Mitigation Strategies to Reduce Acrylamide Formation in Fried Potato Products

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Mitigation Strategies to Reduce Acrylamide Formation in Fried Potato Products FRANCISCO MORALES, a EDOARDO CAPUANO, b AND VINCENZO FOGLIANO b a Instituto del Frio, Consejo Superior de Investigaciones Cient´ ıficas, Madrid, Spain b Dipartimento di Scienza degli Alimenti University of Napoli “Federico II,” Portici, Italy Potato products contain high amounts of acrylamide, which sometimes exceeds the concen- tration of 1 mg/L. However, many strategies for acrylamide reduction in potato products are possible. In this work, the different approaches for reducing acrylamide formation have been reviewed, keeping in mind that in the application of strategies for acrylamide formation, the main criteria to be maintained are the overall organoleptic and nutritional qualities of the final product. Key words: acrylamide; potato; mitigation Agronomic Strategies. Minimizing Reactants in the Potato Tuber During the first studies of acrylamide formation in food, researchers reported that starch-derived prod- ucts are very prone to the formation of acrylamide at concentrations up to 5 mg/kg. 1 One of the first lessons we learned from the systematic analysis of acrylamide in food was that there is a large variability in acry- lamide content between different final products from the same food commodities, even among different lots from the same commercial brand. 1 This observation gives us some clues that there are opportunities to re- duce acrylamide formation by first focusing on the raw material composition and second on the processing conditions. The strong tendency for acrylamide to form in pota- toes is because of the high levels of free asparagine (0.2– 0.4% dry weight, representing 20–60% total amino acids content), compared to the amount of reducing sugars in the potato tuber, which actually represents the limiting factor. In addition, there is a significant relationship between acrylamide formation and re- ducing sugar (glucose, fructose) content, regardless of the potato tuber variety, under the same processing conditions. 27 On the other hand, sucrose content has been found to have less correlation with acrylamide content. 3 Address for correspondence: Professor Vincenzo Fogliano, Via univer- sit` a 100, parco gussone, ed. 84, Portici, Italy. Voice: +39 81 2539356; fax: +39 81 7754942. [email protected] Reduction of sugar content in the potato tuber (Solanum tuberosum ssp. tuberosum L.) was proposed as the first strategy for acrylamide minimization because sugar is the limiting reactant. The results of studies have recommended using potato cultivars with a low reducing sugar content, such as Panda, Saturna, and Lady Clare, which are less susceptible to acrylamide formation when deep frying potato crisps, or the vari- eties Agria, Markies, and Fontane for French fries and hash browns. 2,3,5,8,9 About 4000 cultivars are listed in the World Catalogue of Potato varieties, but only a few of them have acceptable sensory and nutritional quality after processing and should be considered for consumption. The sugar content of potatoes is deter- mined by the genotype and several preharvest and postharvest factors. The major preharvest factors af- fecting sugar content are crop maturity, temperature during growth, mineral nutrition, and irrigation, while important postharvest factors are mechanical stresses and storage conditions. 10 Aspartic acid, asparagine, glutamic acid, and glutamine show no significant cor- relation with the acrylamide concentration in the pro- cessed products. 10 Potatoes used for roasting or frying should contain less than 1 g/kg fresh weight of reducing sugars. 7,11 In this framework, a genetically modified potato va- riety was recently produced in the United States by inhibiting the expression of some specific genes that are responsible for low-temperature sweetening. 12 However, other farming conditions could in- fluence the sugar content of the same potato variety. A relationship between the fertilization method and the susceptibility to acrylamide Ann. N.Y. Acad. Sci. 1126: 89–100 (2008). C 2008 New York Academy of Sciences. doi: 10.1196/annals.1433.051 89

Transcript of Mitigation Strategies to Reduce Acrylamide Formation in Fried Potato Products

Page 1: Mitigation Strategies to Reduce Acrylamide Formation in Fried Potato Products

Mitigation Strategies to Reduce AcrylamideFormation in Fried Potato Products

FRANCISCO MORALES,a EDOARDO CAPUANO,b AND VINCENZO FOGLIANOb

aInstituto del Frio, Consejo Superior de Investigaciones Cientıficas, Madrid, SpainbDipartimento di Scienza degli Alimenti University of Napoli “Federico II,” Portici, Italy

Potato products contain high amounts of acrylamide, which sometimes exceeds the concen-tration of 1 mg/L. However, many strategies for acrylamide reduction in potato products arepossible. In this work, the different approaches for reducing acrylamide formation have beenreviewed, keeping in mind that in the application of strategies for acrylamide formation, themain criteria to be maintained are the overall organoleptic and nutritional qualities of the finalproduct.

Key words: acrylamide; potato; mitigation

Agronomic Strategies. MinimizingReactants in the Potato Tuber

During the first studies of acrylamide formation infood, researchers reported that starch-derived prod-ucts are very prone to the formation of acrylamide atconcentrations up to 5 mg/kg.1 One of the first lessonswe learned from the systematic analysis of acrylamidein food was that there is a large variability in acry-lamide content between different final products fromthe same food commodities, even among different lotsfrom the same commercial brand.1 This observationgives us some clues that there are opportunities to re-duce acrylamide formation by first focusing on the rawmaterial composition and second on the processingconditions.

