been attributed to CGA For instance its hypolipidemiceffect has led to weight reduction in experimental mice [5455] The antioxidant activities of this phytochemical wereexhibited against ischemia-reperfusion injury [56] and inthe protection against oxidative damage of macromoleculessuch as DNA lipids and proteins [57] When administeredto mice under scopolamine-induced amnesia CGA hasshown neuroprotective function via the inhibition of acetylcholinesterase [58]
Different microbial entities are susceptible to CGArsquos anti-microbial activities With respect to viruses CGA has shown
OOH
OHOH
OHHO
HO
O
O
Figure 2 Chemical structure of chlorogenic acid
O H
lt OHOH
H
H
CH3
Figure 3 Chemical structure of the diterpene cafestol
antihepatitis B virus potency in a duckling model [59] andpotential anti-H1N1 influenza virus [60] CGA analogs thatshowed appreciable anti-HIV activities have been synthesized[61] CGA is not only active against viral particles but ithas also antibacterial and antifungal functions At minimuminhibitory concentrations (MIC) of 20ndash80120583gmL the growthof all bacterial pathogens tested was inhibited by CGA [62]It is argued that the high resistance of immature peach fruitsto the brown rot fungus Monilinia laxa is due to their highcontents of CGA [63]
23 Diterpenes Diterpenes are a group of terpenoids com-monly found as secondary metabolites in terrestrial andmarine organisms [64]They often occur in a C-20 backbonewhere isoprene units combine in different forms to give anarray of diterpenes such as abietane [65] cembrane [66]guanacastepene A [67] quinonoid [68] jatropha [69] andcafestol and kahweol [70] typesThese and several othersmaybe found in coffee [71] tea [72] and Salvia spp [73] Sometypes have been isolated from the fungus Trichoderma longi-brachiatum [74] and from sponge family [75]
Diterpenes have displayed several types of bioactivitiesvia different mechanisms A diterpene alkaloid isolated fromthe Caribbean sponge Agelas citrina has shown antifungalfunction [76] Experiment with oridonin type has demon-strated its antiproliferative effect against leukemia-derivedJurkat cells [77] Abietane type was cytotoxic to human pan-creatic cancer cell line MIA PaCa-2 [78] Antioxidant func-tion is found in Salvia officinalis [79] and an isolate of theBrazilian alga Dictyota menstrualis has indicated anti-HIVpotential of this phytochemical [80] Antimicrobial activitiesare found in a recent review [81] Some diterpenes are toxicto insects [82] and to embryos of medaka Japanese rice fish[83] Structure of cafestol is given in Figure 3
24 Trigonelline Trigonelline (TRG) (Figure 4) is a nitroge-nous compound a pyridine alkaloid that is derived from themethylation of the nitrogen atom of nicotinic acid (niacin)
ISRN Nutrition 3
N+
O
O
minus
Figure 4 Chemical structure of trigonelline
hence the name N-methyl nicotinic acid [84ndash86] TRG isfound in pumpkin seeds [87] mangrove legumes [88] Mor-inga oleifera tree [89] and coffee [90 91] It is used as roastinglevel discriminator in both Arabica and Robusta coffees [92]
TRG has a proven antidiabetic effect its administrationto model rats suffering from diabetes mellitus has resultedin reduced blood glucose levels in oral glucose tolerance test[93] It has also shown beneficial effects in rats displayingperipheral neuropathy a condition forwhich there is no effec-tive drug for its treatment [94] Its function as an inhibitor ofNrf2 gene transcription has caused pancreatic cancer cells tobe more susceptible to cell death through apoptosis [95] Atan MIC of 08mgmL TRG content of C canephora extractshas correlated positively with reduction in biofilm formationvia bacteriostatic action on Streptococcus mutans [96]
3 Extraction Methods forBioactive Micronutrients of Coffee
Extraction and preconcentration procedures may be neces-sary for any good and sensitive characterization and deter-mination of analytes especially when these are present invery low concentrations Many traditional and conventionalmethods have been employed in the extraction of bioactivemicronutrients of coffee preparatory to their analysis
31 Solid-Liquid Extraction Different types of coffee brew-ing techniques have profound influence on the types andamounts of chemical compounds in coffee [18] These tech-niques all of which are based on solid-liquid extraction(SLE) include Boiled Morcha Pot French press TurkishPlunger and Espresso types [97 98] On comparison Turkishstyle and French press provided the highest amounts of kah-weol and cafestol compared to others [71] In SLE water isoften the solvent for extraction which is beneficial to polarand water-soluble analytes [70] For analytical determina-tions extraction can be carried out in other solvents but maybe reconstituted in water before further analysis [89] Bi et al[99] however found that a mixture of ethanol and water(5050 vv) was most effective for removal of caffeine fromcoffeewasteDuring a 90min extraction 60methanol and asolventsolid ratio of 40mLg spent coffee grounds providedthe best conditions for obtaining extract with high phe-nolic compounds including CGA [100] Because the maindiscriminator in these SLE methods is polarity it leads tolimited selectivity in extraction when caffeine was analyzedin roasted coffee ground not only caffeine was extractedwith the SLE procedure [101]This method of extraction maytherefore present interference problems during instrumentalanalysis
Other conditions that define the performance of SLE pro-cedures are the effect of temperature and duration of extrac-tion [92 102] As a result of different temperature sensitivitiesof the complex mixture of constituents in coffee it is difficultto satisfy the temperature needs of individual analytes ina single-extraction system In an attempt to eliminate thischallenge a double-extraction method was described whichaccommodated the extraction of both thermolabile CGA andthermostable caffeine with high recoveries [20] In this sys-tem one batch is fed into selected stages at mild temperatureand pressure while another is fed into remaining stages athigher temperature and pressure and 50 of extracts fromeach stream are mixed and lyophilized Apart from beingcumbersome multistep SLE may lead to loss of some ana-lytes It was recently found that proprietary ethanol single-step extraction resulted in higher content of caffeine thanmultistep procedures [103]
32 Liquid-Liquid Extraction and Solid-Phase ExtractionLiquid-liquid extraction (LLE) is one of the most widely usedtraditional sample preparation techniques [104] The dispar-ity in solubility of an analyte in two immiscible solvents is har-nessed for its extraction For the extraction of the four bioac-tive constituents of coffee LLE can be practiced by extractingthese analytes fromaqueousmedium to an organic oneHow-ever because each of these constituents has at least a mod-erate solubility in water application of LLE in this regard islimited In one example caffeine was extracted from waterinto dichloromethane while CGA remained in the residualaqueous solution [105] To solubilize a polar analyte in anorganic solvent during an LLE procedure especially whengas chromatographic analysis is intended it is sometimesnecessary to add ionic surfactants in the extraction medium[106 107]
Solid-phase extraction (SPE) utilizes the sorptive capacityof a stationary sorbent in SPE cartridge in order to extractanalytes It starts by conditioning the cartridge after whichthe sample is run through then dried and finally eluted usinga suitable solvent [108 109] Recently Caprioli et al [110] haveexplained the application of SPE for the extraction of CGAin Arabica and Robusta coffees using Strata-X cartridge Lowtemperatures and methanol as extraction solvent resulted inthe most efficient extraction of CGA
Both LLE and SPE applications are dwarfed by beingmul-tistep and environmentally unfriendly due to large solventvolumes involved especially with regard to LLE
33 Microwave-Assisted and Ultrasound-Assisted ExtractionsMicrowave-assisted extraction (MAE) is a solvent reductionextraction method that uses electromagnetic energy to assist(enhance) extraction of analytes Microwave interacts withmatter in a special way that causes instantaneous heatingthus facilitating desorption of analytes from their matricesand improving mass transfer rate [111 112] Compared toconventional solvent extraction MAE is faster and involvesminimal use of solvent In just under 40 smaximumphenoliccontent was obtained from spent filter coffee under theinfluence of low concentrated ethanol [113] Hongcheng et al
4 ISRN Nutrition
[114] have developed a fastMAEmethod for the simultaneousextraction of TRG caffeine and nicotinic acid from coffeeusing a pressure of 200 psi Other conditions that can affectthis procedure include temperature and wattage At thetemperature of 50∘Candwattage of 800wCGA- and caffeine-rich extracts were prepared from coffee beans [115]
Another assisted extraction procedure is ultrasound-assisted extraction (UAE) a procedure that uses sound fre-quency to agitate extraction medium and speed up contactbetween solvent and matrix It has found a number of appli-cations in the extraction of phytochemicals [50 116] Theenergy burst from UAE equipment causes thermal heatingthat reduces extraction timeWang et al [117] have found thatquantity of caffeine extracted from coffee reached saturationin only 15 s and augmented positivelywith increase in temper-ature at an operating frequency of 28 kHz UAE was success-fully applied to the determination of TRG in coffee powderand instant coffee with excellent recoveries [118]
Some of the demerits of MAE and UAE include the diffi-culty in selecting appropriate extraction conditions (includ-ing type of solvent pressure and frequency) that would notcause excessive heating and lead to degradation of some ana-lytes necessity of clean-up after extraction and relative highcost of equipment
34 Other Extraction Methods The combination of gas-likemass transfer and liquid-like solvating abilities of supercrit-ical fluids is exploited in the extraction method known assupercritical fluid extraction (SFE) In this method a solventat its supercritical state is used to speed up extraction byan increased matrix-penetrating ability and enhanced masstransfer potential Although large industrial application ofSFE is often hindered by the trade-off between selectivityand recovery efficiency this method is still found in routinelaboratory applications [79 119] Among the numerous fac-tors that affect performance of this approach temperatureand pressure are key considerations in recovery and selec-tivity calculations Machmudah et al [120] have found thatrecovery of caffeine and the separation factor of CGA fromcaffeine were positively correlated with increasing height(pressure) of nonpolar recovery section in the separationsystem using supercritical carbon dioxide (SCCO
2) in water
They also found that recovery of caffeine in the SCCO2phase
increased with decreased temperature This could only betrue at pressures below the crossover pressure Above thecrossover pressure (sim200 bar) however an increase in tem-perature resulted in an increased recovery as observed in theextraction of caffeine from Robusta coffee husks [39]
Solid-phase microextraction (SPME) was introduced inthe 1990s in response to the challenges posed by SPE It basi-cally involves sorption of an analyte to a commercial fibercoated with polymeric substance followed by a desorptionstep using a thermal process or suitable solvent SPME allowsfor solvent minimization and provides for higher sampleenrichment Different forms of SPME techniques are prac-ticed but the headspace type (HS-SPME) is very suitablein the analysis of volatile compounds [121 122] Affinity ofan analyte towards the fiber can be enhanced by carefully
selecting the right polymer coating material [123] Lopez-Darias et al [124] found that poly-(ViHIm+Clminus) gave excel-lent performance for aromatic alcohols while polyacrylamidecoating performed better for heterocyclic aromatics Tem-perature and extraction time also influence the performanceof this method as noticed in a different experiment wherepoly-dimethyl-siloxane in combination with divinylbenzene(PDMSDVB) SPME fiber with a 65 120583m thick film coatingwas used for the extraction of caffeine and CGA in coffee[125] Some of the shortcomings of SPME include leaching ofcoatingmaterial breaking of fiber and bending of the syringesupport
4 Methods for Characterizationand Quantification of BioactiveMicronutrients of Coffee
Due to the economic importance of coffee and its constit-uent bioactive substances consumer interest and safetyshould remain paramount Therefore there is an increasingdemand for proper quality control for certification of contentsand reducing counterfeits and substandard products Toachieve these noble goals sensitive and accurate analyticalmethods for both qualitative and quantitative determinationsand characterization of chemical substances in coffee arerequired There are many analytical procedures (Table 1)including chromatographic photometric spectral and elec-trochemical methods that are geared toward this end [126127]
41 Separation-Based Methods To reduce interference andincrease sensitivity an extract is commonly run througha separation system followed by detection of separatedcontents using a suitable detector Among themany analyticaltechniques that have been applied in the determination ofcoffee constituents high performance liquid chromatogra-phy (HPLC) gas chromatography (GC) and capillary elec-trophoresis (CE) in combinationwith various detectors suchas ultravioletvisible (UVVis) detector diode array detector(DAD) refractive index (RI) detector and chemilumines-cence detector are often applied for the determination ofnonvolatile volatile polar and nonpolar classes of analytes
411 HPLC Methods This is one of the most powerful toolsavailable for analytical applications inmany fields Because ofits versatility low limits of detection (LOD) and accessibilityits applications can now be found in numerous methods forthe analyses of industrial chemicals agroallied chemicalsand constituents of foods and beverages It is the singlemost applied separation-based method of quantification forbioactive constituents in coffee and coffee products AHPLC-based method for TRG determination and for the qualitycontrol of coffee products was explained by Liu et al [118]After its separation TRG was detected at 260 nm 120582 The totalcontents of CGA and its isomers in a cup of certified ItalianEspresso coffee were between 15225 and 22234mgKgminus1 asdetermined by HPLC-DAD [110] Results of HPLC-UVRIanalysis of 17 Brazilian Arabica cultivars have revealed that
ISRN Nutrition 5
Table 1 Analytical methods for characterization and quantification of bioactive micronutrients in coffee
Micronutrient Method Figure of merit ReferenceCGA SWV LOD (0049 120583gmLminus1) Yardim 2012 [141]CGA caffeine UV-Vis Ra (91ndash9843) CVb (280ndash545) Belay and Gholap 2009 [105]TRG HPLC R (gt90) RSD (lt3) Liu et al 2011 [118]Caffeine NIRchemometrics RSD (1707) RMSEP (0378mgg) Zhang et al 2013 [152]TRG caffeine HPLC LOD (002mgL) LOQ (0005) Hongcheng et al 2012 [114]Caffeine DART-TOFMS R (97ndash107) RSD (lt5) Danhelova et al 2012 [101]TRG caffeine 1H-NMR CV (24 42) LOD (058 132mgg) del Campo et al 2010 [156]CGA DPP SWV LOD (0236 120583molLminus1 134 nmolLminus1) Araujo et al 2009 [144]CGA isomers 2D-NMR R (75ndash80) R2 (09960ndash09994) Wei et al 2010 [155]Caffeine CE HPLC LOD (087 0021mg100 g) RSD (lt2) Bizzotto et al 2013 [137]Caffeine CVc LOD (0348 120583molLminus1) R2 (0999) Mersal 2012 [142]Caffeine CE RSD (lt2) Li et al 2009 [139]CGA DPV LOD (0148 120583molLminus1) Santos et al 2011 [146]CGA isomers HPLC R (67ndash99) R2 (gt099) Caprioli et al 2013 [110]CGA BiosensorSWV LOD (0915 120583molLminus1) R (932ndash1057) Fernandes et al 2009 [147]Cafestol kahweol HPLC RSD (lt5) Sridevi et al 2011 [71]Caffeine CVSWV LOD (0137 120583molLminus1) R (gt90) Amare and Admassie 2012 [145]aPercent recovery bcoefficient of variation ccyclic voltammetry
semidry processing method showed lower levels of CGAand TRG than coffee processed by wet method which goesto confirm the effect of different processing methods onconstituents of coffee [128] In another experiment HPLC-UVVis analysis revealed that coffee contains 006ndash255caffeine and this value decreases with roasting intensity [129]
HPLC can be performed in either reverse or normalphasemode A caffeine assessment tool (CAT) was developedwith results obtained from a reverse-phase- (RP-) HPLC-UVanalysis of several coffee and coffee-based beverages [130]Moreira and Scarminio [131] have applied RP-HPLC-DADfor the determination of caffeine at 275 nm 120582 using a binaryethanol-dichloromethane solution (1 1) as mobile phaseMobile phase in gradient flow mode is often employed toresolve complex mixtures When different coffee extractionmethods were tested using a mixture of 01 formic acid inwater and 01 formic acid in acetonitrile in this type of flowmode CGA and caffeine contents of the different extractswere different confirming that contents may vary accordingto method of extraction [125]
Two-dimensional HPLC (2D-HPLC) may provide forbetter resolution than in ordinary practiceThe application ofthis system in combination with chemiluminescence detec-tor allowed for increased sensitivity and better selectivityin the determination of antioxidant constituents of threeEspresso coffees (ldquoRistrettordquo ldquoDecaffeinatordquo and ldquoVollutordquo)[132] Elsewhere a C-18 and Bondapak NH
2columns in
series were used for the simultaneous determination of TRGcaffeine and nicotinic acid [114] This method selected con-ditions optimal at 120∘C and 200 psi and good separationwas achieved in just 3min driven by 002Mphosphoric acid-methanol (70 30 vv) mobile phase at 08mLmin
Apart from the common detection systems (UVVisDAD and RI) often employed in liquid chromatographic
applications for the characterization of these coffee con-tents applications of MS detection are also found in the lit-erature By a careful selection of parameters molecularmarkers for distinguishing between different coffee samplesor between constituents can be assigned [133] In a methodof liquid chromatographymultistage spectrometry (LCMS119899) (119899 = 2ndash4) described by Jaiswal and Kuhnert [134]hitherto unreported isomers of CGA (triacyl CGAs) weredetected in Robusta coffee bean extracts and their struc-tures assigned using LCMS119899 fragmentation patterns Incombination with similar fragmentation patterns (LCMS119899119899 = 2-3) relative hydrophobicity and fragmentation analogywere also harnessed to distinguish between two isomericclasses of CGA (CGA lactones and cinnamoylshikimate)which are formed from CGA by loss of water at high pro-cessing temperatures [135] Interestingly a high temperaturereverse phase liquid chromatography coupled with isotoperatio mass spectrometry (HT-RPLCIRMS) was employed todistinguish between natural and synthetic caffeine in coffeedrinks without the painful need for extraction by using 12057513 Cvalues (between 25 and 32permilfor natural caffeine and between33 and 38permilfor synthetic caffeine) as distinguishable groups[136] This method will be a special aid in the fight againstcounterfeiting and adulteration of coffee products
412 CE and Other Methods CE uses a very small diameterbore capillary to effect separation of charged analytes dis-solved in a suitable buffer The driving force for this separa-tion system is the use of high voltage that influences electroki-netic migration of analytes to either of the positive and neg-ative poles Hence a candidate analyte for CE must possess anet negative or positive charge for effective separation In thelast five years CE has been applied in many fields includingthe analysis of plant materials [86] While HPLC did provide
6 ISRN Nutrition
lower values of LOD for the determination of caffeine indecaffeinated coffee than CE the latter was 30 faster hadlower cost of reagents and generated smaller volumes ofresidues [137] In a similar experiment a fast hydrodynamicinjection (50mBar 7 s) was applied in the analysis of caffeinein commercial decaffeinated coffee using a 48 cm times 50 120583mfused-silica capillary [138] Other optimized conditions forthis method include a mixture of sodium carbonate (10mmolLminus1) and sodium dodecyl sulfate (50mmolLminus1) asbuffer 15 kV voltage and 206 nm 120582 Elsewhere Li et al [139]have explained a CEmethod for the determination of caffeinein roasted coffee This method is characterized by extremelyhigh precision percent relative standard deviation (RSD)was less than 08 for retention time and 17 for peak areas
GC determination can be extremely important especiallyin the analysis of volatile components of coffee [108 121]For semivolatile and nonvolatile portions however alter-native methods will be more desirable and effective Oneof such methods is based countercurrent chromatography(CCC) which differs significantly from the preceding typesof separation systems by not involving any solid supportInstead two immiscible solvents are used one solvent apiecefor the stationary and mobile phases This is exemplified inthe method of Machmudah et al [120] where SCCO
2and
water were used in countercurrent flow mode to effect theseparation of CGA from caffeine Recently a method basedon the high-speed mode (HSCCC) which could be used forthe preparative isolation of milligram amount of CGA fromcoffee was explained [140]
42 Separation-Less Methods In many instances determi-nation of analytes is performed without the need to gothrough a separation step Molecular behaviors such as massfragmentation patterns magnetic resonance electrical prop-erties and UVVis or IR absorbance are used for their directcharacterization andor quantificationThesemethods can bedefined by extremely low LODs high throughput and goodselectivity and sensitivity in their applications to the analysisof coffee micronutrients
421 Spectroscopic Methods These methods are based onlight-absorbing or light-emitting properties of molecules asthey interact with electromagnetic radiation As a moleculeabsorbs light energy of defined wavelength electronic tran-sition characteristic of that molecule is elicited and thiscan be used for the characterization and quantification ofsuch molecule At 324 nm CGA has a strong 120587-120587lowast transitionresulting from the delocalized electrons on benzene ringand this was used for its characterization and quantificationin coffee bean extract [105] Null hypothesis was obeyedbetween the results obtained by this method and results ofHPLC analysis
Many determinations of antioxidant activities in coffee bydifferent mechanisms are based on UVVis absorption spec-troscopy [113] CGA and caffeine are among the main antiox-idant micronutrients in coffee Their antioxidant capaci-ties were measured using 221015840-azino-bis(3-ethylbenzothiazo-line-6-sulphonic acid (ABTS) 22-diphenyl-1-picrylhydrazyl
(DPPH) and Folin-Ciocalteau [102] In a similar inves-tigation antioxidant capacities of these hydrophilic com-poundswere also investigated using disodiumnitrosodisulfo-nate (Fremyrsquos salt) and 2266-tetramethyl-1-piperidinyloxy(TEMPO) and results for different coffee brewing techniqueswere obtained as 460ndash1023 (Filter) lt42 (Plunger) and856 (Espresso) [98] DPPH-radical scavenging activitygreater than 75 was recorded in the extract of green coffeebeans containing 22ndash40 caffeine and 31ndash62 CGA [115]
422 Electrochemical Methods Oxidation-reduction behav-iors of analytes at electrode surfaces may be used for thecharacterization of such analytes based on their specificrelationships with potential and current or other electricalquantities Different types of voltammetry and coulometryhave been applied in the determination of coffee constituentswith high sensitivity selectivity and speed For instanceoxidation of CGA at the surface of boron-doped diamondelectrode using adsorptive transfer stripping voltammetricconditions was applied for the electrochemical estimationof antioxidant properties of coffee samples with very lowLOD (49 ngmL) and good linearity within the concentrationrange of 025ndash400120583gmL [141] Direct determination ofcaffeine was achieved by square-wave voltammetry (SWV)using a highly selective pseudo carbon paste electrode versusSCE [142]
Different additives may influence the performance ofthese methods in several ways While milk proteins (caseinand bovine serum albumin) formed complexes with polyphe-nolic constituents in coffee thereby significantly reduc-ing their available OH groups and thus their antioxidantcapacities as revealed by coulometric titration with hexa-cyanoferrate (III) ions [143] addition of cationic surfactant(cetyltrimethylammonium bromide) in the supporting elec-trolyte (004mol Lminus1 phosphate buffer pH 60) significantlyenhanced the reduction of caffeine at hanging mercury dropelectrode determined by both differential-pulse polarogra-phy (DPP) and SWV [144] When the surface of a glassycarbon electrode was modified by the deposition of thin filmof 4-amino-3-hydroxynaphthalene sulfonic acid (AHNSA)highly selective electrocatalyzed oxidation of caffeine wasachieved leading to its high recoveries in coffee extracts [145]
