Seminar Bushra

7/22/2019 Seminar Bushra

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Analytical techniques for determination

of Sudan dyes I IV in food matrixesPresented By:

Bushra IshfaqReg # 2003 ag 1755Supervisor:

Prof. Dr Faqir Muhammad Anjum


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Con

tents

IntroductionApplicationsHealth effectsAnalytical methods Extractiontechniques Detection methods

ConclusionReferences


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Sudan dyes

Synthetic Azo dyesSudan dyes

Sudan I IV

Sudan Red B Sudan Red 7 B Sudan Red G

Sudan Orange G Sudan Black Dimethyl Yellow

Para Red


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General applications

Coloration of diesel oil and fuel oilColoration of wax products

(e.g. shoe polish, candles)Production of ball-point pen ink In solvents

Household commoditiesTextile and leather


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Back ground

In 2003 in ground capsicumsIn 2004 in unrefined palmoils

In 2005 in Worcester sauceCountries of origin: India, Turkey, Pakistan,

Egypt (for raw spices) Ghana, Nigeria, West

Africa (for palm oil)(Rebane et al ., 2010)


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Food applications

Illegally used as food additives particularly Chilli containing foods Palm oil containing foodstuffs Frozen meat products Spice mixtures Seasonings

Curry products

(Hea et al ., 2007)


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In duck and hen feed To enhance the egg yolks colour

(Hea et al., 2007)

Food applications


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Synthetic dyes High stability to light,

oxygen and pH Colour uniformity Low microbiological

contamination Low production cost

Natural colours Less stable Not uniform Less bright Expensive

Why use?


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Health effects

Toxicology: Degradation products are considered Carcinogens Teratogens

Sudan I: Genotoxic and carcinogen Tumours in liver or urinary bladder

Sudan II IV: Potentially genotoxic and possiblycarcinogenicSudan III cause allergic reactions

(Li et al ., 2007)


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Analysis of Sudan dyes

Extraction

Detection


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Extraction techniques

1) Solid phase extraction (SPE) Molecularly imprinted

polymers for solid phase

extraction (MISPE)2) Liquid phase microextraction (LPME)

U-shaped hollow fiber liquid phase microextraction (U-shaped HF-LPME)

Dual solvent-stir barsmicroextraction (DSSBME)


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Extraction techniques

3) Cloud point extraction (CPE)

4) Ultrasonic assisted extraction (USE)5) Pressurized liquid extraction (PLE)


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1) SPESolid sorbent (extracting phase)Sample matrix (liquid phase )Sorption depends on Sample volume

Sorbent massApplication

Product LOD (ppb)

Tomato sauce 0.1 1.67Chilli products 1Chilli powder 100 500

(Stevens et al ., 2008)


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i) MISPEPolymer structureUsed

On line

Off-lineApplication

Product LOD (ppb)

Red chilli pepper 100 500

(Puoci et al ., 2005)


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2) LPMEPartition between

Bulk aqueous phaseSmall volume of organic solvent

It integratesExtractionConcentrationSample introduction for detection

(Yu et al ., 2008)


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i) U-shaped HF-LPME

To increase interface area

Fiber in U shapeCentrifugation is necessary

(Yu et al ., 2008)


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Product LOD (ppb)

Chilli sauce 2.5

Capsicurm oil 2.5

Chilli oil sauce 6.2

Strawberry sauce 5.4

Application

(Yu et al ., 2008)


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19Setup of (a) DSSBME and (b) U-shaped HF LPME.


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ii) DSSBME

Derived from HF-LPMETwo times faster

More stableRequires less aqueous solution

(Yu et al., 2008)


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Application

Product LOD (ppb)

Salted egg 3.2

Chilli oil sauce 4.8

Strawberry sauce 1.6

(Yu et al ., 2008)


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3) CPE

Surfactant-mediated phase separationLess toxic surfactants

Application

Product LOD (ppb)

Chilli powder 2 4

(Liuet al

., 2007)


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4) USE

Product LOD (ppb)

Hot chilli 5000

Hot chilli powder 5

High frequency ultrasound

Application

(Meiju et al ., 2007)


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5) PLE

High temperature results in Solubility Diffusion rate

High pressure keeps Solvent below its boiling point

(Pardo et al ., 2009)


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Application

Product LOD (ppb)

Chilli tomato sauces 0.006Chilli powder 0.002

Curry powder 0.006

(Pardo et al ., 2009)