The strong tendency for acrylamide to form in pota-toes is because of the high levels of free asparagine (0.2–0.4% dry weight, representing 20–60% total aminoacids content), compared to the amount of reducingsugars in the potato tuber, which actually representsthe limiting factor. In addition, there is a significantrelationship between acrylamide formation and re-ducing sugar (glucose, fructose) content, regardless ofthe potato tuber variety, under the same processingconditions.2–7 On the other hand, sucrose content hasbeen found to have less correlation with acrylamidecontent.3

Address for correspondence: Professor Vincenzo Fogliano, Via univer-sita 100, parco gussone, ed. 84, Portici, Italy. Voice: +39 81 2539356; fax:+39 81 7754942.

[email protected]

Reduction of sugar content in the potato tuber(Solanum tuberosum ssp. tuberosum L.) was proposed asthe first strategy for acrylamide minimization becausesugar is the limiting reactant. The results of studieshave recommended using potato cultivars with a lowreducing sugar content, such as Panda, Saturna, andLady Clare, which are less susceptible to acrylamideformation when deep frying potato crisps, or the vari-eties Agria, Markies, and Fontane for French fries andhash browns.2,3,5,8,9 About 4000 cultivars are listed inthe World Catalogue of Potato varieties, but only afew of them have acceptable sensory and nutritionalquality after processing and should be considered forconsumption. The sugar content of potatoes is deter-mined by the genotype and several preharvest andpostharvest factors. The major preharvest factors af-fecting sugar content are crop maturity, temperatureduring growth, mineral nutrition, and irrigation, whileimportant postharvest factors are mechanical stressesand storage conditions.10 Aspartic acid, asparagine,glutamic acid, and glutamine show no significant cor-relation with the acrylamide concentration in the pro-cessed products.10

Potatoes used for roasting or frying should containless than 1 g/kg fresh weight of reducing sugars.7,11

In this framework, a genetically modified potato va-riety was recently produced in the United States byinhibiting the expression of some specific genes thatare responsible for low-temperature sweetening.12

However, other farming conditions could in-fluence the sugar content of the same potatovariety. A relationship between the fertilizationmethod and the susceptibility to acrylamide

Ann. N.Y. Acad. Sci. 1126: 89–100 (2008). C© 2008 New York Academy of Sciences.doi: 10.1196/annals.1433.051 89

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formation has been noted.2 Fertilization strate-gies influence the composition of potato tubers.Nitrogen appears to be indirectly related via its ef-fects on dry matter and relative maturity of harvestedtuber. Plants with adequate nitrogen fertilization pro-duce tubers with lower reducing sugar concentrationat harvest and accumulate less reducing sugars duringstorage.10 Free asparagine content in potato tubers in-creases with increasing nitrogen fertilization13 becausefree asparagine is a nitrogen reservoir.14 An excess innitrogen intake by fertilization leads to the biosynthe-sis of more free asparagine, thus lowering the reduc-ing sugar content since they are used by the tuber forthe biosynthesis of amino acids.15 Consequently, de-creasing nitrogen fertilization causes a reduced sugarcontent which reduces the potato’s quality for frying.13

However, there are other factors that must be consid-ered regarding potato farming, and other conditions,such as type of soil, will influence nutrient uptake andmetabolism by the plant.

Climatic conditions also affect the reducing sugarand asparagine content. Dry summers give rise to alower reducing sugar content, and temperatures above25◦C result in elevated sugar levels because increasedrespiration has a negative effect on the rate of starchbiosynthesis. Consequently, the level of reducing sugarswill be lower at intermediate temperatures (15–25◦C).Low temperatures during the final growing stage resultin unacceptably high sugar levels,16 and excessive rain-fall in the final stages of the growing season gives riseto a lower dry-matter content and to an increase in ni-trogen uptake. Finally, it has been shown that weatherconditions during the growing season influence bio-chemical reactions as well as nutrient uptake by theroots.17

Inadequate potato storage conditions also representa risk; starch can be hydrolyzed, forming high concen-trations of free sugars in the tuber, and this will leadto the formation of acrylamide and an excessive Mail-lard reaction upon frying.5,7,8,9,18 Senescent sweeten-ing occurs with long-term storage after harvest, andthis involves an increase in the sugar content inside thetuber. This process is enhanced at storage temperatureshigher than 8◦C, and it results in potato sprouting. Lowtemperatures mobilize sugars from starch in a processknown as low-temperature sweetening.17,19–20 Sucrosecan be used as an indicator for the reducing sugar po-tential in enzymatic cleavage and thermal breakdown,and the concentration of reducing sugars is used asa criteria for accepting or refusing potato batches atindustrial plants. The level of sucrose should be low tominimize accumulation of reducing sugars, which is anindex of tuber maturity. During cold-induced sweeten-

ing in stored potatoes, starch degradation occurs pri-marily through the action of starch phosphorylase. Useof sprout suppressant will limit the need to use low tem-peratures during storage. Low-temperature sweeteningis partly reversible after reconditioning the cold-storedtubers for some weeks at 15◦C.17

Former variables are further affected if potatoes arenot stored in the dark because light activates sugarmetabolism.5 Finally, low oxygen levels in the storageatmosphere inhibit the cold-induced enzymes and con-sequently decrease the level of reducing sugars in theproduct.