Recently an electrochemical sensor for the selectivedetermination of CGA in coffee samples by differential pulsevoltammetry (DPV) was constructed from the deposition ofa thin film of molecularly imprinted siloxane (MIS) on goldsurface [146] In a similar application by Fernandes et al[147] CGA was selectively determined by SWV at +025V(versus AgAgCl) using a biosensor constructed from 1-n-butyl-3-methylimidazoliumhexafluorophosphate containingdispersed iridium nanoparticles (Ir-BMIPF
6) and polyphe-
nol oxidase
423 Spectral Methods Analytical characterization andquantification can also be achieved through stand-alonespectral revelations MS fragmentation patterns under dif-ferent ionization modes have been employed in chemicalanalysis including analysis of components of coffee [148]
ISRN Nutrition 7
Direct analysis in real time (DART) coupled to time-of-flightmass spectrometry (TOFMS) yielded a high throughput(lt1min per run) analysis of caffeine in coffee samples [101]Without the need for sample preparation or chromatographicseparation the molecular ion (M +H)+ resulting from themethod of DART-MS was used for the identification ofcaffeine in commercial instant coffee samples [149] Caffeinehas a mass to charge ratio (119898119911) of 194 and its characteriza-tion alongside kahweol (119898119911 296) and cafestol (119898119911 298)two marker compounds for C arabica and C canephorawas achieved in the method of single photon ionizationcoupled with TOFMS (SPI-TOFMS) developed by Hertz-Schunemann et al [150] for the recognition of roasting gasprofiles of coffee
Characterization of bioactive components of coffee canalso be achieved by using their near-IR (NIR) (2500ndash4000 cmminus1) absorption spectra Methods based on thisapproach are nondestructive and can offer reliable speed ofdetermination In addition to qualitative analysis chemomet-ric models can assist in quantitative interpretation of NIRspectral data In one example caffeine TRG and CGA weredetermined as components of sensory quality in Arabicaroasted coffee samples using ordered prediction selection(OPS) algorithm partial least squares (PLS) andNIR spectra[151] Recently Zhang et al [152] developed an improvedregression model for NIR determination of caffeine Thismethod is characterized by root mean square error of crossvalidation (RMSECV) of 0375mgg RSD of 1707 andcorrelation coefficient of 0918 at PLS factor of 7
For some time now nuclear magnetic resonance (NMR)spectrometry has been offering good information for theidentification and structural elucidation of compounds andthis has now been extended to coffee constituents Using 1H-NMR and partial least squares discriminant analysis (OPLS-DA) models TRG and CGA were found among the mainmetabolites that can characterize and separate C ara-bica samples according to their geographical origin [153]Recently structures of CGA lactones which hitherto werenot available in the literature were established from NMRdata [140] Self-association and complexation of coffee con-stituents both in coffee brews and in aqueousmedia can poseserious challenge for their analytical resolutions DrsquoAmelioet al [154] have investigated structural features of CGA-caffeine complexation using high resolution 1H-NMR NMRcan also offer quantitative information on chemical com-ponents in coffee Without a nuclear Overhauser effectthree isomers of CGA were identified and quantified ingreen coffee bean extract through integration of 2D NMRcarbon signals by use of relaxation reagent and inverse-gateddecouplingmethod [155] According to del Campo et al [156]caffeine and TRG among other constituents of coffee canbe quantitatively analyzed by use of their singlet 1H-NMRsignals within 76ndash95 ppm and the use of 3-(trimethylsilyl)-2233-tetradeuteropropionic acid both as internal standardand as reference for 120575 = 000 ppm
5 Conclusions
Coffee is a popular beverage that is obtained from differentvarieties of coffee beansThis important drink contains many
micronutrients some of which have proven bioactivitiessuch as anticancer antimicrobial antioxidant and host ofother effects Four important groups of these biologicallyimportant micronutrients namely caffeine CGA diter-penes and TRG have been discussed in this review Becauseof their importance in biological systems recent analyticalmethods for their characterization and quantitative determi-nation have also been reviewed It is envisaged that properapplications of these methods will go a long way in aidingquality assurance and safeguarding consumer safety andsatisfaction
Conflict of Interests
The author declares that there is no conflict of interestsregarding the publication of this paper
References
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[2] A L Oliveira F A CabralM N Eberlin andHM A B Cord-ello ldquoSensory evaluation of black instant coffee beverage withsome volatile compounds present in aromatic oil from roastedcoffeerdquo Ciencia e Tecnologia de Alimentos vol 29 no 1 pp 76ndash80 2009
[3] JMiran ldquoSpace mobility and translocal connections across theRed Sea area since 1500rdquo Northeast African Studies vol 12 no1 pp 9ndash26 2012
[4] K Hundera R Aerts M de Beenhouwer et al ldquoBoth forestfragmentation and coffee cultivation negatively affect epiphyticorchid diversity in Ethiopian moist evergreen Afromontaneforestsrdquo Biological Conservation vol 159 pp 285ndash291 2013
[5] F Serra C G Guillou F Reniero et al ldquoDetermination ofthe geographical origin of green coffee by principal componentanalysis of carbon nitrogen and boron stable isotope ratiosrdquoRapid Communications in Mass Spectrometry vol 19 no 15 pp2111ndash2115 2005
[6] P Moguel and V M Toledo ldquoBiodiversity conservation in tra-ditional coffee systems ofMexicordquoConservation Biology vol 13no 1 pp 11ndash21 1999
[7] F Anthony B Bertrand O Quiros et al ldquoGenetic diversity ofwild coffee (Coffea arabica L) using molecular markersrdquoEuphytica vol 118 no 1 pp 53ndash65 2001
[8] A-M Klein I Steffan-Dewenter and T Tscharntke ldquoBee polli-nation and fruit set of Coffea arabica and C canephora (Rubia-ceae)rdquoTheAmerican Journal of Botany vol 90 no 1 pp 153ndash1572003
[9] A Lecolier P Besse A Charrier T-N Tchakaloff and MNoirot ldquoUnraveling the origin of Coffea arabica ldquoBourbonpointurdquo from la Reunion a historical and scientific perspectiverdquoEuphytica vol 168 no 1 pp 1ndash10 2009
[10] D C Carvalho M R P L Brigagao M H S Santos F B Ade Paula A Giusti-Paiva and L Azevedo ldquoOrganic and Con-ventional Coffea arabica L a comparative study of the chemicalcomposition and physiological biochemical and toxicologicaleffects inWistar ratsrdquo Plant Foods for Human Nutrition vol 66no 2 pp 114ndash121 2011
8 ISRN Nutrition
[11] S Topik J M Talbot and M Samper ldquoIntroduction global-ization neoliberalism and the latin American coffee societiesrdquoLatin American Perspectives vol 37 no 2 pp 5ndash20 2010
[12] C M Tucker H Eakin and E J Castellanos ldquoPerceptions ofrisk and adaptation coffee producers market shocks andextreme weather in Central America and Mexicordquo GlobalEnvironmental Change vol 20 no 1 pp 23ndash32 2010
[13] E G Burbano M G Wright N E Gillette et al ldquoEfficacy oftraps lures and repellents for Xylosandrus compactus (Cole-optera Curculionidae) and other ambrosia beetles on Coffeaarabica plantations and Acacia koa nurseries in Hawaiirdquo Envi-ronmental Entomology vol 41 no 1 pp 133ndash140 2012
[14] C W Kathurima B M Gichimu G M Kenji S M Muhohoand R Boulanger ldquoEvaluation of beverage quality and greenbean physical characteristics of selected Arabica coffee geno-types in Kenyardquo African Journal of Food Science vol 3 no 11pp 365ndash371 2009
[15] W J Rogers S Michaux M Bastin and P Bucheli ldquoChanges tothe content of sugars sugar alcohols myo-inositol carboxylicacids and inorganic anions in developing grains from differentvarieties of Robusta (Coffea canephora) andArabica (C arabica)coffeesrdquo Plant Science vol 149 no 2 pp 115ndash123 1999
[16] R Teuber ldquoGeographical indications of origin as a tool of prod-uct differentiation the case of coffeerdquo Journal of InternationalFood and Agribusiness Marketing vol 22 no 3-4 pp 277ndash2982010
[17] H C Liu C F You C Y Chen Y C Liu and M T ChungldquoGeographic determination of coffee beans usingmulti-elementanalysis and isotope ratios of boron and strontiumrdquo FoodChemistry vol 142 pp 439ndash445 2013
[18] T Niseteo D Komes A Belscak-Cvitanovic D Horzic andM Bude ldquoBioactive composition and antioxidant potential ofdifferent commonly consumed coffee brews affected by theirpreparation technique and milk additionrdquo Food Chemistry vol134 no 4 pp 1870ndash1877 2012
[19] M Oliveira S Casal S Morais et al ldquoIntra- and interspecificmineral composition variability of commercial instant coffeesand coffee substitutes contribution to mineral intakerdquo FoodChemistry vol 130 no 3 pp 702ndash709 2012
[20] J A Vignoli D G Bassoli and M T Benassi ldquoAntioxidantactivity polyphenols caffeine andmelanoidins in soluble coffeethe influence of processing conditions and raw materialrdquo FoodChemistry vol 124 no 3 pp 863ndash868 2011
[21] S I Mussatto L M Carneiro J P A Silva I C Roberto and JA Teixeira ldquoA study on chemical constituents and sugarsextraction from spent coffee groundsrdquo Carbohydrate Polymersvol 83 no 2 pp 368ndash374 2011
[22] Y F Chu P H Brown B J Lyle et al ldquoRoasted coffees high inlipophilic antioxidants and chlorogenic acid lactones are moreneuroprotective than green coffeesrdquo Journal of Agricultural andFood Chemistry vol 57 no 20 pp 9801ndash9808 2009
[23] S Johnson W P Koh R Wang S Govindarajan M C Yu andJ M Yuan ldquoCoffee consumption and reduced risk of hepatocel-lular carcinoma findings from the Singapore Chinese HealthStudyrdquo Cancer Causes and Control vol 22 no 3 pp 503ndash5102011
[24] J Tai S Cheung E Chan and D Hasman ldquoAntiproliferationeffect of commercially brewed coffees on human ovarian cancercells in vitrordquoNutrition and Cancer vol 62 no 8 pp 1044ndash10572010
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[26] U Boettler K Sommerfeld N Volz et al ldquoCoffee constituentsas modulators of Nrf2 nuclear translocation and ARE (EpRE)-dependent gene expressionrdquo Journal of Nutritional Biochem-istry vol 22 no 5 pp 426ndash440 2011
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[29] N Amaresh A R Mullaicharam andM A El-Khider ldquoChem-istry and pharmacology of caffeine in different types of tealeavesrdquo International Journal of Nutrition Pharmacology Neu-rological Diseases vol 1 no 2 pp 110ndash115 2011
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[31] Q V Vuong and P D Roach ldquoCaffeine in green tea its removaland isolationrdquo Separation and Purification Reviews vol 43 no2 pp 155ndash174 2014
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[33] V Olmos N Bardoni A S Ridolfi and E C Villaamil LeporildquoCaffeine levels in beverages from Argentinarsquos market applica-tion to caffeine dietary intake assessmentrdquo Food Additives andContaminants A vol 26 no 3 pp 275ndash281 2009
[34] S Oba C Nagata K Nakamura et al ldquoConsumption of coffeegreen tea oolong tea black tea chocolate snacks and thecaffeine content in relation to risk of diabetes in Japanese menandwomenrdquoBritish Journal of Nutrition vol 103 no 3 pp 453ndash459 2010
[35] S N Bhupathiraju A Pan V S Malik et al ldquoCaffeinated andcaffeine-free beverages and risk of type 2 diabetesrdquoThe Ameri-can Journal of Clinical Nutrition vol 97 pp 155ndash166 2013
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[37] R S J Keast D Sayompark G Sacks B A Swinburn and L JRiddell ldquoThe influence of caffeine on energy content of sugar-sweetened beverages lsquothe caffeine-calorie effectrsquordquo EuropeanJournal of Clinical Nutrition vol 65 no 12 pp 1338ndash1344 2011
[38] P Mazzafera andM B Silvarolla ldquoCaffeine content variation insingle greenArabica coffee seedsrdquo Seed Science Research vol 20no 3 pp 163ndash167 2010
[39] J Tello M Viguera and L Calvo ldquoExtraction of caffeine fromRobusta coffee (Coffea canephora var Robusta) husks usingsupercritical carbon dioxiderdquo Journal of Supercritical Fluids vol59 pp 53ndash60 2011
[40] G Laurence K Wallman and K Guelfi ldquoEffects of caffeine ontime trial performance in sedentary menrdquo Journal of Sports Sci-ences vol 30 no 12 pp 1235ndash1240 2012
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Disease Markers
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Oxidative Medicine and Cellular Longevity
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Research and TreatmentAIDS
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Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
ISRN Nutrition 3
N+
O
O
minus
Figure 4 Chemical structure of trigonelline
hence the name N-methyl nicotinic acid [84ndash86] TRG isfound in pumpkin seeds [87] mangrove legumes [88] Mor-inga oleifera tree [89] and coffee [90 91] It is used as roastinglevel discriminator in both Arabica and Robusta coffees [92]
TRG has a proven antidiabetic effect its administrationto model rats suffering from diabetes mellitus has resultedin reduced blood glucose levels in oral glucose tolerance test[93] It has also shown beneficial effects in rats displayingperipheral neuropathy a condition forwhich there is no effec-tive drug for its treatment [94] Its function as an inhibitor ofNrf2 gene transcription has caused pancreatic cancer cells tobe more susceptible to cell death through apoptosis [95] Atan MIC of 08mgmL TRG content of C canephora extractshas correlated positively with reduction in biofilm formationvia bacteriostatic action on Streptococcus mutans [96]
3 Extraction Methods forBioactive Micronutrients of Coffee
Extraction and preconcentration procedures may be neces-sary for any good and sensitive characterization and deter-mination of analytes especially when these are present invery low concentrations Many traditional and conventionalmethods have been employed in the extraction of bioactivemicronutrients of coffee preparatory to their analysis
31 Solid-Liquid Extraction Different types of coffee brew-ing techniques have profound influence on the types andamounts of chemical compounds in coffee [18] These tech-niques all of which are based on solid-liquid extraction(SLE) include Boiled Morcha Pot French press TurkishPlunger and Espresso types [97 98] On comparison Turkishstyle and French press provided the highest amounts of kah-weol and cafestol compared to others [71] In SLE water isoften the solvent for extraction which is beneficial to polarand water-soluble analytes [70] For analytical determina-tions extraction can be carried out in other solvents but maybe reconstituted in water before further analysis [89] Bi et al[99] however found that a mixture of ethanol and water(5050 vv) was most effective for removal of caffeine fromcoffeewasteDuring a 90min extraction 60methanol and asolventsolid ratio of 40mLg spent coffee grounds providedthe best conditions for obtaining extract with high phe-nolic compounds including CGA [100] Because the maindiscriminator in these SLE methods is polarity it leads tolimited selectivity in extraction when caffeine was analyzedin roasted coffee ground not only caffeine was extractedwith the SLE procedure [101]This method of extraction maytherefore present interference problems during instrumentalanalysis
Other conditions that define the performance of SLE pro-cedures are the effect of temperature and duration of extrac-tion [92 102] As a result of different temperature sensitivitiesof the complex mixture of constituents in coffee it is difficultto satisfy the temperature needs of individual analytes ina single-extraction system In an attempt to eliminate thischallenge a double-extraction method was described whichaccommodated the extraction of both thermolabile CGA andthermostable caffeine with high recoveries [20] In this sys-tem one batch is fed into selected stages at mild temperatureand pressure while another is fed into remaining stages athigher temperature and pressure and 50 of extracts fromeach stream are mixed and lyophilized Apart from beingcumbersome multistep SLE may lead to loss of some ana-lytes It was recently found that proprietary ethanol single-step extraction resulted in higher content of caffeine thanmultistep procedures [103]
32 Liquid-Liquid Extraction and Solid-Phase ExtractionLiquid-liquid extraction (LLE) is one of the most widely usedtraditional sample preparation techniques [104] The dispar-ity in solubility of an analyte in two immiscible solvents is har-nessed for its extraction For the extraction of the four bioac-tive constituents of coffee LLE can be practiced by extractingthese analytes fromaqueousmedium to an organic oneHow-ever because each of these constituents has at least a mod-erate solubility in water application of LLE in this regard islimited In one example caffeine was extracted from waterinto dichloromethane while CGA remained in the residualaqueous solution [105] To solubilize a polar analyte in anorganic solvent during an LLE procedure especially whengas chromatographic analysis is intended it is sometimesnecessary to add ionic surfactants in the extraction medium[106 107]
Solid-phase extraction (SPE) utilizes the sorptive capacityof a stationary sorbent in SPE cartridge in order to extractanalytes It starts by conditioning the cartridge after whichthe sample is run through then dried and finally eluted usinga suitable solvent [108 109] Recently Caprioli et al [110] haveexplained the application of SPE for the extraction of CGAin Arabica and Robusta coffees using Strata-X cartridge Lowtemperatures and methanol as extraction solvent resulted inthe most efficient extraction of CGA
Both LLE and SPE applications are dwarfed by beingmul-tistep and environmentally unfriendly due to large solventvolumes involved especially with regard to LLE
33 Microwave-Assisted and Ultrasound-Assisted ExtractionsMicrowave-assisted extraction (MAE) is a solvent reductionextraction method that uses electromagnetic energy to assist(enhance) extraction of analytes Microwave interacts withmatter in a special way that causes instantaneous heatingthus facilitating desorption of analytes from their matricesand improving mass transfer rate [111 112] Compared toconventional solvent extraction MAE is faster and involvesminimal use of solvent In just under 40 smaximumphenoliccontent was obtained from spent filter coffee under theinfluence of low concentrated ethanol [113] Hongcheng et al
4 ISRN Nutrition
[114] have developed a fastMAEmethod for the simultaneousextraction of TRG caffeine and nicotinic acid from coffeeusing a pressure of 200 psi Other conditions that can affectthis procedure include temperature and wattage At thetemperature of 50∘Candwattage of 800wCGA- and caffeine-rich extracts were prepared from coffee beans [115]
Another assisted extraction procedure is ultrasound-assisted extraction (UAE) a procedure that uses sound fre-quency to agitate extraction medium and speed up contactbetween solvent and matrix It has found a number of appli-cations in the extraction of phytochemicals [50 116] Theenergy burst from UAE equipment causes thermal heatingthat reduces extraction timeWang et al [117] have found thatquantity of caffeine extracted from coffee reached saturationin only 15 s and augmented positivelywith increase in temper-ature at an operating frequency of 28 kHz UAE was success-fully applied to the determination of TRG in coffee powderand instant coffee with excellent recoveries [118]
Some of the demerits of MAE and UAE include the diffi-culty in selecting appropriate extraction conditions (includ-ing type of solvent pressure and frequency) that would notcause excessive heating and lead to degradation of some ana-lytes necessity of clean-up after extraction and relative highcost of equipment
34 Other Extraction Methods The combination of gas-likemass transfer and liquid-like solvating abilities of supercrit-ical fluids is exploited in the extraction method known assupercritical fluid extraction (SFE) In this method a solventat its supercritical state is used to speed up extraction byan increased matrix-penetrating ability and enhanced masstransfer potential Although large industrial application ofSFE is often hindered by the trade-off between selectivityand recovery efficiency this method is still found in routinelaboratory applications [79 119] Among the numerous fac-tors that affect performance of this approach temperatureand pressure are key considerations in recovery and selec-tivity calculations Machmudah et al [120] have found thatrecovery of caffeine and the separation factor of CGA fromcaffeine were positively correlated with increasing height(pressure) of nonpolar recovery section in the separationsystem using supercritical carbon dioxide (SCCO
2) in water
They also found that recovery of caffeine in the SCCO2phase
increased with decreased temperature This could only betrue at pressures below the crossover pressure Above thecrossover pressure (sim200 bar) however an increase in tem-perature resulted in an increased recovery as observed in theextraction of caffeine from Robusta coffee husks [39]
Solid-phase microextraction (SPME) was introduced inthe 1990s in response to the challenges posed by SPE It basi-cally involves sorption of an analyte to a commercial fibercoated with polymeric substance followed by a desorptionstep using a thermal process or suitable solvent SPME allowsfor solvent minimization and provides for higher sampleenrichment Different forms of SPME techniques are prac-ticed but the headspace type (HS-SPME) is very suitablein the analysis of volatile compounds [121 122] Affinity ofan analyte towards the fiber can be enhanced by carefully
selecting the right polymer coating material [123] Lopez-Darias et al [124] found that poly-(ViHIm+Clminus) gave excel-lent performance for aromatic alcohols while polyacrylamidecoating performed better for heterocyclic aromatics Tem-perature and extraction time also influence the performanceof this method as noticed in a different experiment wherepoly-dimethyl-siloxane in combination with divinylbenzene(PDMSDVB) SPME fiber with a 65 120583m thick film coatingwas used for the extraction of caffeine and CGA in coffee[125] Some of the shortcomings of SPME include leaching ofcoatingmaterial breaking of fiber and bending of the syringesupport
4 Methods for Characterizationand Quantification of BioactiveMicronutrients of Coffee
Due to the economic importance of coffee and its constit-uent bioactive substances consumer interest and safetyshould remain paramount Therefore there is an increasingdemand for proper quality control for certification of contentsand reducing counterfeits and substandard products Toachieve these noble goals sensitive and accurate analyticalmethods for both qualitative and quantitative determinationsand characterization of chemical substances in coffee arerequired There are many analytical procedures (Table 1)including chromatographic photometric spectral and elec-trochemical methods that are geared toward this end [126127]
41 Separation-Based Methods To reduce interference andincrease sensitivity an extract is commonly run througha separation system followed by detection of separatedcontents using a suitable detector Among themany analyticaltechniques that have been applied in the determination ofcoffee constituents high performance liquid chromatogra-phy (HPLC) gas chromatography (GC) and capillary elec-trophoresis (CE) in combinationwith various detectors suchas ultravioletvisible (UVVis) detector diode array detector(DAD) refractive index (RI) detector and chemilumines-cence detector are often applied for the determination ofnonvolatile volatile polar and nonpolar classes of analytes
411 HPLC Methods This is one of the most powerful toolsavailable for analytical applications inmany fields Because ofits versatility low limits of detection (LOD) and accessibilityits applications can now be found in numerous methods forthe analyses of industrial chemicals agroallied chemicalsand constituents of foods and beverages It is the singlemost applied separation-based method of quantification forbioactive constituents in coffee and coffee products AHPLC-based method for TRG determination and for the qualitycontrol of coffee products was explained by Liu et al [118]After its separation TRG was detected at 260 nm 120582 The totalcontents of CGA and its isomers in a cup of certified ItalianEspresso coffee were between 15225 and 22234mgKgminus1 asdetermined by HPLC-DAD [110] Results of HPLC-UVRIanalysis of 17 Brazilian Arabica cultivars have revealed that
