《香精香料色谱分析》Chromatography-of-Aroma-Compounds-and-Fragrances.pdf

Chromatography of Aroma Compoundsand FragrancesTibor CserhtiChromatography of AromaCompounds and Fragrances123Prof.Dr.Tibor Cserhti1149 Pillang park 8/BBudapestHungarytevichemres.huISBN 978-3-642-01655-4e-ISBN 978-3-642-01656-1DOI 10.1007/978-3-642-01656-1Springer Heidelberg Dordrecht London New YorkLibrary of Congress Control Number:2009940258 Springer-Verlag Berlin Heidelberg 2010This work is subject to copyright.All rights are reserved,whether the whole or part of the material isconcerned,specifically the rights of translation,reprinting,reuse of illustrations,recitation,broadcasting,reproduction on microfilm or in any other way,and storage in data banks.Duplication of this publicationor parts thereof is permitted only under the provisions of the German Copyright Law of September 9,1965,in its current version,and permission for use must always be obtained from Springer.Violationsare liable to prosecution under the German Copyright Law.The use of general descriptive names,registered names,trademarks,etc.in this publication does notimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevantprotectivelaws and regulations and therefore free for general use.Cover design:WMXDesign GmbHPrinted on acid-free paperSpringer is part of Springer Science+Business Media()PrefaceThe quantity and composition of aroma and flavour compounds in foods and foodproducts exert a marked influence on the consumer acceptance and,consequently,on the commercial value of the products.It has been established many times thatone of the main properties employed for the evaluation of the product quality isthe flavour,that is,an adequate flavour composition considerably enhances the mar-ketability.Traditional analytical methods are generally unsuitable for the accuratedetermination of the quantity of this class of compounds.Moreover,they do notcontain any useful information on the concentration of the individual substances andthey are not suitable for their identification.As the stability of the aroma compoundsand fragrances against hydrolysis,oxidation and other environmental and techno-logical conditions shows marked differences,the exact determination of the flavourcomposition of a food or food product may help for the prediction of the shelf-life of products and the assessment of the influence of technological steps onthe aroma compounds resulting in more consumer-friendly processing methods.Furthermore,the qualitative determination and identification of these substancesmay contribute to the establishment of the provenance of the product facilitatingthe authenticity test.Because of the considerable commercial importance of flavourcomposition,much effort has been devoted to the development of methods suitablefor the separation and quantitative determination of flavour compounds and fra-grancesinfoodsandinotherindustrialproducts.Thehighseparationcapacityofgaschromatography(GC)technologies and the volatility of the majority of aromacompounds make it a method of preference for the analysis of flavour andaroma compounds and fragrances.Other separation technologies such as thin-layer chromatography(TLC),high-performance liquid chromatography(HPLC)and electrically drived techniques have also found application in the separation andquantitative determination of aroma compounds.As the development of chromato-graphic separation techniques is very rapid,the number of new chromatographicmethods employed for the analysis of flavour compounds is also rapidly increasing.The objectives of the book are the compilation of the newest results in this fieldof research,the critical evaluation of the results and the prediction of the futuretrends in the study of these compound classes.The book aims to be self-sufficientin terms of the need of the professional intending to work in this interesting field.IvviPrefaceam confident that the book will be useful as a valuable reference for researchers andadvanced students interested in the topics covered.The author is grateful to Ms.Eva Tarls and Ms.Esther Bartha for their valuabletechnical assistance.Budapest,HungaryTibor CserhtiContents1Chromatography of Aroma Substancesand Fragrances.11.1Theory and Practice of Chromatographic Techniques.11.1.1Preconcentration and Prepurification of Analytes.11.1.2Gas Chromatography(GC).31.1.3Liquid