Processing Strategies. ControllingVariables during Deep Frying

Many stages prior to potato frying can be modi-fied in order to reduce acrylamide formation. Thereare several minimization strategies related to prefry-ing operations and most of them focus on the elim-ination of reducing sugars from the reaction media.It is well known that incorporation of aqueous pre-treatment steps (rinsing, soaking, blanching) of potatoslices will lead to a reduction in acrylamide content.Treatment with various concentrations of citric acidbefore frying suppresses acrylamide in fried potatoes,but there are many concerns about sour flavors in theresulting products.

Soaking potato slices in distilled water for up to90 min will reduce sugar content by about 30% fromprecursors leaching.21 However, blanching (soaking atmoderate temperatures) is more effective and has beenshown to reduce glucose by 76% and asparagine by68%, which results in a very significant reduction inacrylamide and a significant loss of texture.21 Blanch-ing induces gelatinization of the surface starch, reduc-ing oil uptake, but a negative impact on the overallquality is expected.

Addition of certain additives, which reduce the pHof the water, will limit the formation of acrylamide.Immersion of potatoes in up to 2% organic acids (e.g.,citric acid) decreases the pH, which reduces the for-mation of acrylamide at moderate temperatures offrying.21 Surprisingly, this effect was not observed athigher temperatures of frying. Several studies havedemonstrated that pH modification has the potentialto reduce acrylamide formation in food and model sys-tems. Lowering the pH of food to reduce acrylamidegeneration results from protonation of the alpha-aminogroup of asparagine, which then cannot engage the nu-cleophilic addition to the available carbonyls.22–24 Theacrylamide molecule contains an active double bond,

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which may interact with food ingredients, mainly pro-teins. The addition of protein-rich components frommeat will reduce acrylamide by 70%, and this is likelybecause of the reaction of protein nucleophilic groups(-SH, NH2) with the acrylamide double bond.25

Recently, an inhibition of acrylamide formation inasparagine–glucose model system by NaCl additionhas been shown.26 NaCl catalyzes the process of acry-lamide polymerization and the subsequent formationof polyacryalmide. Addition of 1% NaCl (common ad-ditive in many foods) is enough to promote significantpolymerization.27

Recently, Pedreschi et al.28 reported that soakingsolutions of potato slices in NaCl before frying dra-matically reduces acrylamide formation by about 90%compared to control chips. In contrast to the exper-iments with the potato model system29 but in ac-cordance with previous reports,28,30 Mestdagh et al.31

confirmed that soaking potato slices in NaCl solutionssignificantly decreases the acrylamide content and re-ported that the oil content is also significantly reduced(27%) by NaCl addition (0.1%) to the blanching wa-ter. Acrylamide formation has been shown to decreaseupon lowering the oil content of the potato model sys-tem, probably from a lower heat transfer from the oilto the system.32 Therefore, decreased oil uptake seemsa possible mechanism behind acrylamide reduction inthe NaCl-treated crisps.

Recent studies have demonstrated that polyvalentcations also reduce acrylamide formation in ther-mally processed snack foods and bakery products.33,34

Gokmen et al.35 investigated the potential formationand degradation of acrylamide during heating in thepresence of monovalent and divalent cations. Dippingpotatoes into calcium chloride solution inhibits theformation of acrylamide by up to 95% during fryingwithout adversely affecting the sensory quality of friedpotato strips (in terms of color and texture). The inhi-bition was attributed to the presence of monovalent ordivalent cations rather than to the reduction of acry-lamide precursors by dipping. Gokmen and colleaguespostulated that the presence of Ca2+ would prevent theformation of the Schiff base of asparagines, and thus ofacrylamide, during heating. Similar results were foundby Mestdagh et al.31 who showed that dipping potatoslices in CaCl2 solution mitigates acrylamide forma-tion, although only a marginal decrease was observedat the lowest concentration level (0.025 mol/L). As op-posed to Gokmen et al.,35 a more crispy texture anda bitter aftertaste at higher Ca2+ concentrations wasperceived by panelists. It is interesting that several ad-ditives, such as organic acids, NaCl, and Ca2+, are ableto lower the absorption of oil when frying. This fits per-

fectly with the ongoing consumer trend to move towardhealthier and low-fat products in order to counteractobesity and coronary heart diseases. Some other ques-tions, such as the rate of oil degradation during fryingwhen salts are added36,37 and the consequent morerapid oil turnover rate, need to be further investigatedbecause of the impact on process and production costsat the industrial scale.