ISRN Nutrition 5
Table 1 Analytical methods for characterization and quantification of bioactive micronutrients in coffee
Micronutrient Method Figure of merit ReferenceCGA SWV LOD (0049 120583gmLminus1) Yardim 2012 [141]CGA caffeine UV-Vis Ra (91ndash9843) CVb (280ndash545) Belay and Gholap 2009 [105]TRG HPLC R (gt90) RSD (lt3) Liu et al 2011 [118]Caffeine NIRchemometrics RSD (1707) RMSEP (0378mgg) Zhang et al 2013 [152]TRG caffeine HPLC LOD (002mgL) LOQ (0005) Hongcheng et al 2012 [114]Caffeine DART-TOFMS R (97ndash107) RSD (lt5) Danhelova et al 2012 [101]TRG caffeine 1H-NMR CV (24 42) LOD (058 132mgg) del Campo et al 2010 [156]CGA DPP SWV LOD (0236 120583molLminus1 134 nmolLminus1) Araujo et al 2009 [144]CGA isomers 2D-NMR R (75ndash80) R2 (09960ndash09994) Wei et al 2010 [155]Caffeine CE HPLC LOD (087 0021mg100 g) RSD (lt2) Bizzotto et al 2013 [137]Caffeine CVc LOD (0348 120583molLminus1) R2 (0999) Mersal 2012 [142]Caffeine CE RSD (lt2) Li et al 2009 [139]CGA DPV LOD (0148 120583molLminus1) Santos et al 2011 [146]CGA isomers HPLC R (67ndash99) R2 (gt099) Caprioli et al 2013 [110]CGA BiosensorSWV LOD (0915 120583molLminus1) R (932ndash1057) Fernandes et al 2009 [147]Cafestol kahweol HPLC RSD (lt5) Sridevi et al 2011 [71]Caffeine CVSWV LOD (0137 120583molLminus1) R (gt90) Amare and Admassie 2012 [145]aPercent recovery bcoefficient of variation ccyclic voltammetry
semidry processing method showed lower levels of CGAand TRG than coffee processed by wet method which goesto confirm the effect of different processing methods onconstituents of coffee [128] In another experiment HPLC-UVVis analysis revealed that coffee contains 006ndash255caffeine and this value decreases with roasting intensity [129]
HPLC can be performed in either reverse or normalphasemode A caffeine assessment tool (CAT) was developedwith results obtained from a reverse-phase- (RP-) HPLC-UVanalysis of several coffee and coffee-based beverages [130]Moreira and Scarminio [131] have applied RP-HPLC-DADfor the determination of caffeine at 275 nm 120582 using a binaryethanol-dichloromethane solution (1 1) as mobile phaseMobile phase in gradient flow mode is often employed toresolve complex mixtures When different coffee extractionmethods were tested using a mixture of 01 formic acid inwater and 01 formic acid in acetonitrile in this type of flowmode CGA and caffeine contents of the different extractswere different confirming that contents may vary accordingto method of extraction [125]
Two-dimensional HPLC (2D-HPLC) may provide forbetter resolution than in ordinary practiceThe application ofthis system in combination with chemiluminescence detec-tor allowed for increased sensitivity and better selectivityin the determination of antioxidant constituents of threeEspresso coffees (ldquoRistrettordquo ldquoDecaffeinatordquo and ldquoVollutordquo)[132] Elsewhere a C-18 and Bondapak NH
2columns in
series were used for the simultaneous determination of TRGcaffeine and nicotinic acid [114] This method selected con-ditions optimal at 120∘C and 200 psi and good separationwas achieved in just 3min driven by 002Mphosphoric acid-methanol (70 30 vv) mobile phase at 08mLmin
Apart from the common detection systems (UVVisDAD and RI) often employed in liquid chromatographic
applications for the characterization of these coffee con-tents applications of MS detection are also found in the lit-erature By a careful selection of parameters molecularmarkers for distinguishing between different coffee samplesor between constituents can be assigned [133] In a methodof liquid chromatographymultistage spectrometry (LCMS119899) (119899 = 2ndash4) described by Jaiswal and Kuhnert [134]hitherto unreported isomers of CGA (triacyl CGAs) weredetected in Robusta coffee bean extracts and their struc-tures assigned using LCMS119899 fragmentation patterns Incombination with similar fragmentation patterns (LCMS119899119899 = 2-3) relative hydrophobicity and fragmentation analogywere also harnessed to distinguish between two isomericclasses of CGA (CGA lactones and cinnamoylshikimate)which are formed from CGA by loss of water at high pro-cessing temperatures [135] Interestingly a high temperaturereverse phase liquid chromatography coupled with isotoperatio mass spectrometry (HT-RPLCIRMS) was employed todistinguish between natural and synthetic caffeine in coffeedrinks without the painful need for extraction by using 12057513 Cvalues (between 25 and 32permilfor natural caffeine and between33 and 38permilfor synthetic caffeine) as distinguishable groups[136] This method will be a special aid in the fight againstcounterfeiting and adulteration of coffee products
412 CE and Other Methods CE uses a very small diameterbore capillary to effect separation of charged analytes dis-solved in a suitable buffer The driving force for this separa-tion system is the use of high voltage that influences electroki-netic migration of analytes to either of the positive and neg-ative poles Hence a candidate analyte for CE must possess anet negative or positive charge for effective separation In thelast five years CE has been applied in many fields includingthe analysis of plant materials [86] While HPLC did provide
6 ISRN Nutrition
lower values of LOD for the determination of caffeine indecaffeinated coffee than CE the latter was 30 faster hadlower cost of reagents and generated smaller volumes ofresidues [137] In a similar experiment a fast hydrodynamicinjection (50mBar 7 s) was applied in the analysis of caffeinein commercial decaffeinated coffee using a 48 cm times 50 120583mfused-silica capillary [138] Other optimized conditions forthis method include a mixture of sodium carbonate (10mmolLminus1) and sodium dodecyl sulfate (50mmolLminus1) asbuffer 15 kV voltage and 206 nm 120582 Elsewhere Li et al [139]have explained a CEmethod for the determination of caffeinein roasted coffee This method is characterized by extremelyhigh precision percent relative standard deviation (RSD)was less than 08 for retention time and 17 for peak areas
GC determination can be extremely important especiallyin the analysis of volatile components of coffee [108 121]For semivolatile and nonvolatile portions however alter-native methods will be more desirable and effective Oneof such methods is based countercurrent chromatography(CCC) which differs significantly from the preceding typesof separation systems by not involving any solid supportInstead two immiscible solvents are used one solvent apiecefor the stationary and mobile phases This is exemplified inthe method of Machmudah et al [120] where SCCO
2and
water were used in countercurrent flow mode to effect theseparation of CGA from caffeine Recently a method basedon the high-speed mode (HSCCC) which could be used forthe preparative isolation of milligram amount of CGA fromcoffee was explained [140]
42 Separation-Less Methods In many instances determi-nation of analytes is performed without the need to gothrough a separation step Molecular behaviors such as massfragmentation patterns magnetic resonance electrical prop-erties and UVVis or IR absorbance are used for their directcharacterization andor quantificationThesemethods can bedefined by extremely low LODs high throughput and goodselectivity and sensitivity in their applications to the analysisof coffee micronutrients
421 Spectroscopic Methods These methods are based onlight-absorbing or light-emitting properties of molecules asthey interact with electromagnetic radiation As a moleculeabsorbs light energy of defined wavelength electronic tran-sition characteristic of that molecule is elicited and thiscan be used for the characterization and quantification ofsuch molecule At 324 nm CGA has a strong 120587-120587lowast transitionresulting from the delocalized electrons on benzene ringand this was used for its characterization and quantificationin coffee bean extract [105] Null hypothesis was obeyedbetween the results obtained by this method and results ofHPLC analysis
Many determinations of antioxidant activities in coffee bydifferent mechanisms are based on UVVis absorption spec-troscopy [113] CGA and caffeine are among the main antiox-idant micronutrients in coffee Their antioxidant capaci-ties were measured using 221015840-azino-bis(3-ethylbenzothiazo-line-6-sulphonic acid (ABTS) 22-diphenyl-1-picrylhydrazyl
(DPPH) and Folin-Ciocalteau [102] In a similar inves-tigation antioxidant capacities of these hydrophilic com-poundswere also investigated using disodiumnitrosodisulfo-nate (Fremyrsquos salt) and 2266-tetramethyl-1-piperidinyloxy(TEMPO) and results for different coffee brewing techniqueswere obtained as 460ndash1023 (Filter) lt42 (Plunger) and856 (Espresso) [98] DPPH-radical scavenging activitygreater than 75 was recorded in the extract of green coffeebeans containing 22ndash40 caffeine and 31ndash62 CGA [115]
422 Electrochemical Methods Oxidation-reduction behav-iors of analytes at electrode surfaces may be used for thecharacterization of such analytes based on their specificrelationships with potential and current or other electricalquantities Different types of voltammetry and coulometryhave been applied in the determination of coffee constituentswith high sensitivity selectivity and speed For instanceoxidation of CGA at the surface of boron-doped diamondelectrode using adsorptive transfer stripping voltammetricconditions was applied for the electrochemical estimationof antioxidant properties of coffee samples with very lowLOD (49 ngmL) and good linearity within the concentrationrange of 025ndash400120583gmL [141] Direct determination ofcaffeine was achieved by square-wave voltammetry (SWV)using a highly selective pseudo carbon paste electrode versusSCE [142]
Different additives may influence the performance ofthese methods in several ways While milk proteins (caseinand bovine serum albumin) formed complexes with polyphe-nolic constituents in coffee thereby significantly reduc-ing their available OH groups and thus their antioxidantcapacities as revealed by coulometric titration with hexa-cyanoferrate (III) ions [143] addition of cationic surfactant(cetyltrimethylammonium bromide) in the supporting elec-trolyte (004mol Lminus1 phosphate buffer pH 60) significantlyenhanced the reduction of caffeine at hanging mercury dropelectrode determined by both differential-pulse polarogra-phy (DPP) and SWV [144] When the surface of a glassycarbon electrode was modified by the deposition of thin filmof 4-amino-3-hydroxynaphthalene sulfonic acid (AHNSA)highly selective electrocatalyzed oxidation of caffeine wasachieved leading to its high recoveries in coffee extracts [145]
Recently an electrochemical sensor for the selectivedetermination of CGA in coffee samples by differential pulsevoltammetry (DPV) was constructed from the deposition ofa thin film of molecularly imprinted siloxane (MIS) on goldsurface [146] In a similar application by Fernandes et al[147] CGA was selectively determined by SWV at +025V(versus AgAgCl) using a biosensor constructed from 1-n-butyl-3-methylimidazoliumhexafluorophosphate containingdispersed iridium nanoparticles (Ir-BMIPF
6) and polyphe-
nol oxidase
423 Spectral Methods Analytical characterization andquantification can also be achieved through stand-alonespectral revelations MS fragmentation patterns under dif-ferent ionization modes have been employed in chemicalanalysis including analysis of components of coffee [148]
ISRN Nutrition 7
Direct analysis in real time (DART) coupled to time-of-flightmass spectrometry (TOFMS) yielded a high throughput(lt1min per run) analysis of caffeine in coffee samples [101]Without the need for sample preparation or chromatographicseparation the molecular ion (M +H)+ resulting from themethod of DART-MS was used for the identification ofcaffeine in commercial instant coffee samples [149] Caffeinehas a mass to charge ratio (119898119911) of 194 and its characteriza-tion alongside kahweol (119898119911 296) and cafestol (119898119911 298)two marker compounds for C arabica and C canephorawas achieved in the method of single photon ionizationcoupled with TOFMS (SPI-TOFMS) developed by Hertz-Schunemann et al [150] for the recognition of roasting gasprofiles of coffee
Characterization of bioactive components of coffee canalso be achieved by using their near-IR (NIR) (2500ndash4000 cmminus1) absorption spectra Methods based on thisapproach are nondestructive and can offer reliable speed ofdetermination In addition to qualitative analysis chemomet-ric models can assist in quantitative interpretation of NIRspectral data In one example caffeine TRG and CGA weredetermined as components of sensory quality in Arabicaroasted coffee samples using ordered prediction selection(OPS) algorithm partial least squares (PLS) andNIR spectra[151] Recently Zhang et al [152] developed an improvedregression model for NIR determination of caffeine Thismethod is characterized by root mean square error of crossvalidation (RMSECV) of 0375mgg RSD of 1707 andcorrelation coefficient of 0918 at PLS factor of 7
For some time now nuclear magnetic resonance (NMR)spectrometry has been offering good information for theidentification and structural elucidation of compounds andthis has now been extended to coffee constituents Using 1H-NMR and partial least squares discriminant analysis (OPLS-DA) models TRG and CGA were found among the mainmetabolites that can characterize and separate C ara-bica samples according to their geographical origin [153]Recently structures of CGA lactones which hitherto werenot available in the literature were established from NMRdata [140] Self-association and complexation of coffee con-stituents both in coffee brews and in aqueousmedia can poseserious challenge for their analytical resolutions DrsquoAmelioet al [154] have investigated structural features of CGA-caffeine complexation using high resolution 1H-NMR NMRcan also offer quantitative information on chemical com-ponents in coffee Without a nuclear Overhauser effectthree isomers of CGA were identified and quantified ingreen coffee bean extract through integration of 2D NMRcarbon signals by use of relaxation reagent and inverse-gateddecouplingmethod [155] According to del Campo et al [156]caffeine and TRG among other constituents of coffee canbe quantitatively analyzed by use of their singlet 1H-NMRsignals within 76ndash95 ppm and the use of 3-(trimethylsilyl)-2233-tetradeuteropropionic acid both as internal standardand as reference for 120575 = 000 ppm
5 Conclusions
Coffee is a popular beverage that is obtained from differentvarieties of coffee beansThis important drink contains many
micronutrients some of which have proven bioactivitiessuch as anticancer antimicrobial antioxidant and host ofother effects Four important groups of these biologicallyimportant micronutrients namely caffeine CGA diter-penes and TRG have been discussed in this review Becauseof their importance in biological systems recent analyticalmethods for their characterization and quantitative determi-nation have also been reviewed It is envisaged that properapplications of these methods will go a long way in aidingquality assurance and safeguarding consumer safety andsatisfaction
Conflict of Interests
The author declares that there is no conflict of interestsregarding the publication of this paper
References
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[2] A L Oliveira F A CabralM N Eberlin andHM A B Cord-ello ldquoSensory evaluation of black instant coffee beverage withsome volatile compounds present in aromatic oil from roastedcoffeerdquo Ciencia e Tecnologia de Alimentos vol 29 no 1 pp 76ndash80 2009
[3] JMiran ldquoSpace mobility and translocal connections across theRed Sea area since 1500rdquo Northeast African Studies vol 12 no1 pp 9ndash26 2012
[4] K Hundera R Aerts M de Beenhouwer et al ldquoBoth forestfragmentation and coffee cultivation negatively affect epiphyticorchid diversity in Ethiopian moist evergreen Afromontaneforestsrdquo Biological Conservation vol 159 pp 285ndash291 2013
[5] F Serra C G Guillou F Reniero et al ldquoDetermination ofthe geographical origin of green coffee by principal componentanalysis of carbon nitrogen and boron stable isotope ratiosrdquoRapid Communications in Mass Spectrometry vol 19 no 15 pp2111ndash2115 2005
[6] P Moguel and V M Toledo ldquoBiodiversity conservation in tra-ditional coffee systems ofMexicordquoConservation Biology vol 13no 1 pp 11ndash21 1999
[7] F Anthony B Bertrand O Quiros et al ldquoGenetic diversity ofwild coffee (Coffea arabica L) using molecular markersrdquoEuphytica vol 118 no 1 pp 53ndash65 2001
[8] A-M Klein I Steffan-Dewenter and T Tscharntke ldquoBee polli-nation and fruit set of Coffea arabica and C canephora (Rubia-ceae)rdquoTheAmerican Journal of Botany vol 90 no 1 pp 153ndash1572003
[9] A Lecolier P Besse A Charrier T-N Tchakaloff and MNoirot ldquoUnraveling the origin of Coffea arabica ldquoBourbonpointurdquo from la Reunion a historical and scientific perspectiverdquoEuphytica vol 168 no 1 pp 1ndash10 2009
[10] D C Carvalho M R P L Brigagao M H S Santos F B Ade Paula A Giusti-Paiva and L Azevedo ldquoOrganic and Con-ventional Coffea arabica L a comparative study of the chemicalcomposition and physiological biochemical and toxicologicaleffects inWistar ratsrdquo Plant Foods for Human Nutrition vol 66no 2 pp 114ndash121 2011
8 ISRN Nutrition
[11] S Topik J M Talbot and M Samper ldquoIntroduction global-ization neoliberalism and the latin American coffee societiesrdquoLatin American Perspectives vol 37 no 2 pp 5ndash20 2010
[12] C M Tucker H Eakin and E J Castellanos ldquoPerceptions ofrisk and adaptation coffee producers market shocks andextreme weather in Central America and Mexicordquo GlobalEnvironmental Change vol 20 no 1 pp 23ndash32 2010
[13] E G Burbano M G Wright N E Gillette et al ldquoEfficacy oftraps lures and repellents for Xylosandrus compactus (Cole-optera Curculionidae) and other ambrosia beetles on Coffeaarabica plantations and Acacia koa nurseries in Hawaiirdquo Envi-ronmental Entomology vol 41 no 1 pp 133ndash140 2012
[14] C W Kathurima B M Gichimu G M Kenji S M Muhohoand R Boulanger ldquoEvaluation of beverage quality and greenbean physical characteristics of selected Arabica coffee geno-types in Kenyardquo African Journal of Food Science vol 3 no 11pp 365ndash371 2009
[15] W J Rogers S Michaux M Bastin and P Bucheli ldquoChanges tothe content of sugars sugar alcohols myo-inositol carboxylicacids and inorganic anions in developing grains from differentvarieties of Robusta (Coffea canephora) andArabica (C arabica)coffeesrdquo Plant Science vol 149 no 2 pp 115ndash123 1999
[16] R Teuber ldquoGeographical indications of origin as a tool of prod-uct differentiation the case of coffeerdquo Journal of InternationalFood and Agribusiness Marketing vol 22 no 3-4 pp 277ndash2982010
[17] H C Liu C F You C Y Chen Y C Liu and M T ChungldquoGeographic determination of coffee beans usingmulti-elementanalysis and isotope ratios of boron and strontiumrdquo FoodChemistry vol 142 pp 439ndash445 2013
[18] T Niseteo D Komes A Belscak-Cvitanovic D Horzic andM Bude ldquoBioactive composition and antioxidant potential ofdifferent commonly consumed coffee brews affected by theirpreparation technique and milk additionrdquo Food Chemistry vol134 no 4 pp 1870ndash1877 2012
[19] M Oliveira S Casal S Morais et al ldquoIntra- and interspecificmineral composition variability of commercial instant coffeesand coffee substitutes contribution to mineral intakerdquo FoodChemistry vol 130 no 3 pp 702ndash709 2012
[20] J A Vignoli D G Bassoli and M T Benassi ldquoAntioxidantactivity polyphenols caffeine andmelanoidins in soluble coffeethe influence of processing conditions and raw materialrdquo FoodChemistry vol 124 no 3 pp 863ndash868 2011
[21] S I Mussatto L M Carneiro J P A Silva I C Roberto and JA Teixeira ldquoA study on chemical constituents and sugarsextraction from spent coffee groundsrdquo Carbohydrate Polymersvol 83 no 2 pp 368ndash374 2011
[22] Y F Chu P H Brown B J Lyle et al ldquoRoasted coffees high inlipophilic antioxidants and chlorogenic acid lactones are moreneuroprotective than green coffeesrdquo Journal of Agricultural andFood Chemistry vol 57 no 20 pp 9801ndash9808 2009
[23] S Johnson W P Koh R Wang S Govindarajan M C Yu andJ M Yuan ldquoCoffee consumption and reduced risk of hepatocel-lular carcinoma findings from the Singapore Chinese HealthStudyrdquo Cancer Causes and Control vol 22 no 3 pp 503ndash5102011
[24] J Tai S Cheung E Chan and D Hasman ldquoAntiproliferationeffect of commercially brewed coffees on human ovarian cancercells in vitrordquoNutrition and Cancer vol 62 no 8 pp 1044ndash10572010
[25] GWArendash andC Cao ldquoCaffeine and coffee as therapeuticsagainst Alzheimerrsquos diseaserdquo Journal of Alzheimerrsquos Disease vol20 no 1 pp 117ndash126 2010
[26] U Boettler K Sommerfeld N Volz et al ldquoCoffee constituentsas modulators of Nrf2 nuclear translocation and ARE (EpRE)-dependent gene expressionrdquo Journal of Nutritional Biochem-istry vol 22 no 5 pp 426ndash440 2011
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[29] N Amaresh A R Mullaicharam andM A El-Khider ldquoChem-istry and pharmacology of caffeine in different types of tealeavesrdquo International Journal of Nutrition Pharmacology Neu-rological Diseases vol 1 no 2 pp 110ndash115 2011
[30] L Wang L-H Gong C-J Chen H-B Han and H-H LildquoColumn-chromatographic extraction and separation of poly-phenols caffeine and theanine from green teardquo Food Chemistryvol 131 no 4 pp 1539ndash1545 2012
[31] Q V Vuong and P D Roach ldquoCaffeine in green tea its removaland isolationrdquo Separation and Purification Reviews vol 43 no2 pp 155ndash174 2014
[32] M C Borges M A R Vinolo K Nakajima et al ldquoThe effect ofmate tea (Ilex paraguariensis) on metabolic and inflammatoryparameters in high-fat diet-fed Wistar ratsrdquo International Jour-nal of Food Sciences and Nutrition vol 64 no 5 pp 561ndash5692013
[33] V Olmos N Bardoni A S Ridolfi and E C Villaamil LeporildquoCaffeine levels in beverages from Argentinarsquos market applica-tion to caffeine dietary intake assessmentrdquo Food Additives andContaminants A vol 26 no 3 pp 275ndash281 2009
[34] S Oba C Nagata K Nakamura et al ldquoConsumption of coffeegreen tea oolong tea black tea chocolate snacks and thecaffeine content in relation to risk of diabetes in Japanese menandwomenrdquoBritish Journal of Nutrition vol 103 no 3 pp 453ndash459 2010
[35] S N Bhupathiraju A Pan V S Malik et al ldquoCaffeinated andcaffeine-free beverages and risk of type 2 diabetesrdquoThe Ameri-can Journal of Clinical Nutrition vol 97 pp 155ndash166 2013
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[38] P Mazzafera andM B Silvarolla ldquoCaffeine content variation insingle greenArabica coffee seedsrdquo Seed Science Research vol 20no 3 pp 163ndash167 2010
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[40] G Laurence K Wallman and K Guelfi ldquoEffects of caffeine ontime trial performance in sedentary menrdquo Journal of Sports Sci-ences vol 30 no 12 pp 1235ndash1240 2012
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Disease Markers
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Oxidative Medicine and Cellular Longevity
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
4 ISRN Nutrition
[114] have developed a fastMAEmethod for the simultaneousextraction of TRG caffeine and nicotinic acid from coffeeusing a pressure of 200 psi Other conditions that can affectthis procedure include temperature and wattage At thetemperature of 50∘Candwattage of 800wCGA- and caffeine-rich extracts were prepared from coffee beans [115]
Another assisted extraction procedure is ultrasound-assisted extraction (UAE) a procedure that uses sound fre-quency to agitate extraction medium and speed up contactbetween solvent and matrix It has found a number of appli-cations in the extraction of phytochemicals [50 116] Theenergy burst from UAE equipment causes thermal heatingthat reduces extraction timeWang et al [117] have found thatquantity of caffeine extracted from coffee reached saturationin only 15 s and augmented positivelywith increase in temper-ature at an operating frequency of 28 kHz UAE was success-fully applied to the determination of TRG in coffee powderand instant coffee with excellent recoveries [118]
Some of the demerits of MAE and UAE include the diffi-culty in selecting appropriate extraction conditions (includ-ing type of solvent pressure and frequency) that would notcause excessive heating and lead to degradation of some ana-lytes necessity of clean-up after extraction and relative highcost of equipment