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Detection methods

1) Liquid chromatography2) Gas chromatography mass spectrometry (GC MS)3) Ultra performance liquid chromatography (UPLC)4) Enzyme-linked immunosorbent assays (ELISAs)5) Capillary electrophoresis6) Plasmon resonance light scattering (PRLS)


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1) Liquid chromatography (LC)

Ultra-violet visible (UV vis) absorbance Photodiode array (PDA) Mass-spectrometric detector (MSD)

Ionization technique used in LC MS Electrospray ionization (ESI) Atmospheric pressure chemical ionization

(APCI)

(Rebane et al., 2010)


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Conti By LC UV in egg

Limit of detection (LOD) 4.0 4.8g kg1 Limit of quantification (LOQ) 12.3 13.8g

kg1

By LC PDA in chilli powder LOD 200 ppb

(Cornet et al., 2006)2) By GC MS in egg

LOQ 2.0 4.2g kg1(Hea et al., 2007)


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3) UPLC MSD

In duck egg yolk LOD 1.8 2.1 ppb

In Tomato sauce LOD 0.1 1.67 ppb

(Li et al., 2009)


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4) ELISAs

Polyclonal antibody (pAb)(Dan et al ., 2007 )

Monoclonal antibody (mAb)

In Tomato sauce, sausage and chilli sauce LOD 0.07 0.14 ppb

(Wang et al ., 2009)


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Conclusion

Solid liquid extraction is dominating sample preparation procedure

Supplemented by USE and PLELC UV vis and LC MS dominating methods


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References

Cornet V, Govaert Y, Moens G, Loco JV, Degroodt JM(2006) Development of a fast analytical method for thedetermination of Sudan dyes in chilli and currycontaining foodstuffs by high performance liquidchromatography photodiode array detection. J Agric

Food Chem 54: 639 645.Dan H, Yu M, Knopp D, Niessner R, Deng AP (2007)Assay of Sudan I contamination of foodstuff atmospheric pressure chemical ionization tandem massspectrometry and isotope dilution. J Agric Food Chem55: 6424 6428.Hea L, Sub Y, Fang B, Shen X, Zenga Z, Liu Y (2007)Determination of Sudan dye residues in eggs by liquidchromatography and gas chromatography mass

spectrometry. Anal Chimica Acta 594: 139 146.


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Li C, Yang Y, Zhang Y, Wu YL (2009) Atmospheric pressure photoionization: An ionization method for liquid chromatography mass spectrometry. Anal ChemChromatogr 70: 311 319.Li L, Gao HW, Ren JR, Chen L, Li YC, Zhao JF, ZhaoHP, Yuan Y (2007) Development and optimization of ananalytical method for the determination of Sudan dyes

in hot chilli pepper by highperformance liquidchromatography with on-line electrogenerated BrO-luminol chemiluminescence detectio. BMC Struct Biol7: 418 424.Liu W, Zhao WJ, Chen JB, Yang MM (2007)Surfactant-mediated extraction technique usingalkyltrimethylammonium surfactants. Extraction of selected chlorophenols from river water. Anal ChimActa 41: 605 612.


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Meiju D, Xiaogang G, Zihao Z, Shouguo W (2007)Determination of banned Sudan dyes in chilli powder

by capillary electrophoresis. J Food Chem 105: 883 889.Pardo O, Yus V, Len N, Pastor A (2009) An acid-induced phase cloud point separation approach usinganionic surfactants for the extraction and

preconcentration of organic compounds. Talanta 78:178 183.Puoci F, Garreffa C, Lemma F, Muzzalupo R,Spizzirri UG, Picci N (2005) Molecularly imprintedsolid phase extraction for detection of sudan I in foodmatrices. J Food Chem 93: 338 349.


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Rebane R, Leito I, Yurchenko S, Herodes K (2010) Areview of analytical techniques for determination of Sudan I IV dyes in food matrixes. J Chromatogra A1217: 2747 2757.Stevens JM, Crawford M, Robinson G (2006) TotallyAutomated Method for the Determination of Sudan Dyesin Food Via On-line Filtration, SPE and HPLC analysis.Gilson Application Note, Available athttp://www.gilson.com/ (accessed 17.08.09).Wang Y, Dapeng W, Hong Y, Yuan Y, Weiwe X, YuanL, Anping D (2009) Development of a highly sensitiveand specific monoclonal antibody-based enzyme-linkedimmunosorbent assay (ELISA) for detection of Sudan I infood samples. Talanta 77: 1783 1789.


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Yu C, Liu Q, Lan L, Hu B (2008) Separation of Sudan dyes by reverse-phase high performance liquid

chromatography through statistically designedexperiments. J Chromatogra 124: 1182 1188.


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