Another mitigation strategy for acrylamide forma-tion in foods is the use of the enzyme asparaginase (L-asparagine amidohydrolase), which catalyzes the hy-drolysis of asparagine in aspartic acid and ammonia.From a theoretical point of view, this approach seemsto be more useful for cereal products where asparagineis known to be the limiting factor in acrylamide for-mation. In fact, in potatoes, the content of free as-paragine does not correlate with potential acrylamideformation,4,9,38 whereas a highly significant correla-tion between the content of reducing sugars and acry-lamide has been observed.2 In raw tubers, the molarconcentration of asparagine exceeds that of reducingsugars, the latter are also consumed faster during heat-ing.2,3,8,39 Nevertheless, when Zyzak et al.40 evaluatedthe effectiveness of the asparaginase treatment in amashed potato product that had been cooked by mi-crowave, they found that asparaginase pretreatmentresults in an 88% reduction in asparagine and greaterthan 99% reduction in acrylamide compared to sam-ples prepared without the enzyme. A constraint of thisapproach in limiting acrylamide formation is the lim-ited availability and high cost of asparaginase, whilequestions remain about the contribution of free as-paragine and aspartic acid to the flavor profile (e.g.,pyrazines) and to nutritional aspects, as well as country-specific regulatory approval of the enzyme. Two com-mercial products, Acrylaway� (asparaginase form As-

pergillus oryzae) from Novozyme (Bagsvaerd, Denmark)and PreventASe� (asparaginase form A. niger) fromDSM (Delft, Netherlands), are on the market for foodapplications that have been proven to reduce acry-lamide in dough-based products without influencingproduct taste or appearance.

Surface to volume ratio is also important becauseacrylamide formation is a surface phenomenon. Bothhome-made and industrially prepared French friesare usually cuts with different geometries. Matthauset al.41 demonstrated that a surface to volume ra-tio of 3.3:1 cm−1 results in a significantly loweramount of acrylamide than fine strips with a ratioof 5.4:1 cm−1. Another factor to consider is the ra-tio of potato to oil mass, which is recommended tobe less than 10%. This recommendation is impor-tant for catering services and home-frying processes

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where the ratio of potato to oil is not standardizedand the heat load could be very different from onepiece of potato to the other. Drying potatoes by mi-crowave or hot-air treatment before frying results ina significant reduction in oil content, and, in theseconditions, acrylamide is reduced by 44%.42,43 Itshould be stressed that moisture content is an impor-tant quality parameter of potato crisps, which shouldbe crispy not only after frying but also during the shelflife of the product; many investigations have not con-sider this aspect.

The influence of temperature on the formationof acrylamide has been repeatedly demonstrated.44,45

Frying potatoes is based on heat transfer from the hotoil, which results in water removal and oil uptake bythe potato. It has been shown that the acrylamide con-tent of potato strips first increases exponentially withtime, depending on temperature.23 After prolongedheating, a decrease in the acrylamide content is ob-served because acrylamide degradation predominates.The acrylamide yield is the net result of simultane-ous formation and elimination reactants and it can bemodeled by consecutive first-order reactions.46 Con-trolling the temperature and time of frying will have amajor effect on acrylamide reduction in potato prod-ucts, but this could have a negative effect on perceivedproduct quality; it may also be difficult to introduce ona home scale. Temperature and time can be preciselycontrolled at industrial plants but only partly controlledat home. For instance, there are differences in the heattransfer inputs and electrical potency of domestic fry-ers, whereas these are exhaustively controlled at theindustrial scale, and initial and end-frying tempera-tures of the process remain almost constant. It can beconcluded that for home preparation, strategies con-cerning the choice of suitable potato varieties or cul-tivars will be more effective to reduce the acrylamidecontent.

Choice of the frying oil is an important aspect fordeep frying. Frying oil not only acts as a heat transfermedium but also contributes to the taste and aromaof the potato fries. Some studies have focused on theeffect of the type of frying oil on acrylamide formationin the product. Matthaus et al.41 did not find differencesin acrylamide formation in French fries because of thetype of frying oil, and similar results were reported byMestdasgh et al.32 However, Gertz and Klostermann47

found higher amounts of acrylamide in French friesfried with palmolein compared to rapeseed or sun-flower oil. On the other hand, the type of oil has aninfluence on the shelf life and the stability of the fryingmedium during processing. Matthaus et al.41 did notfind a relationship between acrylamide formation and

the aging of the frying oil or the addition of siliconoil as an antifoaming agent. Recently, Mestdash et al.48

reported no evidence that the heat transfer proper-ties of the frying oil (from oxidative or hydrolytic oildegradation) change to such an extent that acrylamideformation during the preparation of French fries wouldbe significantly influenced. In addition, oil degradationproducts (glycerol, monoacylglycerols, and diacylglyc-erols) do not influence acrylamide formation becauseacrylamide formation is independent of oil oxidationand hydrolytic status. This conclusion is importantsince it was suggested that triacylglycerols are partiallyhydrolyzed during frying, followed by dehydratationof glycerol to acrolein. Acrolein may be oxidized toacrylic acid, which can finally react with ammonia toform acrylamide.47,49

The consumer’s perception of color, flavor, andcrispness should be unaffected by a reliable acrylamidemitigation procedure. Frying time should be adjustedto keep final moisture content below 3% to obtaindesirable crispness. Lowering water activity at the sur-face of products for prefrying was proposed as a meansof acrylamide reduction.30 It has been reported thatlow frying temperatures result in moderate acrylamideconcentrations despite the longer frying times, whereastemperatures above 170◦C enhance acrylamide for-mation and enhance color.6 On the other hand, fryingat temperatures below 170◦C will increase fat uptake,and the potato will become soft. It is suggested thatthe frying temperature should be below 175◦C andthe frying time should not be longer than necessary toobtain the right quality parameters of fried products.Therefore, a lower frying temperature will negativelyinfluence the fat content and the moisture of crisps.Alternative heat treatments are under investigation.Granda et al.50 performed vacuum frying experimentsbetween 118 to 140◦C at a vacuum pressure of 1333 Pa.Vacuum frying reduces acrylamide formation by 94%without important changes in the organoleptic param-eters of the potato.