34 Other Extraction Methods The combination of gas-likemass transfer and liquid-like solvating abilities of supercrit-ical fluids is exploited in the extraction method known assupercritical fluid extraction (SFE) In this method a solventat its supercritical state is used to speed up extraction byan increased matrix-penetrating ability and enhanced masstransfer potential Although large industrial application ofSFE is often hindered by the trade-off between selectivityand recovery efficiency this method is still found in routinelaboratory applications [79 119] Among the numerous fac-tors that affect performance of this approach temperatureand pressure are key considerations in recovery and selec-tivity calculations Machmudah et al [120] have found thatrecovery of caffeine and the separation factor of CGA fromcaffeine were positively correlated with increasing height(pressure) of nonpolar recovery section in the separationsystem using supercritical carbon dioxide (SCCO
2) in water
They also found that recovery of caffeine in the SCCO2phase
increased with decreased temperature This could only betrue at pressures below the crossover pressure Above thecrossover pressure (sim200 bar) however an increase in tem-perature resulted in an increased recovery as observed in theextraction of caffeine from Robusta coffee husks [39]
Solid-phase microextraction (SPME) was introduced inthe 1990s in response to the challenges posed by SPE It basi-cally involves sorption of an analyte to a commercial fibercoated with polymeric substance followed by a desorptionstep using a thermal process or suitable solvent SPME allowsfor solvent minimization and provides for higher sampleenrichment Different forms of SPME techniques are prac-ticed but the headspace type (HS-SPME) is very suitablein the analysis of volatile compounds [121 122] Affinity ofan analyte towards the fiber can be enhanced by carefully
selecting the right polymer coating material [123] Lopez-Darias et al [124] found that poly-(ViHIm+Clminus) gave excel-lent performance for aromatic alcohols while polyacrylamidecoating performed better for heterocyclic aromatics Tem-perature and extraction time also influence the performanceof this method as noticed in a different experiment wherepoly-dimethyl-siloxane in combination with divinylbenzene(PDMSDVB) SPME fiber with a 65 120583m thick film coatingwas used for the extraction of caffeine and CGA in coffee[125] Some of the shortcomings of SPME include leaching ofcoatingmaterial breaking of fiber and bending of the syringesupport
4 Methods for Characterizationand Quantification of BioactiveMicronutrients of Coffee
Due to the economic importance of coffee and its constit-uent bioactive substances consumer interest and safetyshould remain paramount Therefore there is an increasingdemand for proper quality control for certification of contentsand reducing counterfeits and substandard products Toachieve these noble goals sensitive and accurate analyticalmethods for both qualitative and quantitative determinationsand characterization of chemical substances in coffee arerequired There are many analytical procedures (Table 1)including chromatographic photometric spectral and elec-trochemical methods that are geared toward this end [126127]
41 Separation-Based Methods To reduce interference andincrease sensitivity an extract is commonly run througha separation system followed by detection of separatedcontents using a suitable detector Among themany analyticaltechniques that have been applied in the determination ofcoffee constituents high performance liquid chromatogra-phy (HPLC) gas chromatography (GC) and capillary elec-trophoresis (CE) in combinationwith various detectors suchas ultravioletvisible (UVVis) detector diode array detector(DAD) refractive index (RI) detector and chemilumines-cence detector are often applied for the determination ofnonvolatile volatile polar and nonpolar classes of analytes
411 HPLC Methods This is one of the most powerful toolsavailable for analytical applications inmany fields Because ofits versatility low limits of detection (LOD) and accessibilityits applications can now be found in numerous methods forthe analyses of industrial chemicals agroallied chemicalsand constituents of foods and beverages It is the singlemost applied separation-based method of quantification forbioactive constituents in coffee and coffee products AHPLC-based method for TRG determination and for the qualitycontrol of coffee products was explained by Liu et al [118]After its separation TRG was detected at 260 nm 120582 The totalcontents of CGA and its isomers in a cup of certified ItalianEspresso coffee were between 15225 and 22234mgKgminus1 asdetermined by HPLC-DAD [110] Results of HPLC-UVRIanalysis of 17 Brazilian Arabica cultivars have revealed that
ISRN Nutrition 5
Table 1 Analytical methods for characterization and quantification of bioactive micronutrients in coffee
Micronutrient Method Figure of merit ReferenceCGA SWV LOD (0049 120583gmLminus1) Yardim 2012 [141]CGA caffeine UV-Vis Ra (91ndash9843) CVb (280ndash545) Belay and Gholap 2009 [105]TRG HPLC R (gt90) RSD (lt3) Liu et al 2011 [118]Caffeine NIRchemometrics RSD (1707) RMSEP (0378mgg) Zhang et al 2013 [152]TRG caffeine HPLC LOD (002mgL) LOQ (0005) Hongcheng et al 2012 [114]Caffeine DART-TOFMS R (97ndash107) RSD (lt5) Danhelova et al 2012 [101]TRG caffeine 1H-NMR CV (24 42) LOD (058 132mgg) del Campo et al 2010 [156]CGA DPP SWV LOD (0236 120583molLminus1 134 nmolLminus1) Araujo et al 2009 [144]CGA isomers 2D-NMR R (75ndash80) R2 (09960ndash09994) Wei et al 2010 [155]Caffeine CE HPLC LOD (087 0021mg100 g) RSD (lt2) Bizzotto et al 2013 [137]Caffeine CVc LOD (0348 120583molLminus1) R2 (0999) Mersal 2012 [142]Caffeine CE RSD (lt2) Li et al 2009 [139]CGA DPV LOD (0148 120583molLminus1) Santos et al 2011 [146]CGA isomers HPLC R (67ndash99) R2 (gt099) Caprioli et al 2013 [110]CGA BiosensorSWV LOD (0915 120583molLminus1) R (932ndash1057) Fernandes et al 2009 [147]Cafestol kahweol HPLC RSD (lt5) Sridevi et al 2011 [71]Caffeine CVSWV LOD (0137 120583molLminus1) R (gt90) Amare and Admassie 2012 [145]aPercent recovery bcoefficient of variation ccyclic voltammetry
semidry processing method showed lower levels of CGAand TRG than coffee processed by wet method which goesto confirm the effect of different processing methods onconstituents of coffee [128] In another experiment HPLC-UVVis analysis revealed that coffee contains 006ndash255caffeine and this value decreases with roasting intensity [129]
HPLC can be performed in either reverse or normalphasemode A caffeine assessment tool (CAT) was developedwith results obtained from a reverse-phase- (RP-) HPLC-UVanalysis of several coffee and coffee-based beverages [130]Moreira and Scarminio [131] have applied RP-HPLC-DADfor the determination of caffeine at 275 nm 120582 using a binaryethanol-dichloromethane solution (1 1) as mobile phaseMobile phase in gradient flow mode is often employed toresolve complex mixtures When different coffee extractionmethods were tested using a mixture of 01 formic acid inwater and 01 formic acid in acetonitrile in this type of flowmode CGA and caffeine contents of the different extractswere different confirming that contents may vary accordingto method of extraction [125]
Two-dimensional HPLC (2D-HPLC) may provide forbetter resolution than in ordinary practiceThe application ofthis system in combination with chemiluminescence detec-tor allowed for increased sensitivity and better selectivityin the determination of antioxidant constituents of threeEspresso coffees (ldquoRistrettordquo ldquoDecaffeinatordquo and ldquoVollutordquo)[132] Elsewhere a C-18 and Bondapak NH
2columns in
series were used for the simultaneous determination of TRGcaffeine and nicotinic acid [114] This method selected con-ditions optimal at 120∘C and 200 psi and good separationwas achieved in just 3min driven by 002Mphosphoric acid-methanol (70 30 vv) mobile phase at 08mLmin
Apart from the common detection systems (UVVisDAD and RI) often employed in liquid chromatographic
applications for the characterization of these coffee con-tents applications of MS detection are also found in the lit-erature By a careful selection of parameters molecularmarkers for distinguishing between different coffee samplesor between constituents can be assigned [133] In a methodof liquid chromatographymultistage spectrometry (LCMS119899) (119899 = 2ndash4) described by Jaiswal and Kuhnert [134]hitherto unreported isomers of CGA (triacyl CGAs) weredetected in Robusta coffee bean extracts and their struc-tures assigned using LCMS119899 fragmentation patterns Incombination with similar fragmentation patterns (LCMS119899119899 = 2-3) relative hydrophobicity and fragmentation analogywere also harnessed to distinguish between two isomericclasses of CGA (CGA lactones and cinnamoylshikimate)which are formed from CGA by loss of water at high pro-cessing temperatures [135] Interestingly a high temperaturereverse phase liquid chromatography coupled with isotoperatio mass spectrometry (HT-RPLCIRMS) was employed todistinguish between natural and synthetic caffeine in coffeedrinks without the painful need for extraction by using 12057513 Cvalues (between 25 and 32permilfor natural caffeine and between33 and 38permilfor synthetic caffeine) as distinguishable groups[136] This method will be a special aid in the fight againstcounterfeiting and adulteration of coffee products
412 CE and Other Methods CE uses a very small diameterbore capillary to effect separation of charged analytes dis-solved in a suitable buffer The driving force for this separa-tion system is the use of high voltage that influences electroki-netic migration of analytes to either of the positive and neg-ative poles Hence a candidate analyte for CE must possess anet negative or positive charge for effective separation In thelast five years CE has been applied in many fields includingthe analysis of plant materials [86] While HPLC did provide
6 ISRN Nutrition
lower values of LOD for the determination of caffeine indecaffeinated coffee than CE the latter was 30 faster hadlower cost of reagents and generated smaller volumes ofresidues [137] In a similar experiment a fast hydrodynamicinjection (50mBar 7 s) was applied in the analysis of caffeinein commercial decaffeinated coffee using a 48 cm times 50 120583mfused-silica capillary [138] Other optimized conditions forthis method include a mixture of sodium carbonate (10mmolLminus1) and sodium dodecyl sulfate (50mmolLminus1) asbuffer 15 kV voltage and 206 nm 120582 Elsewhere Li et al [139]have explained a CEmethod for the determination of caffeinein roasted coffee This method is characterized by extremelyhigh precision percent relative standard deviation (RSD)was less than 08 for retention time and 17 for peak areas
GC determination can be extremely important especiallyin the analysis of volatile components of coffee [108 121]For semivolatile and nonvolatile portions however alter-native methods will be more desirable and effective Oneof such methods is based countercurrent chromatography(CCC) which differs significantly from the preceding typesof separation systems by not involving any solid supportInstead two immiscible solvents are used one solvent apiecefor the stationary and mobile phases This is exemplified inthe method of Machmudah et al [120] where SCCO
2and
water were used in countercurrent flow mode to effect theseparation of CGA from caffeine Recently a method basedon the high-speed mode (HSCCC) which could be used forthe preparative isolation of milligram amount of CGA fromcoffee was explained [140]
42 Separation-Less Methods In many instances determi-nation of analytes is performed without the need to gothrough a separation step Molecular behaviors such as massfragmentation patterns magnetic resonance electrical prop-erties and UVVis or IR absorbance are used for their directcharacterization andor quantificationThesemethods can bedefined by extremely low LODs high throughput and goodselectivity and sensitivity in their applications to the analysisof coffee micronutrients
421 Spectroscopic Methods These methods are based onlight-absorbing or light-emitting properties of molecules asthey interact with electromagnetic radiation As a moleculeabsorbs light energy of defined wavelength electronic tran-sition characteristic of that molecule is elicited and thiscan be used for the characterization and quantification ofsuch molecule At 324 nm CGA has a strong 120587-120587lowast transitionresulting from the delocalized electrons on benzene ringand this was used for its characterization and quantificationin coffee bean extract [105] Null hypothesis was obeyedbetween the results obtained by this method and results ofHPLC analysis
Many determinations of antioxidant activities in coffee bydifferent mechanisms are based on UVVis absorption spec-troscopy [113] CGA and caffeine are among the main antiox-idant micronutrients in coffee Their antioxidant capaci-ties were measured using 221015840-azino-bis(3-ethylbenzothiazo-line-6-sulphonic acid (ABTS) 22-diphenyl-1-picrylhydrazyl
(DPPH) and Folin-Ciocalteau [102] In a similar inves-tigation antioxidant capacities of these hydrophilic com-poundswere also investigated using disodiumnitrosodisulfo-nate (Fremyrsquos salt) and 2266-tetramethyl-1-piperidinyloxy(TEMPO) and results for different coffee brewing techniqueswere obtained as 460ndash1023 (Filter) lt42 (Plunger) and856 (Espresso) [98] DPPH-radical scavenging activitygreater than 75 was recorded in the extract of green coffeebeans containing 22ndash40 caffeine and 31ndash62 CGA [115]
422 Electrochemical Methods Oxidation-reduction behav-iors of analytes at electrode surfaces may be used for thecharacterization of such analytes based on their specificrelationships with potential and current or other electricalquantities Different types of voltammetry and coulometryhave been applied in the determination of coffee constituentswith high sensitivity selectivity and speed For instanceoxidation of CGA at the surface of boron-doped diamondelectrode using adsorptive transfer stripping voltammetricconditions was applied for the electrochemical estimationof antioxidant properties of coffee samples with very lowLOD (49 ngmL) and good linearity within the concentrationrange of 025ndash400120583gmL [141] Direct determination ofcaffeine was achieved by square-wave voltammetry (SWV)using a highly selective pseudo carbon paste electrode versusSCE [142]
Different additives may influence the performance ofthese methods in several ways While milk proteins (caseinand bovine serum albumin) formed complexes with polyphe-nolic constituents in coffee thereby significantly reduc-ing their available OH groups and thus their antioxidantcapacities as revealed by coulometric titration with hexa-cyanoferrate (III) ions [143] addition of cationic surfactant(cetyltrimethylammonium bromide) in the supporting elec-trolyte (004mol Lminus1 phosphate buffer pH 60) significantlyenhanced the reduction of caffeine at hanging mercury dropelectrode determined by both differential-pulse polarogra-phy (DPP) and SWV [144] When the surface of a glassycarbon electrode was modified by the deposition of thin filmof 4-amino-3-hydroxynaphthalene sulfonic acid (AHNSA)highly selective electrocatalyzed oxidation of caffeine wasachieved leading to its high recoveries in coffee extracts [145]
Recently an electrochemical sensor for the selectivedetermination of CGA in coffee samples by differential pulsevoltammetry (DPV) was constructed from the deposition ofa thin film of molecularly imprinted siloxane (MIS) on goldsurface [146] In a similar application by Fernandes et al[147] CGA was selectively determined by SWV at +025V(versus AgAgCl) using a biosensor constructed from 1-n-butyl-3-methylimidazoliumhexafluorophosphate containingdispersed iridium nanoparticles (Ir-BMIPF
6) and polyphe-
nol oxidase
423 Spectral Methods Analytical characterization andquantification can also be achieved through stand-alonespectral revelations MS fragmentation patterns under dif-ferent ionization modes have been employed in chemicalanalysis including analysis of components of coffee [148]
ISRN Nutrition 7
Direct analysis in real time (DART) coupled to time-of-flightmass spectrometry (TOFMS) yielded a high throughput(lt1min per run) analysis of caffeine in coffee samples [101]Without the need for sample preparation or chromatographicseparation the molecular ion (M +H)+ resulting from themethod of DART-MS was used for the identification ofcaffeine in commercial instant coffee samples [149] Caffeinehas a mass to charge ratio (119898119911) of 194 and its characteriza-tion alongside kahweol (119898119911 296) and cafestol (119898119911 298)two marker compounds for C arabica and C canephorawas achieved in the method of single photon ionizationcoupled with TOFMS (SPI-TOFMS) developed by Hertz-Schunemann et al [150] for the recognition of roasting gasprofiles of coffee
Characterization of bioactive components of coffee canalso be achieved by using their near-IR (NIR) (2500ndash4000 cmminus1) absorption spectra Methods based on thisapproach are nondestructive and can offer reliable speed ofdetermination In addition to qualitative analysis chemomet-ric models can assist in quantitative interpretation of NIRspectral data In one example caffeine TRG and CGA weredetermined as components of sensory quality in Arabicaroasted coffee samples using ordered prediction selection(OPS) algorithm partial least squares (PLS) andNIR spectra[151] Recently Zhang et al [152] developed an improvedregression model for NIR determination of caffeine Thismethod is characterized by root mean square error of crossvalidation (RMSECV) of 0375mgg RSD of 1707 andcorrelation coefficient of 0918 at PLS factor of 7
For some time now nuclear magnetic resonance (NMR)spectrometry has been offering good information for theidentification and structural elucidation of compounds andthis has now been extended to coffee constituents Using 1H-NMR and partial least squares discriminant analysis (OPLS-DA) models TRG and CGA were found among the mainmetabolites that can characterize and separate C ara-bica samples according to their geographical origin [153]Recently structures of CGA lactones which hitherto werenot available in the literature were established from NMRdata [140] Self-association and complexation of coffee con-stituents both in coffee brews and in aqueousmedia can poseserious challenge for their analytical resolutions DrsquoAmelioet al [154] have investigated structural features of CGA-caffeine complexation using high resolution 1H-NMR NMRcan also offer quantitative information on chemical com-ponents in coffee Without a nuclear Overhauser effectthree isomers of CGA were identified and quantified ingreen coffee bean extract through integration of 2D NMRcarbon signals by use of relaxation reagent and inverse-gateddecouplingmethod [155] According to del Campo et al [156]caffeine and TRG among other constituents of coffee canbe quantitatively analyzed by use of their singlet 1H-NMRsignals within 76ndash95 ppm and the use of 3-(trimethylsilyl)-2233-tetradeuteropropionic acid both as internal standardand as reference for 120575 = 000 ppm
5 Conclusions
Coffee is a popular beverage that is obtained from differentvarieties of coffee beansThis important drink contains many
micronutrients some of which have proven bioactivitiessuch as anticancer antimicrobial antioxidant and host ofother effects Four important groups of these biologicallyimportant micronutrients namely caffeine CGA diter-penes and TRG have been discussed in this review Becauseof their importance in biological systems recent analyticalmethods for their characterization and quantitative determi-nation have also been reviewed It is envisaged that properapplications of these methods will go a long way in aidingquality assurance and safeguarding consumer safety andsatisfaction
Conflict of Interests
The author declares that there is no conflict of interestsregarding the publication of this paper
References
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[2] A L Oliveira F A CabralM N Eberlin andHM A B Cord-ello ldquoSensory evaluation of black instant coffee beverage withsome volatile compounds present in aromatic oil from roastedcoffeerdquo Ciencia e Tecnologia de Alimentos vol 29 no 1 pp 76ndash80 2009
[3] JMiran ldquoSpace mobility and translocal connections across theRed Sea area since 1500rdquo Northeast African Studies vol 12 no1 pp 9ndash26 2012
[4] K Hundera R Aerts M de Beenhouwer et al ldquoBoth forestfragmentation and coffee cultivation negatively affect epiphyticorchid diversity in Ethiopian moist evergreen Afromontaneforestsrdquo Biological Conservation vol 159 pp 285ndash291 2013
[5] F Serra C G Guillou F Reniero et al ldquoDetermination ofthe geographical origin of green coffee by principal componentanalysis of carbon nitrogen and boron stable isotope ratiosrdquoRapid Communications in Mass Spectrometry vol 19 no 15 pp2111ndash2115 2005
[6] P Moguel and V M Toledo ldquoBiodiversity conservation in tra-ditional coffee systems ofMexicordquoConservation Biology vol 13no 1 pp 11ndash21 1999
[7] F Anthony B Bertrand O Quiros et al ldquoGenetic diversity ofwild coffee (Coffea arabica L) using molecular markersrdquoEuphytica vol 118 no 1 pp 53ndash65 2001
[8] A-M Klein I Steffan-Dewenter and T Tscharntke ldquoBee polli-nation and fruit set of Coffea arabica and C canephora (Rubia-ceae)rdquoTheAmerican Journal of Botany vol 90 no 1 pp 153ndash1572003
[9] A Lecolier P Besse A Charrier T-N Tchakaloff and MNoirot ldquoUnraveling the origin of Coffea arabica ldquoBourbonpointurdquo from la Reunion a historical and scientific perspectiverdquoEuphytica vol 168 no 1 pp 1ndash10 2009
[10] D C Carvalho M R P L Brigagao M H S Santos F B Ade Paula A Giusti-Paiva and L Azevedo ldquoOrganic and Con-ventional Coffea arabica L a comparative study of the chemicalcomposition and physiological biochemical and toxicologicaleffects inWistar ratsrdquo Plant Foods for Human Nutrition vol 66no 2 pp 114ndash121 2011
8 ISRN Nutrition
[11] S Topik J M Talbot and M Samper ldquoIntroduction global-ization neoliberalism and the latin American coffee societiesrdquoLatin American Perspectives vol 37 no 2 pp 5ndash20 2010
[12] C M Tucker H Eakin and E J Castellanos ldquoPerceptions ofrisk and adaptation coffee producers market shocks andextreme weather in Central America and Mexicordquo GlobalEnvironmental Change vol 20 no 1 pp 23ndash32 2010
[13] E G Burbano M G Wright N E Gillette et al ldquoEfficacy oftraps lures and repellents for Xylosandrus compactus (Cole-optera Curculionidae) and other ambrosia beetles on Coffeaarabica plantations and Acacia koa nurseries in Hawaiirdquo Envi-ronmental Entomology vol 41 no 1 pp 133ndash140 2012
[14] C W Kathurima B M Gichimu G M Kenji S M Muhohoand R Boulanger ldquoEvaluation of beverage quality and greenbean physical characteristics of selected Arabica coffee geno-types in Kenyardquo African Journal of Food Science vol 3 no 11pp 365ndash371 2009
[15] W J Rogers S Michaux M Bastin and P Bucheli ldquoChanges tothe content of sugars sugar alcohols myo-inositol carboxylicacids and inorganic anions in developing grains from differentvarieties of Robusta (Coffea canephora) andArabica (C arabica)coffeesrdquo Plant Science vol 149 no 2 pp 115ndash123 1999
[16] R Teuber ldquoGeographical indications of origin as a tool of prod-uct differentiation the case of coffeerdquo Journal of InternationalFood and Agribusiness Marketing vol 22 no 3-4 pp 277ndash2982010
[17] H C Liu C F You C Y Chen Y C Liu and M T ChungldquoGeographic determination of coffee beans usingmulti-elementanalysis and isotope ratios of boron and strontiumrdquo FoodChemistry vol 142 pp 439ndash445 2013
[18] T Niseteo D Komes A Belscak-Cvitanovic D Horzic andM Bude ldquoBioactive composition and antioxidant potential ofdifferent commonly consumed coffee brews affected by theirpreparation technique and milk additionrdquo Food Chemistry vol134 no 4 pp 1870ndash1877 2012
[19] M Oliveira S Casal S Morais et al ldquoIntra- and interspecificmineral composition variability of commercial instant coffeesand coffee substitutes contribution to mineral intakerdquo FoodChemistry vol 130 no 3 pp 702ndash709 2012
[20] J A Vignoli D G Bassoli and M T Benassi ldquoAntioxidantactivity polyphenols caffeine andmelanoidins in soluble coffeethe influence of processing conditions and raw materialrdquo FoodChemistry vol 124 no 3 pp 863ndash868 2011
[21] S I Mussatto L M Carneiro J P A Silva I C Roberto and JA Teixeira ldquoA study on chemical constituents and sugarsextraction from spent coffee groundsrdquo Carbohydrate Polymersvol 83 no 2 pp 368ndash374 2011
[22] Y F Chu P H Brown B J Lyle et al ldquoRoasted coffees high inlipophilic antioxidants and chlorogenic acid lactones are moreneuroprotective than green coffeesrdquo Journal of Agricultural andFood Chemistry vol 57 no 20 pp 9801ndash9808 2009
[23] S Johnson W P Koh R Wang S Govindarajan M C Yu andJ M Yuan ldquoCoffee consumption and reduced risk of hepatocel-lular carcinoma findings from the Singapore Chinese HealthStudyrdquo Cancer Causes and Control vol 22 no 3 pp 503ndash5102011
[24] J Tai S Cheung E Chan and D Hasman ldquoAntiproliferationeffect of commercially brewed coffees on human ovarian cancercells in vitrordquoNutrition and Cancer vol 62 no 8 pp 1044ndash10572010
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[26] U Boettler K Sommerfeld N Volz et al ldquoCoffee constituentsas modulators of Nrf2 nuclear translocation and ARE (EpRE)-dependent gene expressionrdquo Journal of Nutritional Biochem-istry vol 22 no 5 pp 426ndash440 2011
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[29] N Amaresh A R Mullaicharam andM A El-Khider ldquoChem-istry and pharmacology of caffeine in different types of tealeavesrdquo International Journal of Nutrition Pharmacology Neu-rological Diseases vol 1 no 2 pp 110ndash115 2011
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[31] Q V Vuong and P D Roach ldquoCaffeine in green tea its removaland isolationrdquo Separation and Purification Reviews vol 43 no2 pp 155ndash174 2014
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[33] V Olmos N Bardoni A S Ridolfi and E C Villaamil LeporildquoCaffeine levels in beverages from Argentinarsquos market applica-tion to caffeine dietary intake assessmentrdquo Food Additives andContaminants A vol 26 no 3 pp 275ndash281 2009
[34] S Oba C Nagata K Nakamura et al ldquoConsumption of coffeegreen tea oolong tea black tea chocolate snacks and thecaffeine content in relation to risk of diabetes in Japanese menandwomenrdquoBritish Journal of Nutrition vol 103 no 3 pp 453ndash459 2010
[35] S N Bhupathiraju A Pan V S Malik et al ldquoCaffeinated andcaffeine-free beverages and risk of type 2 diabetesrdquoThe Ameri-can Journal of Clinical Nutrition vol 97 pp 155ndash166 2013
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[37] R S J Keast D Sayompark G Sacks B A Swinburn and L JRiddell ldquoThe influence of caffeine on energy content of sugar-sweetened beverages lsquothe caffeine-calorie effectrsquordquo EuropeanJournal of Clinical Nutrition vol 65 no 12 pp 1338ndash1344 2011
[38] P Mazzafera andM B Silvarolla ldquoCaffeine content variation insingle greenArabica coffee seedsrdquo Seed Science Research vol 20no 3 pp 163ndash167 2010
[39] J Tello M Viguera and L Calvo ldquoExtraction of caffeine fromRobusta coffee (Coffea canephora var Robusta) husks usingsupercritical carbon dioxiderdquo Journal of Supercritical Fluids vol59 pp 53ndash60 2011
[40] G Laurence K Wallman and K Guelfi ldquoEffects of caffeine ontime trial performance in sedentary menrdquo Journal of Sports Sci-ences vol 30 no 12 pp 1235ndash1240 2012
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
ISRN Nutrition 5
Table 1 Analytical methods for characterization and quantification of bioactive micronutrients in coffee
Micronutrient Method Figure of merit ReferenceCGA SWV LOD (0049 120583gmLminus1) Yardim 2012 [141]CGA caffeine UV-Vis Ra (91ndash9843) CVb (280ndash545) Belay and Gholap 2009 [105]TRG HPLC R (gt90) RSD (lt3) Liu et al 2011 [118]Caffeine NIRchemometrics RSD (1707) RMSEP (0378mgg) Zhang et al 2013 [152]TRG caffeine HPLC LOD (002mgL) LOQ (0005) Hongcheng et al 2012 [114]Caffeine DART-TOFMS R (97ndash107) RSD (lt5) Danhelova et al 2012 [101]TRG caffeine 1H-NMR CV (24 42) LOD (058 132mgg) del Campo et al 2010 [156]CGA DPP SWV LOD (0236 120583molLminus1 134 nmolLminus1) Araujo et al 2009 [144]CGA isomers 2D-NMR R (75ndash80) R2 (09960ndash09994) Wei et al 2010 [155]Caffeine CE HPLC LOD (087 0021mg100 g) RSD (lt2) Bizzotto et al 2013 [137]Caffeine CVc LOD (0348 120583molLminus1) R2 (0999) Mersal 2012 [142]Caffeine CE RSD (lt2) Li et al 2009 [139]CGA DPV LOD (0148 120583molLminus1) Santos et al 2011 [146]CGA isomers HPLC R (67ndash99) R2 (gt099) Caprioli et al 2013 [110]CGA BiosensorSWV LOD (0915 120583molLminus1) R (932ndash1057) Fernandes et al 2009 [147]Cafestol kahweol HPLC RSD (lt5) Sridevi et al 2011 [71]Caffeine CVSWV LOD (0137 120583molLminus1) R (gt90) Amare and Admassie 2012 [145]aPercent recovery bcoefficient of variation ccyclic voltammetry
semidry processing method showed lower levels of CGAand TRG than coffee processed by wet method which goesto confirm the effect of different processing methods onconstituents of coffee [128] In another experiment HPLC-UVVis analysis revealed that coffee contains 006ndash255caffeine and this value decreases with roasting intensity [129]
HPLC can be performed in either reverse or normalphasemode A caffeine assessment tool (CAT) was developedwith results obtained from a reverse-phase- (RP-) HPLC-UVanalysis of several coffee and coffee-based beverages [130]Moreira and Scarminio [131] have applied RP-HPLC-DADfor the determination of caffeine at 275 nm 120582 using a binaryethanol-dichloromethane solution (1 1) as mobile phaseMobile phase in gradient flow mode is often employed toresolve complex mixtures When different coffee extractionmethods were tested using a mixture of 01 formic acid inwater and 01 formic acid in acetonitrile in this type of flowmode CGA and caffeine contents of the different extractswere different confirming that contents may vary accordingto method of extraction [125]
Two-dimensional HPLC (2D-HPLC) may provide forbetter resolution than in ordinary practiceThe application ofthis system in combination with chemiluminescence detec-tor allowed for increased sensitivity and better selectivityin the determination of antioxidant constituents of threeEspresso coffees (ldquoRistrettordquo ldquoDecaffeinatordquo and ldquoVollutordquo)[132] Elsewhere a C-18 and Bondapak NH
2columns in
series were used for the simultaneous determination of TRGcaffeine and nicotinic acid [114] This method selected con-ditions optimal at 120∘C and 200 psi and good separationwas achieved in just 3min driven by 002Mphosphoric acid-methanol (70 30 vv) mobile phase at 08mLmin
Apart from the common detection systems (UVVisDAD and RI) often employed in liquid chromatographic
applications for the characterization of these coffee con-tents applications of MS detection are also found in the lit-erature By a careful selection of parameters molecularmarkers for distinguishing between different coffee samplesor between constituents can be assigned [133] In a methodof liquid chromatographymultistage spectrometry (LCMS119899) (119899 = 2ndash4) described by Jaiswal and Kuhnert [134]hitherto unreported isomers of CGA (triacyl CGAs) weredetected in Robusta coffee bean extracts and their struc-tures assigned using LCMS119899 fragmentation patterns Incombination with similar fragmentation patterns (LCMS119899119899 = 2-3) relative hydrophobicity and fragmentation analogywere also harnessed to distinguish between two isomericclasses of CGA (CGA lactones and cinnamoylshikimate)which are formed from CGA by loss of water at high pro-cessing temperatures [135] Interestingly a high temperaturereverse phase liquid chromatography coupled with isotoperatio mass spectrometry (HT-RPLCIRMS) was employed todistinguish between natural and synthetic caffeine in coffeedrinks without the painful need for extraction by using 12057513 Cvalues (between 25 and 32permilfor natural caffeine and between33 and 38permilfor synthetic caffeine) as distinguishable groups[136] This method will be a special aid in the fight againstcounterfeiting and adulteration of coffee products
412 CE and Other Methods CE uses a very small diameterbore capillary to effect separation of charged analytes dis-solved in a suitable buffer The driving force for this separa-tion system is the use of high voltage that influences electroki-netic migration of analytes to either of the positive and neg-ative poles Hence a candidate analyte for CE must possess anet negative or positive charge for effective separation In thelast five years CE has been applied in many fields includingthe analysis of plant materials [86] While HPLC did provide
6 ISRN Nutrition
lower values of LOD for the determination of caffeine indecaffeinated coffee than CE the latter was 30 faster hadlower cost of reagents and generated smaller volumes ofresidues [137] In a similar experiment a fast hydrodynamicinjection (50mBar 7 s) was applied in the analysis of caffeinein commercial decaffeinated coffee using a 48 cm times 50 120583mfused-silica capillary [138] Other optimized conditions forthis method include a mixture of sodium carbonate (10mmolLminus1) and sodium dodecyl sulfate (50mmolLminus1) asbuffer 15 kV voltage and 206 nm 120582 Elsewhere Li et al [139]have explained a CEmethod for the determination of caffeinein roasted coffee This method is characterized by extremelyhigh precision percent relative standard deviation (RSD)was less than 08 for retention time and 17 for peak areas
GC determination can be extremely important especiallyin the analysis of volatile components of coffee [108 121]For semivolatile and nonvolatile portions however alter-native methods will be more desirable and effective Oneof such methods is based countercurrent chromatography(CCC) which differs significantly from the preceding typesof separation systems by not involving any solid supportInstead two immiscible solvents are used one solvent apiecefor the stationary and mobile phases This is exemplified inthe method of Machmudah et al [120] where SCCO
2and
water were used in countercurrent flow mode to effect theseparation of CGA from caffeine Recently a method basedon the high-speed mode (HSCCC) which could be used forthe preparative isolation of milligram amount of CGA fromcoffee was explained [140]
42 Separation-Less Methods In many instances determi-nation of analytes is performed without the need to gothrough a separation step Molecular behaviors such as massfragmentation patterns magnetic resonance electrical prop-erties and UVVis or IR absorbance are used for their directcharacterization andor quantificationThesemethods can bedefined by extremely low LODs high throughput and goodselectivity and sensitivity in their applications to the analysisof coffee micronutrients
421 Spectroscopic Methods These methods are based onlight-absorbing or light-emitting properties of molecules asthey interact with electromagnetic radiation As a moleculeabsorbs light energy of defined wavelength electronic tran-sition characteristic of that molecule is elicited and thiscan be used for the characterization and quantification ofsuch molecule At 324 nm CGA has a strong 120587-120587lowast transitionresulting from the delocalized electrons on benzene ringand this was used for its characterization and quantificationin coffee bean extract [105] Null hypothesis was obeyedbetween the results obtained by this method and results ofHPLC analysis
Many determinations of antioxidant activities in coffee bydifferent mechanisms are based on UVVis absorption spec-troscopy [113] CGA and caffeine are among the main antiox-idant micronutrients in coffee Their antioxidant capaci-ties were measured using 221015840-azino-bis(3-ethylbenzothiazo-line-6-sulphonic acid (ABTS) 22-diphenyl-1-picrylhydrazyl
(DPPH) and Folin-Ciocalteau [102] In a similar inves-tigation antioxidant capacities of these hydrophilic com-poundswere also investigated using disodiumnitrosodisulfo-nate (Fremyrsquos salt) and 2266-tetramethyl-1-piperidinyloxy(TEMPO) and results for different coffee brewing techniqueswere obtained as 460ndash1023 (Filter) lt42 (Plunger) and856 (Espresso) [98] DPPH-radical scavenging activitygreater than 75 was recorded in the extract of green coffeebeans containing 22ndash40 caffeine and 31ndash62 CGA [115]
422 Electrochemical Methods Oxidation-reduction behav-iors of analytes at electrode surfaces may be used for thecharacterization of such analytes based on their specificrelationships with potential and current or other electricalquantities Different types of voltammetry and coulometryhave been applied in the determination of coffee constituentswith high sensitivity selectivity and speed For instanceoxidation of CGA at the surface of boron-doped diamondelectrode using adsorptive transfer stripping voltammetricconditions was applied for the electrochemical estimationof antioxidant properties of coffee samples with very lowLOD (49 ngmL) and good linearity within the concentrationrange of 025ndash400120583gmL [141] Direct determination ofcaffeine was achieved by square-wave voltammetry (SWV)using a highly selective pseudo carbon paste electrode versusSCE [142]
Different additives may influence the performance ofthese methods in several ways While milk proteins (caseinand bovine serum albumin) formed complexes with polyphe-nolic constituents in coffee thereby significantly reduc-ing their available OH groups and thus their antioxidantcapacities as revealed by coulometric titration with hexa-cyanoferrate (III) ions [143] addition of cationic surfactant(cetyltrimethylammonium bromide) in the supporting elec-trolyte (004mol Lminus1 phosphate buffer pH 60) significantlyenhanced the reduction of caffeine at hanging mercury dropelectrode determined by both differential-pulse polarogra-phy (DPP) and SWV [144] When the surface of a glassycarbon electrode was modified by the deposition of thin filmof 4-amino-3-hydroxynaphthalene sulfonic acid (AHNSA)highly selective electrocatalyzed oxidation of caffeine wasachieved leading to its high recoveries in coffee extracts [145]
Recently an electrochemical sensor for the selectivedetermination of CGA in coffee samples by differential pulsevoltammetry (DPV) was constructed from the deposition ofa thin film of molecularly imprinted siloxane (MIS) on goldsurface [146] In a similar application by Fernandes et al[147] CGA was selectively determined by SWV at +025V(versus AgAgCl) using a biosensor constructed from 1-n-butyl-3-methylimidazoliumhexafluorophosphate containingdispersed iridium nanoparticles (Ir-BMIPF
6) and polyphe-
nol oxidase
423 Spectral Methods Analytical characterization andquantification can also be achieved through stand-alonespectral revelations MS fragmentation patterns under dif-ferent ionization modes have been employed in chemicalanalysis including analysis of components of coffee [148]
ISRN Nutrition 7
Direct analysis in real time (DART) coupled to time-of-flightmass spectrometry (TOFMS) yielded a high throughput(lt1min per run) analysis of caffeine in coffee samples [101]Without the need for sample preparation or chromatographicseparation the molecular ion (M +H)+ resulting from themethod of DART-MS was used for the identification ofcaffeine in commercial instant coffee samples [149] Caffeinehas a mass to charge ratio (119898119911) of 194 and its characteriza-tion alongside kahweol (119898119911 296) and cafestol (119898119911 298)two marker compounds for C arabica and C canephorawas achieved in the method of single photon ionizationcoupled with TOFMS (SPI-TOFMS) developed by Hertz-Schunemann et al [150] for the recognition of roasting gasprofiles of coffee
Characterization of bioactive components of coffee canalso be achieved by using their near-IR (NIR) (2500ndash4000 cmminus1) absorption spectra Methods based on thisapproach are nondestructive and can offer reliable speed ofdetermination In addition to qualitative analysis chemomet-ric models can assist in quantitative interpretation of NIRspectral data In one example caffeine TRG and CGA weredetermined as components of sensory quality in Arabicaroasted coffee samples using ordered prediction selection(OPS) algorithm partial least squares (PLS) andNIR spectra[151] Recently Zhang et al [152] developed an improvedregression model for NIR determination of caffeine Thismethod is characterized by root mean square error of crossvalidation (RMSECV) of 0375mgg RSD of 1707 andcorrelation coefficient of 0918 at PLS factor of 7
For some time now nuclear magnetic resonance (NMR)spectrometry has been offering good information for theidentification and structural elucidation of compounds andthis has now been extended to coffee constituents Using 1H-NMR and partial least squares discriminant analysis (OPLS-DA) models TRG and CGA were found among the mainmetabolites that can characterize and separate C ara-bica samples according to their geographical origin [153]Recently structures of CGA lactones which hitherto werenot available in the literature were established from NMRdata [140] Self-association and complexation of coffee con-stituents both in coffee brews and in aqueousmedia can poseserious challenge for their analytical resolutions DrsquoAmelioet al [154] have investigated structural features of CGA-caffeine complexation using high resolution 1H-NMR NMRcan also offer quantitative information on chemical com-ponents in coffee Without a nuclear Overhauser effectthree isomers of CGA were identified and quantified ingreen coffee bean extract through integration of 2D NMRcarbon signals by use of relaxation reagent and inverse-gateddecouplingmethod [155] According to del Campo et al [156]caffeine and TRG among other constituents of coffee canbe quantitatively analyzed by use of their singlet 1H-NMRsignals within 76ndash95 ppm and the use of 3-(trimethylsilyl)-2233-tetradeuteropropionic acid both as internal standardand as reference for 120575 = 000 ppm
5 Conclusions
Coffee is a popular beverage that is obtained from differentvarieties of coffee beansThis important drink contains many
micronutrients some of which have proven bioactivitiessuch as anticancer antimicrobial antioxidant and host ofother effects Four important groups of these biologicallyimportant micronutrients namely caffeine CGA diter-penes and TRG have been discussed in this review Becauseof their importance in biological systems recent analyticalmethods for their characterization and quantitative determi-nation have also been reviewed It is envisaged that properapplications of these methods will go a long way in aidingquality assurance and safeguarding consumer safety andsatisfaction
Conflict of Interests
The author declares that there is no conflict of interestsregarding the publication of this paper
References
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[2] A L Oliveira F A CabralM N Eberlin andHM A B Cord-ello ldquoSensory evaluation of black instant coffee beverage withsome volatile compounds present in aromatic oil from roastedcoffeerdquo Ciencia e Tecnologia de Alimentos vol 29 no 1 pp 76ndash80 2009
[3] JMiran ldquoSpace mobility and translocal connections across theRed Sea area since 1500rdquo Northeast African Studies vol 12 no1 pp 9ndash26 2012
[4] K Hundera R Aerts M de Beenhouwer et al ldquoBoth forestfragmentation and coffee cultivation negatively affect epiphyticorchid diversity in Ethiopian moist evergreen Afromontaneforestsrdquo Biological Conservation vol 159 pp 285ndash291 2013
[5] F Serra C G Guillou F Reniero et al ldquoDetermination ofthe geographical origin of green coffee by principal componentanalysis of carbon nitrogen and boron stable isotope ratiosrdquoRapid Communications in Mass Spectrometry vol 19 no 15 pp2111ndash2115 2005
[6] P Moguel and V M Toledo ldquoBiodiversity conservation in tra-ditional coffee systems ofMexicordquoConservation Biology vol 13no 1 pp 11ndash21 1999
[7] F Anthony B Bertrand O Quiros et al ldquoGenetic diversity ofwild coffee (Coffea arabica L) using molecular markersrdquoEuphytica vol 118 no 1 pp 53ndash65 2001
[8] A-M Klein I Steffan-Dewenter and T Tscharntke ldquoBee polli-nation and fruit set of Coffea arabica and C canephora (Rubia-ceae)rdquoTheAmerican Journal of Botany vol 90 no 1 pp 153ndash1572003
[9] A Lecolier P Besse A Charrier T-N Tchakaloff and MNoirot ldquoUnraveling the origin of Coffea arabica ldquoBourbonpointurdquo from la Reunion a historical and scientific perspectiverdquoEuphytica vol 168 no 1 pp 1ndash10 2009
[10] D C Carvalho M R P L Brigagao M H S Santos F B Ade Paula A Giusti-Paiva and L Azevedo ldquoOrganic and Con-ventional Coffea arabica L a comparative study of the chemicalcomposition and physiological biochemical and toxicologicaleffects inWistar ratsrdquo Plant Foods for Human Nutrition vol 66no 2 pp 114ndash121 2011
8 ISRN Nutrition
[11] S Topik J M Talbot and M Samper ldquoIntroduction global-ization neoliberalism and the latin American coffee societiesrdquoLatin American Perspectives vol 37 no 2 pp 5ndash20 2010
[12] C M Tucker H Eakin and E J Castellanos ldquoPerceptions ofrisk and adaptation coffee producers market shocks andextreme weather in Central America and Mexicordquo GlobalEnvironmental Change vol 20 no 1 pp 23ndash32 2010
[13] E G Burbano M G Wright N E Gillette et al ldquoEfficacy oftraps lures and repellents for Xylosandrus compactus (Cole-optera Curculionidae) and other ambrosia beetles on Coffeaarabica plantations and Acacia koa nurseries in Hawaiirdquo Envi-ronmental Entomology vol 41 no 1 pp 133ndash140 2012
[14] C W Kathurima B M Gichimu G M Kenji S M Muhohoand R Boulanger ldquoEvaluation of beverage quality and greenbean physical characteristics of selected Arabica coffee geno-types in Kenyardquo African Journal of Food Science vol 3 no 11pp 365ndash371 2009
[15] W J Rogers S Michaux M Bastin and P Bucheli ldquoChanges tothe content of sugars sugar alcohols myo-inositol carboxylicacids and inorganic anions in developing grains from differentvarieties of Robusta (Coffea canephora) andArabica (C arabica)coffeesrdquo Plant Science vol 149 no 2 pp 115ndash123 1999
[16] R Teuber ldquoGeographical indications of origin as a tool of prod-uct differentiation the case of coffeerdquo Journal of InternationalFood and Agribusiness Marketing vol 22 no 3-4 pp 277ndash2982010
[17] H C Liu C F You C Y Chen Y C Liu and M T ChungldquoGeographic determination of coffee beans usingmulti-elementanalysis and isotope ratios of boron and strontiumrdquo FoodChemistry vol 142 pp 439ndash445 2013
[18] T Niseteo D Komes A Belscak-Cvitanovic D Horzic andM Bude ldquoBioactive composition and antioxidant potential ofdifferent commonly consumed coffee brews affected by theirpreparation technique and milk additionrdquo Food Chemistry vol134 no 4 pp 1870ndash1877 2012
[19] M Oliveira S Casal S Morais et al ldquoIntra- and interspecificmineral composition variability of commercial instant coffeesand coffee substitutes contribution to mineral intakerdquo FoodChemistry vol 130 no 3 pp 702ndash709 2012
[20] J A Vignoli D G Bassoli and M T Benassi ldquoAntioxidantactivity polyphenols caffeine andmelanoidins in soluble coffeethe influence of processing conditions and raw materialrdquo FoodChemistry vol 124 no 3 pp 863ndash868 2011
[21] S I Mussatto L M Carneiro J P A Silva I C Roberto and JA Teixeira ldquoA study on chemical constituents and sugarsextraction from spent coffee groundsrdquo Carbohydrate Polymersvol 83 no 2 pp 368ndash374 2011
[22] Y F Chu P H Brown B J Lyle et al ldquoRoasted coffees high inlipophilic antioxidants and chlorogenic acid lactones are moreneuroprotective than green coffeesrdquo Journal of Agricultural andFood Chemistry vol 57 no 20 pp 9801ndash9808 2009
[23] S Johnson W P Koh R Wang S Govindarajan M C Yu andJ M Yuan ldquoCoffee consumption and reduced risk of hepatocel-lular carcinoma findings from the Singapore Chinese HealthStudyrdquo Cancer Causes and Control vol 22 no 3 pp 503ndash5102011
[24] J Tai S Cheung E Chan and D Hasman ldquoAntiproliferationeffect of commercially brewed coffees on human ovarian cancercells in vitrordquoNutrition and Cancer vol 62 no 8 pp 1044ndash10572010
[25] GWArendash andC Cao ldquoCaffeine and coffee as therapeuticsagainst Alzheimerrsquos diseaserdquo Journal of Alzheimerrsquos Disease vol20 no 1 pp 117ndash126 2010
[26] U Boettler K Sommerfeld N Volz et al ldquoCoffee constituentsas modulators of Nrf2 nuclear translocation and ARE (EpRE)-dependent gene expressionrdquo Journal of Nutritional Biochem-istry vol 22 no 5 pp 426ndash440 2011
[27] A S Dore N Robertson J C Errey et al ldquoStructure of theadenosine A
2119860receptor in complex with ZM241385 and the
xanthines XAC and caffeinerdquo Structure vol 19 no 9 pp 1283ndash1293 2011
[28] M A Heckman J Weil and E G de Mejia ldquoCaffeine (1 3 7-trimethylxanthine) in foods a comprehensive review on con-sumption functionality safety and regulatory mattersrdquo Journalof Food Science vol 75 no 3 pp R77ndashR87 2010
[29] N Amaresh A R Mullaicharam andM A El-Khider ldquoChem-istry and pharmacology of caffeine in different types of tealeavesrdquo International Journal of Nutrition Pharmacology Neu-rological Diseases vol 1 no 2 pp 110ndash115 2011
[30] L Wang L-H Gong C-J Chen H-B Han and H-H LildquoColumn-chromatographic extraction and separation of poly-phenols caffeine and theanine from green teardquo Food Chemistryvol 131 no 4 pp 1539ndash1545 2012
[31] Q V Vuong and P D Roach ldquoCaffeine in green tea its removaland isolationrdquo Separation and Purification Reviews vol 43 no2 pp 155ndash174 2014
[32] M C Borges M A R Vinolo K Nakajima et al ldquoThe effect ofmate tea (Ilex paraguariensis) on metabolic and inflammatoryparameters in high-fat diet-fed Wistar ratsrdquo International Jour-nal of Food Sciences and Nutrition vol 64 no 5 pp 561ndash5692013