Finally, postfrying treatment has also been consid-ered. Kita et al.51 reported that applying a postdryingstep after frying results in a decreased acrylamide con-tent in crisps. When crisps were fried in oil at 185◦C,it was possible to obtain a 70% decrease of acrylamidecontent after 2 min of frying and 75 min at 105◦C ofpostdrying.

Acrylamide is a very polar, low mass, and volatilesubstance. These particular properties could be usedto eliminate it after processing. A combination ofadequate temperature and vacuum after the fryingprocess could be an alternative for removing acry-lamide from the matrix. However, there are many

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FIGURE 1. Acrylamide formation from asparagine and glucose. The R-NH2 group of asparagine participates in anucelophilic-addition reaction with the aldehyde group of glucose to form a Schiff base, which then undergoes an Amadorirearrangement to the shown glucose–asparagine derivative (N-glycoside). The latter can then undergo decarboxylativedeamination, losing the COOH and R-NH2 groups associated with asparagine to form acrylamide. Addition of glycinecan reduce acrylamide level in two ways: 1) competing effectively with asparagine in the Maillard reaction or 2) reactingwith acrylamide after its formation.

issues that should be overcome, such as loss of flavoror fragility of the potato crisp, which probably breaks.Such an alternative is possible, however, because eventhough the vapor pressure of acrylamide is low (i.e.,0.93 Pa at 25◦C, 9.3 Pa at 50◦C), it has been measuredin air. On the other hand, it has been reported thatacrylamide, added to foods before heating, is not com-pletely recovered in analysis,5 so it appears that acry-lamide is eliminated either by further reactions (ad-dition reactions or polymerization) with food compo-nents or evaporates during heating.23,52,53

Therefore, it is possible that adopting postfryingsteps will reduce the concentration of acrylamide but

may also reduce the concentration of many volatileproducts, thus affecting the sensorial quality of the fi-nal product.

Inhibition of the Reaction byCompetitive Compounds toward

Reducing Sugars Instead ofAsparagine

It is well known that acrylamide is mainly formedfrom asparagine and reducing sugars through theMaillard reaction (FIG. 1).44,54,55 The first step is the

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TABLE 1. Effect of the addition of glycine or other amino acids on acrylamide formation in the potatomodel system or potato-based foodstuffs

Authors Amino acids used Effect on acrylamide content

Kim et al.61 Glycine, lysine, cysteine Addition of 0.1 and 0.5% glycine to pallets reduced acrylamideconcentration by 43% and by more than 70%, respectively; soakingpotato slices in a 3% solution of either lysine or glycine reduced theformation of acrylamide by more than 80% in potato chips fried for1.5 min at 185◦C

Claeys et al.46 Cysteine, lysine, alanine, andglutamine

Addition of cysteine and lysine to the asparagine–glucose model systemheated at 140–200◦C, lowered acrylamide yield. A alanine has noeffect while glutamine increased acrylamide yield

Rydberg et al.23 Various amino acids or protein-richcomponents

Addition of several amino acids or a protein-rich component to potatoslurries decreased acrylamide content by more than 80%; glycineand glutamine were almost twice as effective as alanine, lysine, andglutamic acid in suppressing acrylamide levels at low concentrations

Brathen et al.52 Glycine and glutamine Addition of glycine and glutamine to a starch model system, reduced acrylamide formation by 30% compared to no addition while noeffect was found on French fries

Glycine Addition of glycine to a model system consisting of starch, asparagine,and glucose decreased acrylamide content upon prolonged heatingtreatment

Low et al.64 Glycine Addition of glycine to a potato model system reduced acrylamidecontent, increased the total volatile yield by promoting the formationof certain alkylprazines

Mestdagh et al.29 Glycine and lysine Addition of glycine and lysine reduced acrylamide formation in potatoslices (up to 85%) by addition to the blanching water. No effects onpH and oil content. Strong effect on browning

reaction between the alpha-amino group of the freeasparagine and a carbonyl source, forming a Shiffbase. Results from mechanistic studies indicate that theside-chain amide group of asparagine is incorporatedin the amide bond of acrylamide.4,40,56

From this reaction pathway, it is clear that one possi-bility for reducing acrylamide formation is to use com-pounds able to compete with asparagine for carbonylgroups; this means, in particular, other free amino acids(e.g., glycine) or proteins. As a matter of fact, among theseveral patent applications for the reduction of acry-lamide in heat-treated foodstuffs, applications basedon the addition of amino compounds, including aminoacids, have been proposed.57,58

Amino acids may compete effectively with as-paragine in the Maillard reaction or may react withacrylamide after its formation (FIG. 1). Acrylamidehas two reactive sites, the conjugated double bondand the amide group, and can thus be eliminatedby reaction with numerous food constituents. In thissense, other nucleophilic compounds could work inthis way and lead to a reduction in acrylamidecontent.