[33] V Olmos N Bardoni A S Ridolfi and E C Villaamil LeporildquoCaffeine levels in beverages from Argentinarsquos market applica-tion to caffeine dietary intake assessmentrdquo Food Additives andContaminants A vol 26 no 3 pp 275ndash281 2009
[34] S Oba C Nagata K Nakamura et al ldquoConsumption of coffeegreen tea oolong tea black tea chocolate snacks and thecaffeine content in relation to risk of diabetes in Japanese menandwomenrdquoBritish Journal of Nutrition vol 103 no 3 pp 453ndash459 2010
[35] S N Bhupathiraju A Pan V S Malik et al ldquoCaffeinated andcaffeine-free beverages and risk of type 2 diabetesrdquoThe Ameri-can Journal of Clinical Nutrition vol 97 pp 155ndash166 2013
[36] C J Reissig E C Strain andR R Griffiths ldquoCaffeinated energydrinksmdasha growing problemrdquo Drug and Alcohol Dependencevol 99 no 1ndash3 pp 1ndash10 2009
[37] R S J Keast D Sayompark G Sacks B A Swinburn and L JRiddell ldquoThe influence of caffeine on energy content of sugar-sweetened beverages lsquothe caffeine-calorie effectrsquordquo EuropeanJournal of Clinical Nutrition vol 65 no 12 pp 1338ndash1344 2011
[38] P Mazzafera andM B Silvarolla ldquoCaffeine content variation insingle greenArabica coffee seedsrdquo Seed Science Research vol 20no 3 pp 163ndash167 2010
[39] J Tello M Viguera and L Calvo ldquoExtraction of caffeine fromRobusta coffee (Coffea canephora var Robusta) husks usingsupercritical carbon dioxiderdquo Journal of Supercritical Fluids vol59 pp 53ndash60 2011
[40] G Laurence K Wallman and K Guelfi ldquoEffects of caffeine ontime trial performance in sedentary menrdquo Journal of Sports Sci-ences vol 30 no 12 pp 1235ndash1240 2012
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Disease Markers
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6 ISRN Nutrition
lower values of LOD for the determination of caffeine indecaffeinated coffee than CE the latter was 30 faster hadlower cost of reagents and generated smaller volumes ofresidues [137] In a similar experiment a fast hydrodynamicinjection (50mBar 7 s) was applied in the analysis of caffeinein commercial decaffeinated coffee using a 48 cm times 50 120583mfused-silica capillary [138] Other optimized conditions forthis method include a mixture of sodium carbonate (10mmolLminus1) and sodium dodecyl sulfate (50mmolLminus1) asbuffer 15 kV voltage and 206 nm 120582 Elsewhere Li et al [139]have explained a CEmethod for the determination of caffeinein roasted coffee This method is characterized by extremelyhigh precision percent relative standard deviation (RSD)was less than 08 for retention time and 17 for peak areas
GC determination can be extremely important especiallyin the analysis of volatile components of coffee [108 121]For semivolatile and nonvolatile portions however alter-native methods will be more desirable and effective Oneof such methods is based countercurrent chromatography(CCC) which differs significantly from the preceding typesof separation systems by not involving any solid supportInstead two immiscible solvents are used one solvent apiecefor the stationary and mobile phases This is exemplified inthe method of Machmudah et al [120] where SCCO
2and
water were used in countercurrent flow mode to effect theseparation of CGA from caffeine Recently a method basedon the high-speed mode (HSCCC) which could be used forthe preparative isolation of milligram amount of CGA fromcoffee was explained [140]
42 Separation-Less Methods In many instances determi-nation of analytes is performed without the need to gothrough a separation step Molecular behaviors such as massfragmentation patterns magnetic resonance electrical prop-erties and UVVis or IR absorbance are used for their directcharacterization andor quantificationThesemethods can bedefined by extremely low LODs high throughput and goodselectivity and sensitivity in their applications to the analysisof coffee micronutrients
421 Spectroscopic Methods These methods are based onlight-absorbing or light-emitting properties of molecules asthey interact with electromagnetic radiation As a moleculeabsorbs light energy of defined wavelength electronic tran-sition characteristic of that molecule is elicited and thiscan be used for the characterization and quantification ofsuch molecule At 324 nm CGA has a strong 120587-120587lowast transitionresulting from the delocalized electrons on benzene ringand this was used for its characterization and quantificationin coffee bean extract [105] Null hypothesis was obeyedbetween the results obtained by this method and results ofHPLC analysis
Many determinations of antioxidant activities in coffee bydifferent mechanisms are based on UVVis absorption spec-troscopy [113] CGA and caffeine are among the main antiox-idant micronutrients in coffee Their antioxidant capaci-ties were measured using 221015840-azino-bis(3-ethylbenzothiazo-line-6-sulphonic acid (ABTS) 22-diphenyl-1-picrylhydrazyl
(DPPH) and Folin-Ciocalteau [102] In a similar inves-tigation antioxidant capacities of these hydrophilic com-poundswere also investigated using disodiumnitrosodisulfo-nate (Fremyrsquos salt) and 2266-tetramethyl-1-piperidinyloxy(TEMPO) and results for different coffee brewing techniqueswere obtained as 460ndash1023 (Filter) lt42 (Plunger) and856 (Espresso) [98] DPPH-radical scavenging activitygreater than 75 was recorded in the extract of green coffeebeans containing 22ndash40 caffeine and 31ndash62 CGA [115]
422 Electrochemical Methods Oxidation-reduction behav-iors of analytes at electrode surfaces may be used for thecharacterization of such analytes based on their specificrelationships with potential and current or other electricalquantities Different types of voltammetry and coulometryhave been applied in the determination of coffee constituentswith high sensitivity selectivity and speed For instanceoxidation of CGA at the surface of boron-doped diamondelectrode using adsorptive transfer stripping voltammetricconditions was applied for the electrochemical estimationof antioxidant properties of coffee samples with very lowLOD (49 ngmL) and good linearity within the concentrationrange of 025ndash400120583gmL [141] Direct determination ofcaffeine was achieved by square-wave voltammetry (SWV)using a highly selective pseudo carbon paste electrode versusSCE [142]
Different additives may influence the performance ofthese methods in several ways While milk proteins (caseinand bovine serum albumin) formed complexes with polyphe-nolic constituents in coffee thereby significantly reduc-ing their available OH groups and thus their antioxidantcapacities as revealed by coulometric titration with hexa-cyanoferrate (III) ions [143] addition of cationic surfactant(cetyltrimethylammonium bromide) in the supporting elec-trolyte (004mol Lminus1 phosphate buffer pH 60) significantlyenhanced the reduction of caffeine at hanging mercury dropelectrode determined by both differential-pulse polarogra-phy (DPP) and SWV [144] When the surface of a glassycarbon electrode was modified by the deposition of thin filmof 4-amino-3-hydroxynaphthalene sulfonic acid (AHNSA)highly selective electrocatalyzed oxidation of caffeine wasachieved leading to its high recoveries in coffee extracts [145]
Recently an electrochemical sensor for the selectivedetermination of CGA in coffee samples by differential pulsevoltammetry (DPV) was constructed from the deposition ofa thin film of molecularly imprinted siloxane (MIS) on goldsurface [146] In a similar application by Fernandes et al[147] CGA was selectively determined by SWV at +025V(versus AgAgCl) using a biosensor constructed from 1-n-butyl-3-methylimidazoliumhexafluorophosphate containingdispersed iridium nanoparticles (Ir-BMIPF
6) and polyphe-
nol oxidase
423 Spectral Methods Analytical characterization andquantification can also be achieved through stand-alonespectral revelations MS fragmentation patterns under dif-ferent ionization modes have been employed in chemicalanalysis including analysis of components of coffee [148]
ISRN Nutrition 7
Direct analysis in real time (DART) coupled to time-of-flightmass spectrometry (TOFMS) yielded a high throughput(lt1min per run) analysis of caffeine in coffee samples [101]Without the need for sample preparation or chromatographicseparation the molecular ion (M +H)+ resulting from themethod of DART-MS was used for the identification ofcaffeine in commercial instant coffee samples [149] Caffeinehas a mass to charge ratio (119898119911) of 194 and its characteriza-tion alongside kahweol (119898119911 296) and cafestol (119898119911 298)two marker compounds for C arabica and C canephorawas achieved in the method of single photon ionizationcoupled with TOFMS (SPI-TOFMS) developed by Hertz-Schunemann et al [150] for the recognition of roasting gasprofiles of coffee
Characterization of bioactive components of coffee canalso be achieved by using their near-IR (NIR) (2500ndash4000 cmminus1) absorption spectra Methods based on thisapproach are nondestructive and can offer reliable speed ofdetermination In addition to qualitative analysis chemomet-ric models can assist in quantitative interpretation of NIRspectral data In one example caffeine TRG and CGA weredetermined as components of sensory quality in Arabicaroasted coffee samples using ordered prediction selection(OPS) algorithm partial least squares (PLS) andNIR spectra[151] Recently Zhang et al [152] developed an improvedregression model for NIR determination of caffeine Thismethod is characterized by root mean square error of crossvalidation (RMSECV) of 0375mgg RSD of 1707 andcorrelation coefficient of 0918 at PLS factor of 7
For some time now nuclear magnetic resonance (NMR)spectrometry has been offering good information for theidentification and structural elucidation of compounds andthis has now been extended to coffee constituents Using 1H-NMR and partial least squares discriminant analysis (OPLS-DA) models TRG and CGA were found among the mainmetabolites that can characterize and separate C ara-bica samples according to their geographical origin [153]Recently structures of CGA lactones which hitherto werenot available in the literature were established from NMRdata [140] Self-association and complexation of coffee con-stituents both in coffee brews and in aqueousmedia can poseserious challenge for their analytical resolutions DrsquoAmelioet al [154] have investigated structural features of CGA-caffeine complexation using high resolution 1H-NMR NMRcan also offer quantitative information on chemical com-ponents in coffee Without a nuclear Overhauser effectthree isomers of CGA were identified and quantified ingreen coffee bean extract through integration of 2D NMRcarbon signals by use of relaxation reagent and inverse-gateddecouplingmethod [155] According to del Campo et al [156]caffeine and TRG among other constituents of coffee canbe quantitatively analyzed by use of their singlet 1H-NMRsignals within 76ndash95 ppm and the use of 3-(trimethylsilyl)-2233-tetradeuteropropionic acid both as internal standardand as reference for 120575 = 000 ppm
5 Conclusions
Coffee is a popular beverage that is obtained from differentvarieties of coffee beansThis important drink contains many
micronutrients some of which have proven bioactivitiessuch as anticancer antimicrobial antioxidant and host ofother effects Four important groups of these biologicallyimportant micronutrients namely caffeine CGA diter-penes and TRG have been discussed in this review Becauseof their importance in biological systems recent analyticalmethods for their characterization and quantitative determi-nation have also been reviewed It is envisaged that properapplications of these methods will go a long way in aidingquality assurance and safeguarding consumer safety andsatisfaction
Conflict of Interests
The author declares that there is no conflict of interestsregarding the publication of this paper
References
[1] T C Salinardi K H Rubin R M Black and M-P St-Onge ldquoCoffee mannooligosaccharides consumed as part of afree-living weight-maintaining diet increase the proportionalreduction in body volume in overweight menrdquo The Journal ofNutrition vol 140 no 11 pp 1943ndash1948 2010
[2] A L Oliveira F A CabralM N Eberlin andHM A B Cord-ello ldquoSensory evaluation of black instant coffee beverage withsome volatile compounds present in aromatic oil from roastedcoffeerdquo Ciencia e Tecnologia de Alimentos vol 29 no 1 pp 76ndash80 2009
[3] JMiran ldquoSpace mobility and translocal connections across theRed Sea area since 1500rdquo Northeast African Studies vol 12 no1 pp 9ndash26 2012
[4] K Hundera R Aerts M de Beenhouwer et al ldquoBoth forestfragmentation and coffee cultivation negatively affect epiphyticorchid diversity in Ethiopian moist evergreen Afromontaneforestsrdquo Biological Conservation vol 159 pp 285ndash291 2013
[5] F Serra C G Guillou F Reniero et al ldquoDetermination ofthe geographical origin of green coffee by principal componentanalysis of carbon nitrogen and boron stable isotope ratiosrdquoRapid Communications in Mass Spectrometry vol 19 no 15 pp2111ndash2115 2005
[6] P Moguel and V M Toledo ldquoBiodiversity conservation in tra-ditional coffee systems ofMexicordquoConservation Biology vol 13no 1 pp 11ndash21 1999
[7] F Anthony B Bertrand O Quiros et al ldquoGenetic diversity ofwild coffee (Coffea arabica L) using molecular markersrdquoEuphytica vol 118 no 1 pp 53ndash65 2001
[8] A-M Klein I Steffan-Dewenter and T Tscharntke ldquoBee polli-nation and fruit set of Coffea arabica and C canephora (Rubia-ceae)rdquoTheAmerican Journal of Botany vol 90 no 1 pp 153ndash1572003
[9] A Lecolier P Besse A Charrier T-N Tchakaloff and MNoirot ldquoUnraveling the origin of Coffea arabica ldquoBourbonpointurdquo from la Reunion a historical and scientific perspectiverdquoEuphytica vol 168 no 1 pp 1ndash10 2009
[10] D C Carvalho M R P L Brigagao M H S Santos F B Ade Paula A Giusti-Paiva and L Azevedo ldquoOrganic and Con-ventional Coffea arabica L a comparative study of the chemicalcomposition and physiological biochemical and toxicologicaleffects inWistar ratsrdquo Plant Foods for Human Nutrition vol 66no 2 pp 114ndash121 2011
8 ISRN Nutrition
[11] S Topik J M Talbot and M Samper ldquoIntroduction global-ization neoliberalism and the latin American coffee societiesrdquoLatin American Perspectives vol 37 no 2 pp 5ndash20 2010
[12] C M Tucker H Eakin and E J Castellanos ldquoPerceptions ofrisk and adaptation coffee producers market shocks andextreme weather in Central America and Mexicordquo GlobalEnvironmental Change vol 20 no 1 pp 23ndash32 2010
[13] E G Burbano M G Wright N E Gillette et al ldquoEfficacy oftraps lures and repellents for Xylosandrus compactus (Cole-optera Curculionidae) and other ambrosia beetles on Coffeaarabica plantations and Acacia koa nurseries in Hawaiirdquo Envi-ronmental Entomology vol 41 no 1 pp 133ndash140 2012
[14] C W Kathurima B M Gichimu G M Kenji S M Muhohoand R Boulanger ldquoEvaluation of beverage quality and greenbean physical characteristics of selected Arabica coffee geno-types in Kenyardquo African Journal of Food Science vol 3 no 11pp 365ndash371 2009
[15] W J Rogers S Michaux M Bastin and P Bucheli ldquoChanges tothe content of sugars sugar alcohols myo-inositol carboxylicacids and inorganic anions in developing grains from differentvarieties of Robusta (Coffea canephora) andArabica (C arabica)coffeesrdquo Plant Science vol 149 no 2 pp 115ndash123 1999
[16] R Teuber ldquoGeographical indications of origin as a tool of prod-uct differentiation the case of coffeerdquo Journal of InternationalFood and Agribusiness Marketing vol 22 no 3-4 pp 277ndash2982010
[17] H C Liu C F You C Y Chen Y C Liu and M T ChungldquoGeographic determination of coffee beans usingmulti-elementanalysis and isotope ratios of boron and strontiumrdquo FoodChemistry vol 142 pp 439ndash445 2013
[18] T Niseteo D Komes A Belscak-Cvitanovic D Horzic andM Bude ldquoBioactive composition and antioxidant potential ofdifferent commonly consumed coffee brews affected by theirpreparation technique and milk additionrdquo Food Chemistry vol134 no 4 pp 1870ndash1877 2012
[19] M Oliveira S Casal S Morais et al ldquoIntra- and interspecificmineral composition variability of commercial instant coffeesand coffee substitutes contribution to mineral intakerdquo FoodChemistry vol 130 no 3 pp 702ndash709 2012
[20] J A Vignoli D G Bassoli and M T Benassi ldquoAntioxidantactivity polyphenols caffeine andmelanoidins in soluble coffeethe influence of processing conditions and raw materialrdquo FoodChemistry vol 124 no 3 pp 863ndash868 2011
[21] S I Mussatto L M Carneiro J P A Silva I C Roberto and JA Teixeira ldquoA study on chemical constituents and sugarsextraction from spent coffee groundsrdquo Carbohydrate Polymersvol 83 no 2 pp 368ndash374 2011
[22] Y F Chu P H Brown B J Lyle et al ldquoRoasted coffees high inlipophilic antioxidants and chlorogenic acid lactones are moreneuroprotective than green coffeesrdquo Journal of Agricultural andFood Chemistry vol 57 no 20 pp 9801ndash9808 2009
[23] S Johnson W P Koh R Wang S Govindarajan M C Yu andJ M Yuan ldquoCoffee consumption and reduced risk of hepatocel-lular carcinoma findings from the Singapore Chinese HealthStudyrdquo Cancer Causes and Control vol 22 no 3 pp 503ndash5102011
[24] J Tai S Cheung E Chan and D Hasman ldquoAntiproliferationeffect of commercially brewed coffees on human ovarian cancercells in vitrordquoNutrition and Cancer vol 62 no 8 pp 1044ndash10572010
[25] GWArendash andC Cao ldquoCaffeine and coffee as therapeuticsagainst Alzheimerrsquos diseaserdquo Journal of Alzheimerrsquos Disease vol20 no 1 pp 117ndash126 2010
[26] U Boettler K Sommerfeld N Volz et al ldquoCoffee constituentsas modulators of Nrf2 nuclear translocation and ARE (EpRE)-dependent gene expressionrdquo Journal of Nutritional Biochem-istry vol 22 no 5 pp 426ndash440 2011
[27] A S Dore N Robertson J C Errey et al ldquoStructure of theadenosine A
2119860receptor in complex with ZM241385 and the
xanthines XAC and caffeinerdquo Structure vol 19 no 9 pp 1283ndash1293 2011
[28] M A Heckman J Weil and E G de Mejia ldquoCaffeine (1 3 7-trimethylxanthine) in foods a comprehensive review on con-sumption functionality safety and regulatory mattersrdquo Journalof Food Science vol 75 no 3 pp R77ndashR87 2010
[29] N Amaresh A R Mullaicharam andM A El-Khider ldquoChem-istry and pharmacology of caffeine in different types of tealeavesrdquo International Journal of Nutrition Pharmacology Neu-rological Diseases vol 1 no 2 pp 110ndash115 2011
[30] L Wang L-H Gong C-J Chen H-B Han and H-H LildquoColumn-chromatographic extraction and separation of poly-phenols caffeine and theanine from green teardquo Food Chemistryvol 131 no 4 pp 1539ndash1545 2012
[31] Q V Vuong and P D Roach ldquoCaffeine in green tea its removaland isolationrdquo Separation and Purification Reviews vol 43 no2 pp 155ndash174 2014
[32] M C Borges M A R Vinolo K Nakajima et al ldquoThe effect ofmate tea (Ilex paraguariensis) on metabolic and inflammatoryparameters in high-fat diet-fed Wistar ratsrdquo International Jour-nal of Food Sciences and Nutrition vol 64 no 5 pp 561ndash5692013
[33] V Olmos N Bardoni A S Ridolfi and E C Villaamil LeporildquoCaffeine levels in beverages from Argentinarsquos market applica-tion to caffeine dietary intake assessmentrdquo Food Additives andContaminants A vol 26 no 3 pp 275ndash281 2009
[34] S Oba C Nagata K Nakamura et al ldquoConsumption of coffeegreen tea oolong tea black tea chocolate snacks and thecaffeine content in relation to risk of diabetes in Japanese menandwomenrdquoBritish Journal of Nutrition vol 103 no 3 pp 453ndash459 2010
[35] S N Bhupathiraju A Pan V S Malik et al ldquoCaffeinated andcaffeine-free beverages and risk of type 2 diabetesrdquoThe Ameri-can Journal of Clinical Nutrition vol 97 pp 155ndash166 2013
[36] C J Reissig E C Strain andR R Griffiths ldquoCaffeinated energydrinksmdasha growing problemrdquo Drug and Alcohol Dependencevol 99 no 1ndash3 pp 1ndash10 2009
[37] R S J Keast D Sayompark G Sacks B A Swinburn and L JRiddell ldquoThe influence of caffeine on energy content of sugar-sweetened beverages lsquothe caffeine-calorie effectrsquordquo EuropeanJournal of Clinical Nutrition vol 65 no 12 pp 1338ndash1344 2011
[38] P Mazzafera andM B Silvarolla ldquoCaffeine content variation insingle greenArabica coffee seedsrdquo Seed Science Research vol 20no 3 pp 163ndash167 2010
[39] J Tello M Viguera and L Calvo ldquoExtraction of caffeine fromRobusta coffee (Coffea canephora var Robusta) husks usingsupercritical carbon dioxiderdquo Journal of Supercritical Fluids vol59 pp 53ndash60 2011
[40] G Laurence K Wallman and K Guelfi ldquoEffects of caffeine ontime trial performance in sedentary menrdquo Journal of Sports Sci-ences vol 30 no 12 pp 1235ndash1240 2012
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
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ISRN Nutrition 7
Direct analysis in real time (DART) coupled to time-of-flightmass spectrometry (TOFMS) yielded a high throughput(lt1min per run) analysis of caffeine in coffee samples [101]Without the need for sample preparation or chromatographicseparation the molecular ion (M +H)+ resulting from themethod of DART-MS was used for the identification ofcaffeine in commercial instant coffee samples [149] Caffeinehas a mass to charge ratio (119898119911) of 194 and its characteriza-tion alongside kahweol (119898119911 296) and cafestol (119898119911 298)two marker compounds for C arabica and C canephorawas achieved in the method of single photon ionizationcoupled with TOFMS (SPI-TOFMS) developed by Hertz-Schunemann et al [150] for the recognition of roasting gasprofiles of coffee
Characterization of bioactive components of coffee canalso be achieved by using their near-IR (NIR) (2500ndash4000 cmminus1) absorption spectra Methods based on thisapproach are nondestructive and can offer reliable speed ofdetermination In addition to qualitative analysis chemomet-ric models can assist in quantitative interpretation of NIRspectral data In one example caffeine TRG and CGA weredetermined as components of sensory quality in Arabicaroasted coffee samples using ordered prediction selection(OPS) algorithm partial least squares (PLS) andNIR spectra[151] Recently Zhang et al [152] developed an improvedregression model for NIR determination of caffeine Thismethod is characterized by root mean square error of crossvalidation (RMSECV) of 0375mgg RSD of 1707 andcorrelation coefficient of 0918 at PLS factor of 7
For some time now nuclear magnetic resonance (NMR)spectrometry has been offering good information for theidentification and structural elucidation of compounds andthis has now been extended to coffee constituents Using 1H-NMR and partial least squares discriminant analysis (OPLS-DA) models TRG and CGA were found among the mainmetabolites that can characterize and separate C ara-bica samples according to their geographical origin [153]Recently structures of CGA lactones which hitherto werenot available in the literature were established from NMRdata [140] Self-association and complexation of coffee con-stituents both in coffee brews and in aqueousmedia can poseserious challenge for their analytical resolutions DrsquoAmelioet al [154] have investigated structural features of CGA-caffeine complexation using high resolution 1H-NMR NMRcan also offer quantitative information on chemical com-ponents in coffee Without a nuclear Overhauser effectthree isomers of CGA were identified and quantified ingreen coffee bean extract through integration of 2D NMRcarbon signals by use of relaxation reagent and inverse-gateddecouplingmethod [155] According to del Campo et al [156]caffeine and TRG among other constituents of coffee canbe quantitatively analyzed by use of their singlet 1H-NMRsignals within 76ndash95 ppm and the use of 3-(trimethylsilyl)-2233-tetradeuteropropionic acid both as internal standardand as reference for 120575 = 000 ppm
5 Conclusions
Coffee is a popular beverage that is obtained from differentvarieties of coffee beansThis important drink contains many
micronutrients some of which have proven bioactivitiessuch as anticancer antimicrobial antioxidant and host ofother effects Four important groups of these biologicallyimportant micronutrients namely caffeine CGA diter-penes and TRG have been discussed in this review Becauseof their importance in biological systems recent analyticalmethods for their characterization and quantitative determi-nation have also been reviewed It is envisaged that properapplications of these methods will go a long way in aidingquality assurance and safeguarding consumer safety andsatisfaction
Conflict of Interests
The author declares that there is no conflict of interestsregarding the publication of this paper
References
[1] T C Salinardi K H Rubin R M Black and M-P St-Onge ldquoCoffee mannooligosaccharides consumed as part of afree-living weight-maintaining diet increase the proportionalreduction in body volume in overweight menrdquo The Journal ofNutrition vol 140 no 11 pp 1943ndash1948 2010