In a model system consisting of starch, asparagine,and glucose, acrylamide content decreases upon pro-longed heating,52 indicating that acrylamide reacts

with amino acids. The reaction of acrylamide with theamino group of glycine was demonstrated previously,59

and the effects of amino acids on acrylamide forma-tion and elimination have been extensively studied (seeTABLE 1).

Claeys et al.46 reported that the addition of cysteineand/or lysine to the asparagine–glucose model systemand heated at temperatures between 140 and 200◦Csignificantly lower the acrylamide yield. According tothe activation energies for acrylamide formation andelimination when these amino acids are added, Claeysand colleagues concluded that lysine would act mainlyby competing with asparagines in the Maillard reactionwhile cysteine would increase the elimination rate ofacrylamide by reacting with its SH group and formingcysteinyl-S-β-propionammide. SH groups are reportedto be 100–300 times more reactive than amino groupswith conjugated vinyl compounds,59 while cysteine isclassified as an amino acid with low reactivity in theMaillard reaction.60 As such, sulfur amino acids orsulfhydryl compounds could reduce acrylamide con-tent in heated foods. Unfortunately, their use is re-stricted by the unpleasant off-flavors they can generatein foods. The same authors reported that addition ofalanine to the same model system has no effect onacrylamide yield, while glutamine increases the rate

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of acrylamide formation, thus leading to higher acry-lamide levels.

The effect of soaking potato slices in a solution ofamino acids in order to reduce acrylamide in friedpotato slices was investigated by Kim et al.61 Theyfound that the longer the soaking time and the moreconcentrated the solution, the more effective the treat-ment. They reported that dipping potato slices in a3% solution of either lysine and glycine reduces theformation of acrylamide by more than 80% in potatochips fried for 1.5 min at 185◦C; however, a significantreduction (more than 40%) is obtained by using 0.1or 0.5% lysine and glycine solutions. Of course, theoverall inhibitory effect results from both the leachingof acrylamide precursors and the competitive action ofamino acids. The same authors reported that the addi-tion of lysine and glycine to potato model snacks beforefrying reduces the acrylamide content upon heating. Inparticular, the addition of 0.1 and 0.5% glycine to pal-lets reduces acrylamide concentration by 43% and bymore than 70%, respectively.

Rydberg et al.23 examined the effects of variousamino acids on the formation of acrylamide in ho-mogenized potatoes heated at 180◦C for 25 min. Theaddition of glycine, alanine, lysine, glutamine, and glu-tamic acid at a concentration of 35 mmol/kg was foundto reduce acrylamide levels by 42% to 70%. They alsodemonstrated that glycine and glutamine are almosttwice as effective as alanine, lysine, and glutamic acidin suppressing acrylamide levels at low concentrations.Rydberg and colleagues also investigated the effect ofprotein addition (lean fish) to potato patties. Like freeamino acids, proteins were found to significantly loweracrylamide content, as already reported by several au-thors working on different matrices.5,62 Proteins couldact both by inhibiting acrylamide formation reactionand eliminating acrylamide formed via reaction withamino and/or sulfhydryl groups of amino acid sidechains. For that purpose, Rydberg et al.23 added dif-ferent amounts of minced cod to potato slurries andobtained a reduction of up to 70% of acrylamide con-tent after heating.

Similar results were found by Vattem et al.63 whoused chickpea butter to coat potato chips during frying.They postulated that proteins might also be involvedin complexing starch on the surface of the slices andstabilizing the complex even at higher temperatures,making the sugars in the starch less available for theMaillard reaction. The legume proteins may also beinvolved in delocalizing the electrons from the sugarcarbonyl via their aromatic amino acids. This delocal-ization prevents the keto-enolization of the sugars and,therefore, the breakdown of the six-carbon chain to hy-

droxyacetone, which eventually may form acrylamidethrough a series of condensation reactions.

Brathen et al.52 found that the addition of glycineand glutamine during blanching of crisps reduces theamount of acrylamide by 30%, but no effect was foundon French fries. Furthermore, they found that glycine ismore effective than glutamine in reducing acrylamide,while Rydberg et al.23 found comparable effects forboth amino acids. This apparent discrepancy couldbe explained by the different systems used. Rydbergand colleagues23 used homogenized potato slurrieswith amino acids added during the homogenization,which ensured that the amino acids were evenly dis-tributed. On the other hand, in common industrialconditions, potato crisps are made from sliced pota-toes and are not reconstituted. In the nonreconstitutedpotato crisps, the amino acid has to enter the potatotissue, and glutamine, being larger then glycine, will betransported more slowly into potato tissues. All in all,glycine is known to be more reactive in the Maillardreaction than glutamine, which may be of importanceif the effect from the addition of glycine is caused bycompetition in the Maillard reaction. However, a re-action between glycine and the acrylamide previouslyformed seems to be the more likely cause of the de-crease in measured acrylamide content when glycine isadded.

As the Maillard reaction plays a major role in acry-lamide formation, its suppression would, therefore, re-duce the levels of acrylamide. However, the Maillardreaction is also a major route for the generation of de-sirable flavors and colors in food, ensuring the sensoryquality expected by consumers. It is important to studythe relationship between flavor generation, taste, andacrylamide production to develop a strategy to mini-mize acrylamide without adverse effects on the flavorand taste of foods. In this respect, Low et al.64 studiedthe effect of treatment with citric acid or glycine on thevolatile profile and acrylamide levels in a potato modelsystem. After cooking at 180◦C for 10–60 min, thesetreatments were found to affect the volatile profiles and,in particular, Strecker aldehydes and alkylpyrazines,key flavor compounds of cooked potato. Citric acidlimits the generation of volatiles, particularly thealkylpyrazines. Glycine increases the total volatile yieldby promoting the formation of certain alkylpyrazines,namely 2,3-dimethylpyrazine, trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, tetramethylpyrazine, and2,5-diethyl-3-methylpyrazine. However, the formationof other pyrazines and Strecker aldehydes is sup-pressed. The authors concluded that a combined treat-ment of lower levels of citric acid and glycine wouldhave less impact on the flavor profile than a higher

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TABLE 2. Effect of the addition of antioxidants on acrylamide formation in different matrices and foodmodels

Authors Antioxidant used Foodstuff Effect on acrylamide content

Becalski et al.70 Rosemary herb Oil used to fry potato slices Reduction of acrylamide formationFernandez et al.71 Liquid spice mix rich in

flavonoidsPotato slices before and after

fryingReduction by up to 50%

Biedermann et al.5 Ascorbic acid Potato-based model system Weak inhibitionZhang et al.67–69 Different solutions of

antioxidant of bambooleaves (AOB)

Potato crisps and French fries Reduction of 74.1% and 76.1% when AOBaddition ratio was 0.1% and 0.01% (w/w);no significant effects on crispness andflavor

Different solutions of AOB Fried chicken wings Nearly 57.8 and 59.0% reduction withaddition ratios of 0.1 and 0.5% (w/w),respectively

Different solutions of AOB orextract of green tea (EGT)

Fried bread sticks Nearly 82.9% and 72.5% reduction withAOB and EGT addition levels of 1 and0.1 g/kg, respectively; no significant effectson crispness and flavor

Tareke et al.62 Butylated hydroxytoluene,sesamol, Vitamin E

Meat Enhancement of acrylamide formation

Vattem et al.63 Phenolic antioxidants fromcranberry and oregano

Fried potato slices Slight increase

Rydberg et al.23 Ascorbyl palmitate andsodium ascorbate; benzoilperoxide and hydrogenperoxide

Homogenized potato heatedin an oven

Effect on acrylamide content small ornonexistent

Levine et al.72 Ferulic acid, ascorbic acid Model system based on wheatflour and water; resembledcrackers

Reduction of acrylamide formation;increasing acrylamide elimination

level of either treatment on its own, which would beneeded to achieve the same reduction in acrylamide.Low and colleagues also suggested the possibility ofusing a combination of different amino acids to boostthe desired Strecker aldehydes and alkylpyrazines andat the same time mitigate acrylamide levels.

In a similar way, Mestdagh et al.29 investigated theeffect of the addition of free glycine and L-lysine topotato crisp blanching water at different concentra-tion levels. They showed that the addition of thesecomponents did not markedly change the pH of thepotato at a low concentration (0.05%) as they had pre-viously pointed out.31 At this concentration level, theseadditives markedly influence the final oil content of thecrisps, compared to the control. L-lysine appeared tomore efficiently reduce the formation of acrylamide(by up to 85%), although the differences are less pro-nounced at the 0.05 and 0.025 mol/L concentrationlevels. However, the authors found that this treatmentstrongly affects the color of the final product. Darkerproducts are obtained upon frying when glycine or L-lysine is added to the blanching water. This differenceis most pronounced for L-lysine, which is not surpris-ing because L-lysine is known to be very reactive in the

Maillard reaction. Moreover, at the applied concentra-tions, both amino acids could counteract the inhibitionof browning caused by the addition of acetic or citricacid.

Many other authors have reported an increasedbrowning of their potato model system when glycinewas added, and the same effect has been reported byseveral authors for bread and cereal products.52,65,66

All in all, it is possible to conclude that the use ofamino acids, and particularly of glycine, represent anattractive and promising strategy to reduce acrylamideformation in potato-based products.

Affecting Some Steps of the Reactionsby Addition of Chemically ReactiveCompounds that are Able to React

with Intermediates

A significant part of mitigation research has con-sisted of studies testing the effects of the addition ofchemically reactive compounds to potatoes. Most ofthese compounds are antioxidants, which are used inpure form, added as vegetable extracts, or present inwhole spices.

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It is difficult to draw firm conclusions from thesestudies as the reports published thus far have reportedconflicting evidence. In some cases, retarding effectshave been demonstrated with spice extracts, but it isclear that the effect is not necessarily a result of antiox-idative properties of those additives. The main studiesdealing with the effects of antioxidants on acrylamideformation are summarized in TABLE 2.