[2] A L Oliveira F A CabralM N Eberlin andHM A B Cord-ello ldquoSensory evaluation of black instant coffee beverage withsome volatile compounds present in aromatic oil from roastedcoffeerdquo Ciencia e Tecnologia de Alimentos vol 29 no 1 pp 76ndash80 2009
[3] JMiran ldquoSpace mobility and translocal connections across theRed Sea area since 1500rdquo Northeast African Studies vol 12 no1 pp 9ndash26 2012
[4] K Hundera R Aerts M de Beenhouwer et al ldquoBoth forestfragmentation and coffee cultivation negatively affect epiphyticorchid diversity in Ethiopian moist evergreen Afromontaneforestsrdquo Biological Conservation vol 159 pp 285ndash291 2013
[5] F Serra C G Guillou F Reniero et al ldquoDetermination ofthe geographical origin of green coffee by principal componentanalysis of carbon nitrogen and boron stable isotope ratiosrdquoRapid Communications in Mass Spectrometry vol 19 no 15 pp2111ndash2115 2005
[6] P Moguel and V M Toledo ldquoBiodiversity conservation in tra-ditional coffee systems ofMexicordquoConservation Biology vol 13no 1 pp 11ndash21 1999
[7] F Anthony B Bertrand O Quiros et al ldquoGenetic diversity ofwild coffee (Coffea arabica L) using molecular markersrdquoEuphytica vol 118 no 1 pp 53ndash65 2001
[8] A-M Klein I Steffan-Dewenter and T Tscharntke ldquoBee polli-nation and fruit set of Coffea arabica and C canephora (Rubia-ceae)rdquoTheAmerican Journal of Botany vol 90 no 1 pp 153ndash1572003
[9] A Lecolier P Besse A Charrier T-N Tchakaloff and MNoirot ldquoUnraveling the origin of Coffea arabica ldquoBourbonpointurdquo from la Reunion a historical and scientific perspectiverdquoEuphytica vol 168 no 1 pp 1ndash10 2009
[10] D C Carvalho M R P L Brigagao M H S Santos F B Ade Paula A Giusti-Paiva and L Azevedo ldquoOrganic and Con-ventional Coffea arabica L a comparative study of the chemicalcomposition and physiological biochemical and toxicologicaleffects inWistar ratsrdquo Plant Foods for Human Nutrition vol 66no 2 pp 114ndash121 2011
8 ISRN Nutrition
[11] S Topik J M Talbot and M Samper ldquoIntroduction global-ization neoliberalism and the latin American coffee societiesrdquoLatin American Perspectives vol 37 no 2 pp 5ndash20 2010
[12] C M Tucker H Eakin and E J Castellanos ldquoPerceptions ofrisk and adaptation coffee producers market shocks andextreme weather in Central America and Mexicordquo GlobalEnvironmental Change vol 20 no 1 pp 23ndash32 2010
[13] E G Burbano M G Wright N E Gillette et al ldquoEfficacy oftraps lures and repellents for Xylosandrus compactus (Cole-optera Curculionidae) and other ambrosia beetles on Coffeaarabica plantations and Acacia koa nurseries in Hawaiirdquo Envi-ronmental Entomology vol 41 no 1 pp 133ndash140 2012
[14] C W Kathurima B M Gichimu G M Kenji S M Muhohoand R Boulanger ldquoEvaluation of beverage quality and greenbean physical characteristics of selected Arabica coffee geno-types in Kenyardquo African Journal of Food Science vol 3 no 11pp 365ndash371 2009
[15] W J Rogers S Michaux M Bastin and P Bucheli ldquoChanges tothe content of sugars sugar alcohols myo-inositol carboxylicacids and inorganic anions in developing grains from differentvarieties of Robusta (Coffea canephora) andArabica (C arabica)coffeesrdquo Plant Science vol 149 no 2 pp 115ndash123 1999
[16] R Teuber ldquoGeographical indications of origin as a tool of prod-uct differentiation the case of coffeerdquo Journal of InternationalFood and Agribusiness Marketing vol 22 no 3-4 pp 277ndash2982010
[17] H C Liu C F You C Y Chen Y C Liu and M T ChungldquoGeographic determination of coffee beans usingmulti-elementanalysis and isotope ratios of boron and strontiumrdquo FoodChemistry vol 142 pp 439ndash445 2013
[18] T Niseteo D Komes A Belscak-Cvitanovic D Horzic andM Bude ldquoBioactive composition and antioxidant potential ofdifferent commonly consumed coffee brews affected by theirpreparation technique and milk additionrdquo Food Chemistry vol134 no 4 pp 1870ndash1877 2012
[19] M Oliveira S Casal S Morais et al ldquoIntra- and interspecificmineral composition variability of commercial instant coffeesand coffee substitutes contribution to mineral intakerdquo FoodChemistry vol 130 no 3 pp 702ndash709 2012
[20] J A Vignoli D G Bassoli and M T Benassi ldquoAntioxidantactivity polyphenols caffeine andmelanoidins in soluble coffeethe influence of processing conditions and raw materialrdquo FoodChemistry vol 124 no 3 pp 863ndash868 2011
[21] S I Mussatto L M Carneiro J P A Silva I C Roberto and JA Teixeira ldquoA study on chemical constituents and sugarsextraction from spent coffee groundsrdquo Carbohydrate Polymersvol 83 no 2 pp 368ndash374 2011
[22] Y F Chu P H Brown B J Lyle et al ldquoRoasted coffees high inlipophilic antioxidants and chlorogenic acid lactones are moreneuroprotective than green coffeesrdquo Journal of Agricultural andFood Chemistry vol 57 no 20 pp 9801ndash9808 2009
[23] S Johnson W P Koh R Wang S Govindarajan M C Yu andJ M Yuan ldquoCoffee consumption and reduced risk of hepatocel-lular carcinoma findings from the Singapore Chinese HealthStudyrdquo Cancer Causes and Control vol 22 no 3 pp 503ndash5102011
[24] J Tai S Cheung E Chan and D Hasman ldquoAntiproliferationeffect of commercially brewed coffees on human ovarian cancercells in vitrordquoNutrition and Cancer vol 62 no 8 pp 1044ndash10572010
[25] GWArendash andC Cao ldquoCaffeine and coffee as therapeuticsagainst Alzheimerrsquos diseaserdquo Journal of Alzheimerrsquos Disease vol20 no 1 pp 117ndash126 2010
[26] U Boettler K Sommerfeld N Volz et al ldquoCoffee constituentsas modulators of Nrf2 nuclear translocation and ARE (EpRE)-dependent gene expressionrdquo Journal of Nutritional Biochem-istry vol 22 no 5 pp 426ndash440 2011
[27] A S Dore N Robertson J C Errey et al ldquoStructure of theadenosine A
2119860receptor in complex with ZM241385 and the
xanthines XAC and caffeinerdquo Structure vol 19 no 9 pp 1283ndash1293 2011
[28] M A Heckman J Weil and E G de Mejia ldquoCaffeine (1 3 7-trimethylxanthine) in foods a comprehensive review on con-sumption functionality safety and regulatory mattersrdquo Journalof Food Science vol 75 no 3 pp R77ndashR87 2010
[29] N Amaresh A R Mullaicharam andM A El-Khider ldquoChem-istry and pharmacology of caffeine in different types of tealeavesrdquo International Journal of Nutrition Pharmacology Neu-rological Diseases vol 1 no 2 pp 110ndash115 2011
[30] L Wang L-H Gong C-J Chen H-B Han and H-H LildquoColumn-chromatographic extraction and separation of poly-phenols caffeine and theanine from green teardquo Food Chemistryvol 131 no 4 pp 1539ndash1545 2012
[31] Q V Vuong and P D Roach ldquoCaffeine in green tea its removaland isolationrdquo Separation and Purification Reviews vol 43 no2 pp 155ndash174 2014
[32] M C Borges M A R Vinolo K Nakajima et al ldquoThe effect ofmate tea (Ilex paraguariensis) on metabolic and inflammatoryparameters in high-fat diet-fed Wistar ratsrdquo International Jour-nal of Food Sciences and Nutrition vol 64 no 5 pp 561ndash5692013
[33] V Olmos N Bardoni A S Ridolfi and E C Villaamil LeporildquoCaffeine levels in beverages from Argentinarsquos market applica-tion to caffeine dietary intake assessmentrdquo Food Additives andContaminants A vol 26 no 3 pp 275ndash281 2009
[34] S Oba C Nagata K Nakamura et al ldquoConsumption of coffeegreen tea oolong tea black tea chocolate snacks and thecaffeine content in relation to risk of diabetes in Japanese menandwomenrdquoBritish Journal of Nutrition vol 103 no 3 pp 453ndash459 2010
[35] S N Bhupathiraju A Pan V S Malik et al ldquoCaffeinated andcaffeine-free beverages and risk of type 2 diabetesrdquoThe Ameri-can Journal of Clinical Nutrition vol 97 pp 155ndash166 2013
[36] C J Reissig E C Strain andR R Griffiths ldquoCaffeinated energydrinksmdasha growing problemrdquo Drug and Alcohol Dependencevol 99 no 1ndash3 pp 1ndash10 2009
[37] R S J Keast D Sayompark G Sacks B A Swinburn and L JRiddell ldquoThe influence of caffeine on energy content of sugar-sweetened beverages lsquothe caffeine-calorie effectrsquordquo EuropeanJournal of Clinical Nutrition vol 65 no 12 pp 1338ndash1344 2011
[38] P Mazzafera andM B Silvarolla ldquoCaffeine content variation insingle greenArabica coffee seedsrdquo Seed Science Research vol 20no 3 pp 163ndash167 2010
[39] J Tello M Viguera and L Calvo ldquoExtraction of caffeine fromRobusta coffee (Coffea canephora var Robusta) husks usingsupercritical carbon dioxiderdquo Journal of Supercritical Fluids vol59 pp 53ndash60 2011
[40] G Laurence K Wallman and K Guelfi ldquoEffects of caffeine ontime trial performance in sedentary menrdquo Journal of Sports Sci-ences vol 30 no 12 pp 1235ndash1240 2012
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
Stem CellsInternational
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Disease Markers
BioMed Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Oxidative Medicine and Cellular Longevity
PPARRe sea rch
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Immunology ResearchHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
ObesityJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Computational and Mathematical Methods in Medicine
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Diabetes ResearchJournal of
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Research and TreatmentAIDS
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Gastroenterology Research and Practice
Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
8 ISRN Nutrition
[11] S Topik J M Talbot and M Samper ldquoIntroduction global-ization neoliberalism and the latin American coffee societiesrdquoLatin American Perspectives vol 37 no 2 pp 5ndash20 2010
[12] C M Tucker H Eakin and E J Castellanos ldquoPerceptions ofrisk and adaptation coffee producers market shocks andextreme weather in Central America and Mexicordquo GlobalEnvironmental Change vol 20 no 1 pp 23ndash32 2010
[13] E G Burbano M G Wright N E Gillette et al ldquoEfficacy oftraps lures and repellents for Xylosandrus compactus (Cole-optera Curculionidae) and other ambrosia beetles on Coffeaarabica plantations and Acacia koa nurseries in Hawaiirdquo Envi-ronmental Entomology vol 41 no 1 pp 133ndash140 2012
[14] C W Kathurima B M Gichimu G M Kenji S M Muhohoand R Boulanger ldquoEvaluation of beverage quality and greenbean physical characteristics of selected Arabica coffee geno-types in Kenyardquo African Journal of Food Science vol 3 no 11pp 365ndash371 2009
[15] W J Rogers S Michaux M Bastin and P Bucheli ldquoChanges tothe content of sugars sugar alcohols myo-inositol carboxylicacids and inorganic anions in developing grains from differentvarieties of Robusta (Coffea canephora) andArabica (C arabica)coffeesrdquo Plant Science vol 149 no 2 pp 115ndash123 1999
[16] R Teuber ldquoGeographical indications of origin as a tool of prod-uct differentiation the case of coffeerdquo Journal of InternationalFood and Agribusiness Marketing vol 22 no 3-4 pp 277ndash2982010
[17] H C Liu C F You C Y Chen Y C Liu and M T ChungldquoGeographic determination of coffee beans usingmulti-elementanalysis and isotope ratios of boron and strontiumrdquo FoodChemistry vol 142 pp 439ndash445 2013
[18] T Niseteo D Komes A Belscak-Cvitanovic D Horzic andM Bude ldquoBioactive composition and antioxidant potential ofdifferent commonly consumed coffee brews affected by theirpreparation technique and milk additionrdquo Food Chemistry vol134 no 4 pp 1870ndash1877 2012
[19] M Oliveira S Casal S Morais et al ldquoIntra- and interspecificmineral composition variability of commercial instant coffeesand coffee substitutes contribution to mineral intakerdquo FoodChemistry vol 130 no 3 pp 702ndash709 2012
[20] J A Vignoli D G Bassoli and M T Benassi ldquoAntioxidantactivity polyphenols caffeine andmelanoidins in soluble coffeethe influence of processing conditions and raw materialrdquo FoodChemistry vol 124 no 3 pp 863ndash868 2011
[21] S I Mussatto L M Carneiro J P A Silva I C Roberto and JA Teixeira ldquoA study on chemical constituents and sugarsextraction from spent coffee groundsrdquo Carbohydrate Polymersvol 83 no 2 pp 368ndash374 2011
[22] Y F Chu P H Brown B J Lyle et al ldquoRoasted coffees high inlipophilic antioxidants and chlorogenic acid lactones are moreneuroprotective than green coffeesrdquo Journal of Agricultural andFood Chemistry vol 57 no 20 pp 9801ndash9808 2009
[23] S Johnson W P Koh R Wang S Govindarajan M C Yu andJ M Yuan ldquoCoffee consumption and reduced risk of hepatocel-lular carcinoma findings from the Singapore Chinese HealthStudyrdquo Cancer Causes and Control vol 22 no 3 pp 503ndash5102011
[24] J Tai S Cheung E Chan and D Hasman ldquoAntiproliferationeffect of commercially brewed coffees on human ovarian cancercells in vitrordquoNutrition and Cancer vol 62 no 8 pp 1044ndash10572010
[25] GWArendash andC Cao ldquoCaffeine and coffee as therapeuticsagainst Alzheimerrsquos diseaserdquo Journal of Alzheimerrsquos Disease vol20 no 1 pp 117ndash126 2010
[26] U Boettler K Sommerfeld N Volz et al ldquoCoffee constituentsas modulators of Nrf2 nuclear translocation and ARE (EpRE)-dependent gene expressionrdquo Journal of Nutritional Biochem-istry vol 22 no 5 pp 426ndash440 2011
[27] A S Dore N Robertson J C Errey et al ldquoStructure of theadenosine A
2119860receptor in complex with ZM241385 and the
xanthines XAC and caffeinerdquo Structure vol 19 no 9 pp 1283ndash1293 2011
[28] M A Heckman J Weil and E G de Mejia ldquoCaffeine (1 3 7-trimethylxanthine) in foods a comprehensive review on con-sumption functionality safety and regulatory mattersrdquo Journalof Food Science vol 75 no 3 pp R77ndashR87 2010
[29] N Amaresh A R Mullaicharam andM A El-Khider ldquoChem-istry and pharmacology of caffeine in different types of tealeavesrdquo International Journal of Nutrition Pharmacology Neu-rological Diseases vol 1 no 2 pp 110ndash115 2011
[30] L Wang L-H Gong C-J Chen H-B Han and H-H LildquoColumn-chromatographic extraction and separation of poly-phenols caffeine and theanine from green teardquo Food Chemistryvol 131 no 4 pp 1539ndash1545 2012
[31] Q V Vuong and P D Roach ldquoCaffeine in green tea its removaland isolationrdquo Separation and Purification Reviews vol 43 no2 pp 155ndash174 2014
[32] M C Borges M A R Vinolo K Nakajima et al ldquoThe effect ofmate tea (Ilex paraguariensis) on metabolic and inflammatoryparameters in high-fat diet-fed Wistar ratsrdquo International Jour-nal of Food Sciences and Nutrition vol 64 no 5 pp 561ndash5692013
[33] V Olmos N Bardoni A S Ridolfi and E C Villaamil LeporildquoCaffeine levels in beverages from Argentinarsquos market applica-tion to caffeine dietary intake assessmentrdquo Food Additives andContaminants A vol 26 no 3 pp 275ndash281 2009
[34] S Oba C Nagata K Nakamura et al ldquoConsumption of coffeegreen tea oolong tea black tea chocolate snacks and thecaffeine content in relation to risk of diabetes in Japanese menandwomenrdquoBritish Journal of Nutrition vol 103 no 3 pp 453ndash459 2010
[35] S N Bhupathiraju A Pan V S Malik et al ldquoCaffeinated andcaffeine-free beverages and risk of type 2 diabetesrdquoThe Ameri-can Journal of Clinical Nutrition vol 97 pp 155ndash166 2013
[36] C J Reissig E C Strain andR R Griffiths ldquoCaffeinated energydrinksmdasha growing problemrdquo Drug and Alcohol Dependencevol 99 no 1ndash3 pp 1ndash10 2009
[37] R S J Keast D Sayompark G Sacks B A Swinburn and L JRiddell ldquoThe influence of caffeine on energy content of sugar-sweetened beverages lsquothe caffeine-calorie effectrsquordquo EuropeanJournal of Clinical Nutrition vol 65 no 12 pp 1338ndash1344 2011
[38] P Mazzafera andM B Silvarolla ldquoCaffeine content variation insingle greenArabica coffee seedsrdquo Seed Science Research vol 20no 3 pp 163ndash167 2010
[39] J Tello M Viguera and L Calvo ldquoExtraction of caffeine fromRobusta coffee (Coffea canephora var Robusta) husks usingsupercritical carbon dioxiderdquo Journal of Supercritical Fluids vol59 pp 53ndash60 2011
[40] G Laurence K Wallman and K Guelfi ldquoEffects of caffeine ontime trial performance in sedentary menrdquo Journal of Sports Sci-ences vol 30 no 12 pp 1235ndash1240 2012
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MEDIATORSINFLAMMATION
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Oxidative Medicine and Cellular Longevity
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
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ObesityJournal of
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Diabetes ResearchJournal of
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Research and TreatmentAIDS
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Gastroenterology Research and Practice
Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
ISRN Nutrition 9
[41] R D S Prediger ldquoEffects of caffeine in Parkinsonrsquos disease fromneuroprotection to the management of motor and non-motorsymptomsrdquo Journal of Alzheimerrsquos Disease vol 20 no 1 pp205ndash220 2010
[42] Y F Chu W H Chang R M Black et al ldquoCrude caffeinereduces memory impairment and amyloid 1205731mdash42 levels in anAlzheimerrsquos mouse modelrdquo Food Chemistry vol 135 no 3 pp2095ndash2102 2012
[43] Y F Chu Y Chen P H Brown et al ldquoBioactivities of crudecaffeine antioxidant activity cyclooxygenase-2 inhibition andenhanced glucose uptakerdquo Food Chemistry vol 131 no 2 pp564ndash568 2012
[44] W Dworzanski G Opielak and F Burdan ldquoSide effects of caf-feinerdquo Polski Merkuriusz Lekarski vol 7 no 161 pp 357ndash3612009
[45] P J Rogers S V Heatherley E L Mullings and J E SmithldquoFaster but not smarter effects of caffeine and caffeine with-drawal on alertness and performancerdquo Psychopharmacologyvol 226 no 2 pp 229ndash240 2013
[46] Y Narita and K Inouye ldquoDegradation kinetics of chlorogenicacid at various pH values and effects of ascorbic acid and epi-gallocatechin gallate on its stability under alkaline conditionsrdquoJournal of Agricultural and Food Chemistry vol 61 no 4 pp966ndash972 2013
[47] P Gornas G Neunert K Baczynski and K Polewski ldquoBeta-cyclodextrin complexes with chlorogenic and caffeic acids fromcoffee brew spectroscopic thermodynamic and molecularmodelling studyrdquo Food Chemistry vol 114 no 1 pp 190ndash1962009
[48] R Upadhyay and L J M Rao ldquoAn outlook on chlorogenicacidsmdashoccurrence chemistry technology and biological activ-itiesrdquo Critical Reviews in Food Science and Nutrition vol 53 no9 pp 968ndash984 2013
[49] M Zhao HWang B Yang andH Tao ldquoIdentification of cyclo-dextrin inclusion complex of chlorogenic acid and its antimi-crobial activityrdquo Food Chemistry vol 120 no 4 pp 1138ndash11422010
[50] A A Memon N Memon D L Luthria M I Bhanger and AA Pitafi ldquoPhenolic acids profiling and antioxidant potential ofmulberry (Morus laevigata W Morus nigra L Morus alba L)leaves and fruits grown in Pakistanrdquo Polish Journal of Food andNutrition Sciences vol 60 no 1 pp 25ndash32 2010
[51] T Joet J Salmona A Laffargue F Descroix and S DussertldquoUse of the growing environment as a source of variation toidentify the quantitative trait transcripts and modules of co-expressed genes that determine chlorogenic acid accumulationrdquoPlant Cell and Environment vol 33 no 7 pp 1220ndash1233 2010
[52] J-K Moon H S Yoo and T Shibamoto ldquoRole of roasting con-ditions in the level of chlorogenic acid content in coffee beanscorrelation with coffee acidityrdquo Journal of Agricultural and FoodChemistry vol 57 no 12 pp 5365ndash5369 2009
[53] M T L Kreuml D Majchrzak B Ploederl and J KoenigldquoChanges in sensory quality characteristics of coffee duringstoragerdquo Food Science and Nutrition vol 1 no 4 pp 267ndash2722013
[54] K W Ong A Hsu and B K H Tan ldquoAnti-diabetic and anti-lipidemic effects of chlorogenic acid aremediated by ampk acti-vationrdquo Biochemical Pharmacology vol 85 no 9 pp 1341ndash13512013
[55] A-S Cho S-M JeonM-J Kim et al ldquoChlorogenic acid exhib-its anti-obesity property and improves lipid metabolism in
high-fat diet-induced-obese micerdquo Food and Chemical Toxicol-ogy vol 48 no 3 pp 937ndash943 2010
[56] Y Sato S Itagaki T Kurokawa et al ldquoIn vitro and in vivoantioxidant properties of chlorogenic acid and caffeic acidrdquoInternational Journal of Pharmaceutics vol 403 no 1-2 pp 136ndash138 2011
[57] C Hoelzl S Knasmuller K-H Wagner et al ldquoInstant coffeewith high chlorogenic acid levels protects humans againstoxidative damage of macromoleculesrdquoMolecular Nutrition andFood Research vol 54 no 12 pp 1722ndash1733 2010
[58] S-H Kwon H-K Lee J-A Kim et al ldquoNeuroprotectiveeffects of chlorogenic acid on scopolamine-induced amnesia viaanti-acetylcholinesterase and anti-oxidative activities in micerdquoEuropean Journal of Pharmacology vol 649 no 1ndash3 pp 210ndash2172010
[59] G-F Wang L-P Shi Y-D Ren et al ldquoAnti-hepatitis B virusactivity of chlorogenic acid quinic acid and caffeic acid in vivoand in vitrordquoAntiviral Research vol 83 no 2 pp 186ndash190 2009
[60] T Urushisaki T Takemura S Tazawa et al ldquoCaffeoylquinicacids aremajor constituentswith potent anti-influenza effects inbrazilian green propolis water extractrdquo Evidence-based Comple-mentary and Alternative Medicine vol 2011 Article ID 2549147 pages 2011
[61] C-M Ma T Kawahata M Hattori T Otake L Wang and MDaneshtalab ldquoSynthesis anti-HIV and anti-oxidant activitiesof caffeoyl 56-anhydroquinic acid derivativesrdquo Bioorganic andMedicinal Chemistry vol 18 no 2 pp 863ndash869 2010
[62] Z Lou H Wang S Zhu C Ma and Z Wang ldquoAntibacterialactivity and mechanism of action of chlorogenic acidrdquo Journalof Food Science vol 76 no 6 pp M398ndashM403 2011
[63] M Villarino P Sandın-Espana P Melgarejo and A de CalldquoHigh chlorogenic and neochlorogenic acid levels in immaturepeaches reduce Monilinia laxa infection by interfering withfungal melanin biosynthesisrdquo Journal of Agricultural and FoodChemistry vol 59 no 7 pp 3205ndash3213 2011
[64] M Ashour M Wink and J Gershenzon ldquoBiochemistry ofterpenoids monoterpenes sesquiterpenes and diterpenesrdquo inAnnual Plant Review M Wink Ed vol 40 of Biochemistryof Plant Secondary Metabolism pp 258ndash303 Wiley-BlackwellOxford UK 2nd edition 2010
[65] I Cordova-Guerrero L S Andres A E Leal-Orozco J MPadron J M Cornejo-Bravo and F Leon ldquoNew strategytoward the diverted synthesis of oxidized abietane diterpenesvia oxidation of 6 7-dehydroferruginol methyl ether with dim-ethyldioxiranerdquo Tetrahedron Letters vol 54 no 33 pp 4479ndash4482 2013
[66] B Yang X-F Zhou X-P Lin et al ldquoCembrane diterpeneschemistry and biological propertiesrdquo Current Organic Chem-istry vol 16 no 12 pp 1512ndash1539 2012
[67] C M Gampe and E M Carreira ldquoCyclohexyne cycloinsertionin the divergent synthesis of guanacastepenesrdquo Chemistry vol18 no 49 pp 15761ndash15771 2012
[68] P de Araujo Rodrigues S M de Morais C M de Souza etal ldquoGastroprotective effect of barbatusin and 3-beta-hydroxy-3-deoxibarbatusin quinonoid diterpenes isolated from Plec-tranthus grandis in ethanol-induced gastric lesions in micerdquoJournal of Ethnopharmacology vol 127 no 3 pp 725ndash730 2010
[69] R K Devappa H P S Makkar and K Becker ldquoJatropha diter-penes a reviewrdquo Journal of the American Oil Chemistsrsquo Societyvol 88 no 3 pp 301ndash322 2011
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
Stem CellsInternational
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MEDIATORSINFLAMMATION
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Behavioural Neurology
International Journal of
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Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Disease Markers
BioMed Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OncologyJournal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Oxidative Medicine and Cellular Longevity
PPARRe sea rch
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Immunology ResearchHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
ObesityJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Computational and Mathematical Methods in Medicine
OphthalmologyJournal of
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Diabetes ResearchJournal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Research and TreatmentAIDS
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Gastroenterology Research and Practice
Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
10 ISRN Nutrition
[70] K A Lee J I Chae and J H Shim ldquoNatural diterpenes fromcoffee cafestol and kahweol induce apoptosis through regu-lation of specificity protein 1 expression in human malignantpleuralmesotheliomardquo Journal of Biomedical Science vol 19 no60 pp 1ndash10 2012
[71] V Sridevi P Giridhar and G A Ravishankar ldquoEvaluation ofroasting and brewing effect on antinutritional diterpenes-cafes-tol and kahweol in coffeerdquo Global Journal of Medical Researchvol 11 no 5 pp 1ndash7 2011
[72] F He and W Harding ldquoNew labdane diterpenes from Leonotisleonurus and their biological activitiesrdquo Planta Medica vol 78no 11 2012