Zhang et al.67 demonstrated that 74.1% and 76.1%of acrylamide is reduced in potato crisps and Frenchfries, respectively, dipped into different solutions ofantioxidants of bamboo (AOB), a pale brown pow-der extracted from bamboo leaves. The reduction de-pends on the AOB addition:product ratio and on im-mersion time. Sensory evaluation results showed thatorganoleptic features of products are not affected bythe treatment; the crispness and flavor of the potatocrisps and French fries processed by AOB solutions arenot significantly different from the normal potato ma-trix when the AOB solution to product ratio is <0.05%.Similar results were found by the same authors in otherfoodstuffs, such as fried chicken wings and fried breadsticks.68,69 Thus, the addition of plant extracts couldbe a possible technique for reducing acrylamide inmany products. Becalski et al.70 found that acrylamidecould be reduced when adding rosemary herb to theoil used for frying potato slices. It should be noted,however, that these findings could not be confirmed byothers.41 Rosemary is known for its antioxidant con-tent, but this effect could also be a result of many otherfactors. A decreasing effect of a flavonoid spice mixhas also been reported by Fernandez et al.71 A liq-uid spice mix was added to potato slices before frying,and a powder spice mix was also added to the potatoslices after frying. The acrylamide levels were reportedto be reduced by up to 50% by the spice-mix treat-ment. Biedermann et al.5 showed a weak inhibitioneffect upon addition of ascorbic acid to a potato-basedmodel.

The ability of ferulic acid to inhibit acrylamide for-mation was attributed to its ability to react with acry-lamide precursors or intermediates in the chemicalprocess of its generation.72 The same authors reportedthat ascorbic acid is effective in increasing acrylamideelimination and decreasing the net amount of acry-lamide formed in a wheat–water model system whenbaked at 180◦C.

In one pivotal study, Tareke et al.62 found that theaddition of antioxidants (butylated hydroxytoluene,sesamol, vitamin E) to meat before heating enhancesthe formation of acrylamide. This author introducedthe hypothesis that antioxidants might protect the acry-lamide from further radical-initiated reactions. On the

other hand, studies of the effect of the antioxidant com-pounds present in the oil on acrylamide formation arescarce. It is possible that the minor oil componentstocopherols, phenols, and sterols can influence acry-lamide formation during the exposure of potatoes tothese oils at high temperatures.

Vattem et al.63 reported that formation of acrylamidein fried potato slices previously treated with phenolicantioxidants from cranberry and oregano or cooked inchickpea batter is not reduced but actually increaseswhen exogenous phenolic is present. Based on theseresults, authors hypothesized a nonoxidative model forthe formation of acrylamide in fried products. Ryd-berg et al.,23 to investigate the effects of antioxidants onacrylamide formation, used two antioxidants, ascorbylpalmitate and sodium ascorbate, as well as oxidants,such as benzoil peroxide and hydrogen peroxide, inhomogenized potato heated in an oven. They foundthat the effect on acrylamide content is small or nonex-istent, thus suggesting that involvement of radicals orperoxidation in the formation of acrylamide may be ofsome, but only minor, importance; low levels of antiox-idants cause a small increase, probably via protectionof the acrylamide formed.

Conclusions and Future Perspectives

Many studies have attempted to find strategies tominimize the levels of acrylamide in different foodcommodities. This objective can be achieved eitherby modifying processing parameters, such as pH, tem-perature or time of heating, acting on precursors or keyintermediates, or reducing concentration of reactantsin the raw material as formerly discussed. Strategiesto reduce acrylamide formation should maintain theoverall organoleptic, nutritional properties, and mi-crobiological safety of the food during its shelf life.Different approaches have been investigated to reducethe formation of acrylamide in food, but, in reality,only few of them could be implemented without anysignificant alteration of the food product.

It is very likely that the total elimination of acry-lamide from fried products cannot be achieved. Then,the ALARA principle (as low as reasonably or techni-cally achievable) should be applied by the different ac-tors. And, as outlined in this review, there are many dif-ferent opportunities to reduce acrylamide in fried pota-toes. However, potential negative effects on the sensorycharacteristics of the final product have to be carefullyevaluated. In this context, there will not be a uniquestrategy, and a combination of agronomical selec-tion and lighter processing conditions will significantly

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reduce the levels of acrylamide in the final productat an industrial level. Additional strategies should beimplemented on the domestic scale, mainly focusedon processing conditions. We should keep in mind thatthe overall objective is to reduce the acrylamide intake,and many sources of acrylamide come from foods pro-cessed at home. Consumers must be aware that it isimportant not to fry in excess and to limit the exces-sive intake of over-fried products. Also, informationon potato varieties particularly suitable for frying andrecommendations about potato home storage shouldbe released.

In conclusion, the reduction of the overall intakeof acrylamide is not only a food company’s task; infact, companies must implement an intensive mitiga-tion strategy for different food items. The onus alsofalls on the final cookers who should be aware that it istheir responsibility to serve customers and/or relativesfoods having a low acrylamide content.

Conflict of Interest

The authors declare no conflicts of interest.

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