[73] L Faiella F D Piaz A Bisio A Tosco and N de TommasildquoA chemical proteomics approach reveals Hsp27 as a target forproapoptotic clerodane diterpenesrdquo Molecular BioSystems vol8 pp 2637ndash2644 2012
[74] F PMiao X R Liang X L Yin GWang andN Y Ji ldquoAbsoluteconfigurations of unique harziane diterpenes fromTrichodermaspeciesrdquo Organic Letters vol 14 no 15 pp 3815ndash3817 2012
[75] M J Schnermann C M Beaudry N E Genung et al ldquoDiver-gent synthesis and chemical reactivity of bicyclic lactone frag-ments of complex rearranged spongian diterpenesrdquo Journal ofthe American Chemical Society vol 133 no 43 pp 17494ndash175032011
[76] E P Stout L C Yu and T E Molinski ldquoAntifungal diterpenealkaloids from the Caribbean sponge Agelas citrina unifiedconfigurational assignments of agelasidines and agelasinesrdquoEuropean Journal of Organic Chemistry no 27 pp 5131ndash51352012
[77] F D Piaz R Cotugno L Lepore et al ldquoChemical proteomicsreveals HSP70 1A as a target for the anticancer diterpeneoridonin in Jurkat cellsrdquo Journal of Proteomics vol 82 no 26pp 14ndash26 2013
[78] M Fronza E Lamy S Gunther B Heinzmann S Laufer and IMerfort ldquoAbietane diterpenes induce cytotoxic effects in humanpancreatic cancer cell lineMIAPaCa-2 through differentmodesof actionrdquo Phytochemistry vol 78 pp 107ndash119 2012
[79] S Glisic J Ivanovic M Ristic and D Skala ldquoExtraction of sage(Salvia officinalis L) by supercritical CO
2 kinetic data chemi-
cal composition and selectivity of diterpenesrdquo Journal of Super-critical Fluids vol 52 no 1 pp 62ndash70 2010
[80] DNCavalcantiM-A R deOliveira J C de-Paula et al ldquoVari-ability of a diterpene with potential anti-HIV activity isolatedfrom the Brazilian brown alga Dictyota menstrualisrdquo Journal ofApplied Phycology vol 23 no 5 pp 873ndash876 2011
[81] S J Greay and K A Hammer ldquoRecent developments in thebioactivity of mono- and diterpenes anticancer and antimicro-bial activityrdquo Phytochemistry Reviews pp 1ndash6 2011
[82] C L Cespedes J R Salazar and J Alarcon ldquoChemistry andbiological activities of Calceolaria spp (Calceolariaceae scro-phulariaceae)rdquo Phytochemistry Reviews vol 12 no 4 pp 733ndash749 2013
[83] L Rakotobe K Mezhoud M Berkal et al ldquoAcute toxic effectsof 8-epidiosbulbin E a 19-norclerodane diterpene from yamDioscorea antaly on medaka Oryzias latipes embryosrdquo Journalof Fish Biology vol 77 no 4 pp 870ndash878 2010
[84] J Zhou L Chan and S Zhou ldquoTrigonelline a plant alkaloidwith therapeutic potential for diabetes and central nervoussystem diseaserdquo Current Medicinal Chemistry vol 19 no 21 pp3523ndash3531 2012
[85] K F Allred K M Yackley J Vanamala and C D AllredldquoTrigonelline is a novel phytoestrogen in coffee beansrdquo Journalof Nutrition vol 139 no 10 pp 1833ndash1838 2009
[86] L Sanchez-Hernandez P Puchalska C Garcıa-Ruiz A LCrego and M L Marina ldquoDetermination of trigonelline inseeds and vegetable oils by capillary electrophoresis as a novelmarker for the detection of adulterations in olive oilsrdquo Journal ofAgricultural and Food Chemistry vol 58 no 13 pp 7489ndash74962010
[87] G G Adams S Imran S Wang et al ldquoThe hypoglycemic effectof pumpkin seeds trigonelline (TRG) nicotinic acid (NA) andD-chiro-inositol (DCI) in controlling glycaemic levels in dia-betes mellitusrdquo Critical Reviews in Food Science and Nutrition2013
[88] Y Yin H Sasamoto and H Ashihara ldquoPyridine metabolismand trigonelline synthesis in leaves of the mangrove legumetrees Derris indica (Millettia pinnata) and Caesalpinia cristardquoNatural Product Communications vol 6 no 12 pp 1835ndash18382011
[89] MMathur andRKamal ldquoStudies on trigonelline fromMoringaoleifera and its in vitro regulation by feeding precursor in cellculturesrdquo Revista Brasileira de Farmacognosia vol 22 no 5 pp994ndash1001 2012
[90] A E van Dijk M R Olthof J C Meeuse E Seebus R J Heineand R M van Dam ldquoAcute effects of decaffeinated coffee andthe major coffee components chlorogenic acid and trigonellineon glucose tolerancerdquo Diabetes Care vol 32 no 6 pp 1023ndash1025 2009
[91] H Ashihara W-W Deng and C Nagai ldquoTrigonelline biosyn-thesis and the pyridine nucleotide cycle in Coffea arabicafruits metabolic fate of [carboxyl-14C]nicotinic acid ribosiderdquoPhytochemistry Letters vol 4 no 3 pp 235ndash239 2011
[92] N C Bicho A E Leitao J C Ramalho and F C LidonldquoIdentification of chemical clusters discriminators of the roastdegree in Arabica and Robusta coffee beansrdquo European FoodResearch and Technology vol 233 no 2 pp 303ndash311 2011
[93] O Yoshinari andK Igarashi ldquoAnti-diabetic effect of trigonellineand nicotinic acid on KK-Ay micerdquo Current Medicinal Chem-istry vol 17 no 20 pp 2196ndash2202 2010
[94] J Y Zhou and S W Zhou ldquoProtection of trigonelline on exper-imental diabetic peripheral neuropathyrdquo Evidence-Based Com-plementary and Alternative Medicine vol 2012 Article ID164219 8 pages 2012
[95] A Arlt S Sebens S Krebs et al ldquoInhibition of the Nrf2 tran-scription factor by the alkaloid trigonelline renders pancreaticcancer cells more susceptible to apoptosis through decreasedproteasomal gene expression and proteasome activityrdquo Onco-gene vol 32 pp 4825ndash4835 2013
[96] A G Antonio R S Moraes D Perrone et al ldquoSpecies roastingdegree and decaffeination influence the antibacterial activity ofcoffee against Streptococcus mutansrdquo Food Chemistry vol 118no 3 pp 782ndash788 2010
[97] C Zhang R Linforth and I D Fisk ldquoCafestol extraction yieldfrom different coffee brewmechanismsrdquo Food Research Interna-tional vol 49 no 1 pp 27ndash31 2012
[98] J Bravo I Juaniz C Monente et al ldquoEvaluation of spent coffeeobtained from the most common coffeemakers as a source ofhydrophilic bioactive compoundsrdquo Journal of Agricultural andFood Chemistry vol 60 no 51 pp 12565ndash12573 2012
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
Stem CellsInternational
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MEDIATORSINFLAMMATION
of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Behavioural Neurology
International Journal of
EndocrinologyHindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Disease Markers
BioMed Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OncologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Oxidative Medicine and Cellular Longevity
PPARRe sea rch
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Immunology ResearchHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
ObesityJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Computational and Mathematical Methods in Medicine
OphthalmologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Diabetes ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Research and TreatmentAIDS
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Gastroenterology Research and Practice
Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
ISRN Nutrition 11
[99] W Bi J Zhou and K H Row ldquoDecaffeination of coffee beanwaste by solid-liquid extractionrdquo Korean Journal of ChemicalEngineering vol 28 no 1 pp 221ndash224 2011
[100] S I Mussatto L F Ballesteros S Martins and J A TeixeiraldquoExtraction of antioxidant phenolic compounds from spentcoffee groundsrdquo Separation and Purification Technology vol 83no 1 pp 173ndash179 2011
[101] H Danhelova J Hradecky S Prinosilova et al ldquoRapid analysisof caffeine in various coffee samples employing direct analysis inreal-time ionization-high-resolution mass spectrometryrdquo Ana-lytical and Bioanalytical Chemistry vol 403 no 10 pp 2883ndash2889 2012
[102] I A Ludwig L Sanchez B Caemmerer L W Kroh M P dePena and C Cid ldquoExtraction of coffee antioxidants impact ofbrewing time andmethodrdquo Food Research International vol 48no 1 pp 57ndash64 2012
[103] WMullen B Nemzer B Ou et al ldquoThe antioxidant and chloro-genic acid profiles of whole coffee fruits are influenced by theextraction proceduresrdquo Journal of Agricultural and Food Chem-istry vol 59 no 8 pp 3754ndash3762 2011
[104] F Pena-Pereira I Lavilla and C Bendicho ldquoMiniaturized pre-concentration methods based on liquid-liquid extraction andtheir application in inorganic ultratrace analysis and speciationa reviewrdquo Spectrochimica Acta B vol 64 no 1 pp 1ndash15 2009
[105] A Belay andAVGholap ldquoCharacterization and determinationof chlorogenic acids (CGA) in coffee beans by UV-Vis spec-troscopyrdquo African Journal of Pure and Applied Chemistry vol3 no 11 pp 234ndash240 2009
[106] S Shipovskov K M Kragh B S Laursen C H Poulsen FBesenbacher and D S Sutherland ldquoMannanase transfer intohexane and xylene by liquid-liquid extractionrdquo Applied Bio-chemistry and Biotechnology vol 160 no 4 pp 1124ndash1129 2010
[107] A A Nuhu C Basheer K Alhooshani and A R Al-ArfajldquoDetermination of phenoxy herbicides in water samples usingphase transfer microextraction with simultaneous derivatiza-tion followed byGC-MS analysisrdquo Journal of Separation Sciencevol 35 pp 3381ndash3388 2012
[108] K Cecilia K Glaston M Simon B Renaud and N FredrickldquoVolatile organic compounds in brewed Kenyan Arabica coffeegenotypes by solid phase extraction gas chromatography massspectrometryrdquo Food Science andQualityManagement vol 8 pp18ndash26 2012
[109] H Fan Z Deng H Zhong and Q Yao ldquoDevelopment of newsolid phase extraction techniques in the last ten yearsrdquo Journalof Chinese Pharmaceutical Sciences vol 22 no 4 pp 293ndash3022013
[110] G CaprioliMCortese LOdello et al ldquoImportance of espressocoffee machine parameters on the extraction of chlorogenicacids in a certified Italian Espresso by using SPE-HPLC-DADrdquoJournal of Food Research vol 2 no 3 pp 55ndash64 2013
[111] G Spigno and D M de Faveri ldquoMicrowave-assisted extractionof tea phenols a phenomenological studyrdquo Journal of Food Engi-neering vol 93 no 2 pp 210ndash217 2009
[112] R C E Dias A F Faria A Mercadante N Bragagnolo andM T Benassi ldquoComparison of extraction methods for kahweoland cafestol analysis in roasted coffeerdquo Journal of the BrazilianChemical Society vol 24 no 3 pp 492ndash499 2013
[113] M D Pavlovic A V Buntic S Siler-Marinkovic and S IDimitrijevic-Brankovic ldquoEthanol influenced fast microwave-assisted extraction for natural antioxidants obtaining from
spent filter coffeerdquo Separation and Purification Technology vol118 pp 503ndash510 2013
[114] L Hongcheng S Jinliang L Qiwan L Yangang Y H Meiand H Lizhong ldquoDetermination of trigonelline nicotinic acidand caffeine in Yunnan Arabica coffee by microwave-assistedextraction and HPLC with two columns in seriesrdquo Journal ofAOAC International vol 95 no 4 pp 1138ndash1141 2012
[115] R Upadhyay K Ramalakshmi and L J M Rao ldquoMicrowave-assisted extraction of chlorogenic acids from green coffeebeansrdquo Food Chemistry vol 130 no 1 pp 184ndash188 2012
[116] J Xi D Shen S Zhao B Lu Y Li and R Zhang ldquoCharac-terization of polyphenols from green tea leaves using a highhydrostatic pressure extractionrdquo International Journal of Phar-maceutics vol 382 no 1-2 pp 139ndash143 2009
[117] C-CWang Y-Y Chou S-R Sheu M-J Jang and T-H ChenldquoApplication of ultrasound thermal process on extracting flavorand caffeine of coffeerdquo Thermal Science vol 15 supplement 1pp S69ndashS74 2011
[118] H Liu Q Li J Shao H Yan and S Lan ldquoDetermination oftrigonelline in coffee powder and instant coffee by ultrasonicextraction and high performance liquid chromatographyrdquo SePu vol 29 no 11 pp 1103ndash1106 2011
[119] L-H Wang Y-H Mei F Wang X-S Liu and Y Chen ldquoAnovel and efficient method combining SFE and liquid-liquidextraction for separation of coumarins fromAngelica dahuricardquoSeparation and Purification Technology vol 77 no 3 pp 397ndash401 2011
[120] S Machmudah K Kitada M Sasaki M Goto J Munemasaand M Yamagata ldquoSimultaneous extraction and separationprocess for coffee beans with supercritical CO
2and waterrdquo
Industrial and Engineering Chemistry Research vol 50 no 4pp 2227ndash2235 2011
[121] C Petisca T Perez-Palacios A Farah O Pinho and I M P VO Ferreira ldquoFurans and other volatile compounds in groundroasted and espresso coffee using headspace solid-phasemicroextraction effect of roasting speedrdquo Food and BioproductsProcessing vol 91 no 3 pp 233ndash241 2013
[122] E Liberto M R Ruosi C Cordero P Rubiolo C Bicchiand B Sgorbini ldquoNon-separative headspace solid phase micro-extractionndashmass spectrometry profile as a marker to monitorcoffee roasting degreerdquo Journal of Agricultural and Food Chem-istry vol 61 no 8 pp 1652ndash1660 2013
[123] J S Ribeiro R F Teofilo F Augusto and M M C FerreiraldquoSimultaneous optimization of the microextraction of coffeevolatiles using response surface methodology and principalcomponent analysisrdquo Chemometrics and Intelligent LaboratorySystems vol 102 no 1 pp 45ndash52 2010
[124] J Lopez-Darias J L Anderson V Pino and A M AfonsoldquoDeveloping qualitative extraction profiles of coffee aromas uti-lizing polymeric ionic liquid sorbent coatings in headspacesolid-phase microextraction gas chromatography-mass spec-trometryrdquo Analytical and Bioanalytical Chemistry vol 401 no9 pp 2965ndash2976 2011
[125] A N Gloess B Schonbachler B Klopprogge et al ldquoCompar-ison of nine common coffee extraction methods instrumentaland sensory analysisrdquo European Food Research and Technologyvol 236 no 4 pp 607ndash627 2013
[126] I Ignat I Volf and V I Popa ldquoA critical review of methodsfor characterisation of polyphenolic compounds in fruits andvegetablesrdquo Food Chemistry vol 126 no 4 pp 1821ndash1835 2011
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
Stem CellsInternational
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MEDIATORSINFLAMMATION
of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Behavioural Neurology
International Journal of
EndocrinologyHindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Disease Markers
BioMed Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OncologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Oxidative Medicine and Cellular Longevity
PPARRe sea rch
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Immunology ResearchHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
ObesityJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Computational and Mathematical Methods in Medicine
OphthalmologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Diabetes ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Research and TreatmentAIDS
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Gastroenterology Research and Practice
Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
12 ISRN Nutrition
[127] A Belay ldquoSome biochemical compounds in coffee beans andmethods developed for their analysisrdquo International Journal ofthe Physical Sciences vol 6 no 28 pp 6373ndash6378 2011
[128] G S Duarte A A Pereira and A Farah ldquoChlorogenic acidsand other relevant compounds in Brazilian coffees processed bysemi-dry and wet post-harvesting methodsrdquo Food Chemistryvol 118 no 3 pp 851ndash855 2010
[129] I Hecimovic A Belscak-Cvitanovic D Horzic and D KomesldquoComparative study of polyphenols and caffeine in different cof-fee varieties affected by the degree of roastingrdquo Food Chemistryvol 129 no 3 pp 991ndash1000 2011
[130] E Rudolph A Farbinger and J Konig ldquoDetermination of thecaffeine contents of various food items within the Austrianmarket and validation of a caffeine assessment tool (CAT)rdquoFoodAdditives and Contaminants A vol 29 no 12 pp 1849ndash18602012
[131] I Moreira and I S Scarminio ldquoChemometric discriminationof genetically modified Coffea arabica cultivars using spectro-scopic and chromatographic fingerprintsrdquo Talanta vol 107 pp416ndash422 2013
[132] M Mnatsakanyan P G Stevenson X A Conlan et al ldquoTheanalysis of cafe espresso using two-dimensional reversed phase-reversed phase high performance liquid chromatography withUV-absorbance and chemiluminescence detectionrdquo Talantavol 82 no 4 pp 1358ndash1363 2010
[133] N Kuhnert R Jaiswal P Eravuchira R M El-Abassy B Kam-mer and A Materny ldquoScope and limitations of principal com-ponent analysis of high resolution LC-TOF-MS data the anal-ysis of the chlorogenic acid fraction in green coffee beans as acase studyrdquo Analytical Methods vol 3 no 1 pp 144ndash155 2011
[134] R Jaiswal and N Kuhnert ldquoHierarchical scheme for liquidchromatography multi-stage spectrometric identification of345-triacyl chlorogenic acids in green Robusta coffee beansrdquoRapid Communications inMass Spectrometry vol 24 no 15 pp2283ndash2294 2010
[135] R Jaiswal M F Matei F Ullrich and N Kuhnert ldquoHow to dis-tinguish between cinnamoylshikimate esters and chlorogenicacid lactones by liquid chromatography-tandem mass spec-trometryrdquo Journal of Mass Spectrometry vol 46 no 9 pp 933ndash942 2011
[136] L Zhang D M Kujawinski E Federherr T C Schmidt andM A Jochmann ldquoCaffeine in your drink natural or syntheticrdquoAnalytical Chemistry vol 84 no 6 pp 2805ndash2810 2012
[137] C S Bizzotto A D Meinhart C A Ballus G Ghiselli andH T Godoy ldquoComparison of capillary electrophoresis andhigh performance liquid chromatography methods for caffeinedetermination in decaffeinated coffeerdquo Food Science and Tech-nology vol 33 no 1 pp 186ndash191 2013
[138] A D Meinhart C S Bizzotto C A Ballus et al ldquoOptimisationof a CE method for caffeine analysis in decaffeinated coffeerdquoFood Chemistry vol 120 no 4 pp 1155ndash1161 2010
[139] M Li J Zhou X Gu Y Wang X J Huang and C YanldquoQuantitative capillary electrophoresis and its application inanalysis of alkaloids in tea coffee coca cola and theophyllinetabletsrdquo Journal of Separation Science vol 32 no 2 pp 267ndash2742009
[140] N Kaiser D Birkholz S Colomban L Navarini and U HEngelhardt ldquoA new method for the preparative isolation ofchlorogenic acid lactones from coffee and model roasts of 5-caffeoylquinic acidrdquo Journal of Agricultural and Food Chemistryvol 61 no 28 pp 6937ndash6941 2013
[141] Y Yardim ldquoElectrochemical behavior of chlorogenic acid at aboron-doped diamond electrode and estimation of the antioxi-dant capacity in the coffee samples based on its oxidation peakrdquoJournal of Food Science vol 77 no 4 pp C408ndashC413 2012
[142] G A M Mersal ldquoExperimental and computational studies onthe electrochemical oxidation of caffeine at pseudo carbon pasteelectrode and its voltammetric determination in different realsamplesrdquo Food Analytical Methods vol 5 no 3 pp 520ndash5292012
[143] G Ziyatdinova A Nizamova and H Budnikov ldquoNovel coulo-metric approach to evaluation of total free polyphenols intea and coffee beverages in presence of milk proteinsrdquo FoodAnalytical Methods vol 4 no 3 pp 334ndash340 2011
[144] T A Araujo J C Cardoso A M Barbosa and V S FerreiraldquoInfluence of the surfactant bromide of cetyltrimetyl ammo-nium in the determination of chlorogenic acid in instant coffeeandmate tea samplesrdquoColloids and Surfaces B vol 73 no 2 pp408ndash414 2009
[145] M Amare and S Admassie ldquoPolymer modified glassy carbonelectrode for the electrochemical determination of caffeine incoffeerdquo Talanta vol 93 pp 122ndash128 2012
[146] W J R Santos M Santhiago I V P Yoshida and L T KubotaldquoNovel electrochemical sensor for the selective recognition ofchlorogenic acidrdquo Analytica Chimica Acta vol 695 no 1-2 pp44ndash50 2011
[147] S C Fernandes S K Moccelini C W Scheeren et al ldquoBiosen-sor for chlorogenic acid based on an ionic liquid containingiridium nanoparticles and polyphenol oxidaserdquo Talanta vol 79no 2 pp 222ndash228 2009
[148] R Jaiswal M F Matei A Golon M Witt and N KuhnertldquoUnderstanding the fate of chlorogenic acids in coffee roastingusing mass spectrometry based targeted and non-targetedanalytical strategiesrdquo Food and Function vol 3 pp 976ndash9842012
[149] W Lei Z Pengyue Z Fengzu B Aijuan and P CanpingldquoDetection of caffeine in tea instant coffee green tea beverageand soft drink by direct analysis in real time (DART) sourcecoupled to single-quadrupole mass spectrometryrdquo Journal ofAOAC International vol 96 no 2 pp 353ndash356 2013
[150] R Hertz-Schunemann T Streibel S Ehlert and R Zimmer-mann ldquoLooking into individual coffee beans during the roast-ing process direct micro-probe sampling online photo-ioni-sation mass spectrometric analysis of coffee roasting gasesrdquoAnalytical and Bioanalytical Chemistry vol 405 no 22 pp7083ndash7096 2013
[151] J S RibeiroMM C Ferreira and T J G Salva ldquoChemometricmodels for the quantitative descriptive sensory analysis of Ara-bica coffee beverages using near infrared spectroscopyrdquoTalantavol 83 no 5 pp 1352ndash1358 2011
[152] X Zhang W Li B Yin et al ldquoImprovement of near infraredspectroscopic (NIRS) analysis of caffeine in roasted Arabicacoffee by variable selection method of stability competitiveadaptive reweighted sampling (SCARS)rdquo SpectrochimicaActaAvol 114 pp 350ndash356 2013
[153] R Consonni L R Cagliani and C Cogliati ldquoNMR basedgeographical characterization of roasted coffeerdquoTalanta vol 88pp 420ndash426 2012
[154] N DrsquoAmelio L Fontanive F Uggeri F Suggi-Liverani and LNavarini ldquoNMR reinvestigation of the caffeine-chlorogenatecomplex in aqueous solution and in coffee brewsrdquo Food Bio-physics vol 4 no 4 pp 321ndash330 2009
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
Stem CellsInternational
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MEDIATORSINFLAMMATION
of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Behavioural Neurology
International Journal of
EndocrinologyHindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Disease Markers
BioMed Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OncologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Oxidative Medicine and Cellular Longevity
PPARRe sea rch
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Immunology ResearchHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
ObesityJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Computational and Mathematical Methods in Medicine
OphthalmologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Diabetes ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Research and TreatmentAIDS
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Gastroenterology Research and Practice
Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
ISRN Nutrition 13
[155] F Wei K Furihata F Hu T Miyakawa and M TanokuraldquoComplex mixture analysis of organic compounds in greencoffee bean extract by two-dimensional NMR spectroscopyrdquoMagnetic Resonance in Chemistry vol 48 no 11 pp 857ndash8652010
[156] G del Campo I Berregi R Caracena and J Zuriarrain ldquoQuan-titative determination of caffeine formic acid trigonellineand 5-(hydroxymethyl)furfural in soluble coffees by 1H NMRspectrometryrdquo Talanta vol 81 no 1-2 pp 367ndash371 2010
Submit your manuscripts athttpwwwhindawicom
Stem CellsInternational
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MEDIATORSINFLAMMATION
of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Behavioural Neurology
International Journal of
EndocrinologyHindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Disease Markers
BioMed Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OncologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Oxidative Medicine and Cellular Longevity
PPARRe sea rch
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Immunology ResearchHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
ObesityJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Computational and Mathematical Methods in Medicine
OphthalmologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Diabetes ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Research and TreatmentAIDS
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Gastroenterology Research and Practice
Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
Submit your manuscripts athttpwwwhindawicom
Stem CellsInternational
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MEDIATORSINFLAMMATION
of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Behavioural Neurology
International Journal of
EndocrinologyHindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Disease Markers
BioMed Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OncologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Oxidative Medicine and Cellular Longevity
PPARRe sea rch
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Immunology ResearchHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
ObesityJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Computational and Mathematical Methods in Medicine
OphthalmologyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Diabetes ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Research and TreatmentAIDS
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Gastroenterology Research and Practice
Parkinsonrsquos DiseaseHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Evidence-Based Complementary and Alternative Medicine
Volume 2014Hindawi Publishing Corporationhttpwwwhindawicom