Chromatography(LC).61.1.4Electrically Drived Chromatographic Systems.9References.102Food and Food Products.132.1Fruits.132.1.1Tropical Fruits.142.1.2Non-tropical Fruits.262.2Legumes and Vegetables.422.3Cereals.502.4Edible Oils.552.5Meat and Meat Products.662.6Milk and Dairy Products.1042.7Non-alcoholic Beverages.1242.8Alcoholic Beverages.1332.8.1Wines.1332.8.2Other Alcoholic Beverages.1662.9Coffee,Tea and Cocoa.1842.10Spices.2042.11Other Food Products.233References.2523Essential Oils.2693.1General Considerations.2693.2Essential Oils with Favourable Biological Actions.2713.3Other Essential Oils.295References.312viiviiiContents4Biological Effect.3174.1Biochemistry and Biophysics.3174.2Toxicity Studies.330References.3415Environmental Pollution.3455.1Ground and Surface Water.3455.2Waste Water and Sludge.3625.3Miscellaneous Environmental Matrices.372References.379Index.383Abbreviations2-AAP2-aminoacetophenoneACNacetonitrileADair-dryingAEDatomic emission detectionAPCIatmospheric pressure chemical ionisationBP-ANNback-propagation feed-forward artificial networkCARcarboxenCEcapillary electrophoresisCFcold finger distillationCGAchlorogenic acidCGEcapillary gel electrophoresisCIEFcapllary isoelectric focusingCITPcapillary isotachophoresisCLNDchemiluminescence nitrogen detectionCLSAclosed-loop stripping analysisCTAHcetyltrimethylammonium hydroxideCZEcapillary zone electrophoresisDFAdetection frequency analysisDGGEdenaturing gradient gel electrophoresisDHSdynamic headspace extractionD-HSdynamic headspace samplingDI-SPMEdirect-immersion solid-phase microextractionDLLMEdispersive liquidliquid microextractionDTDdirect thermal desorptionDVBdivinylbenzeneEDelectrochemical detectionECDelectron capture detectorEI-MSelectron impact mass spectrometryELSDevaporative light-scattering detectorEnantio-MDGC-MSenantioselective multidimensional gaschromatography-mass spectrometryESI-MSelectron spray ionisation mass spectrometryFAAfree amino acidsixxAbbreviationsFAB-MSfast atom bombardment mass spectrometryFDAfactorial discriminate analysisFFAfree fatty acidsFIDflame ionisation detectorFPDflame photometric detectorGCgas chromatographyGCO,GC-Ogas chromatography-olfactometryGCO-Hgas chromatography-olfactometry of headspaceGLCgasliquid chromatographyGSCgassolid chromatographyHtheoretical plate heightHCC-HShigh concentration capacity headspace samplingHDhydrodistillationHMFhydroxymethylfurfurolHPGFChigh-performance gel filtration chromatographyHPLChigh-performance liquid chromatographyHPSEChigh-performance size exclusion chromatographyHRGC-IRMSgas chromatography-isotope ratio mass spectrometryHS-LPMEheadspace liquid-phase microextractionHP-SPMEheadspace solid-phase microextractionHSSEheadspace sorptive extractionHVDhigh-vacuum distillationIretention indexi.d.internal diameterIECion-exchange chromatographyIGCinverse gas chromatographyISinternal standardKDdistribution constantkcapacity factorLCliquid chromatographyLDlimit of detectionLDAlinear discriminant analysisLLEliquidliquid extractionLODlimit of detectionLOQlimit of quantitationMADmicrowave-accelerated distillationMDGC-Omultidimensional GC-olfactometryMEKCmicellar electrokinetic chromatographyMNmethyl nicotinateMSmass spectrometryNCInegative chemical ionisationNMRnuclear magnetic resonanceNPSDnitrogen purge steam distillationODSoctadecyl silicaPAGEpolyacrylamide gel electrophoresisAbbreviationsxiPCAprincipal component analysisPDMSpolydimethylsiloxanePDOprotected designation of originPFPDpulsed flame photometric detectionPGCporous graphitised carbonPHWpressurised hot waterPLSpartial least squaresPTVprogrammable temperature vaporisation injectorPy-GC-MSpyrolysis gas chromatography mass spectrometryRPreversed-phaseRP-HPLCreversed-phase high-performance liquid chromatographyRP-TLCreversed-phase thin-layer chromatographyRSDrelative standard deviationSbCWEsubcritical water extractionSBFsimulated beef flavourSBSEstir bar sorptive extractionSDsteam distillationSDEsimulataneous distillation extractionSECsize exclusion chromatographySFEsupercritical fluid extractionSIMselected ion monitoringSAFEsolvent-assisted flavour evaporationSFSIsolvent-free solid injectionSPACEsolid-phase aroma concentrate extractionSPEsolid-phase extractionSPIsoy protein isolateSPMEsolid-phase microextractionTRretention timeTDCTthermal desorption cold-trapTFAtrifluoroacetic acidTLCthin-layer chromatographyTOFStime-of-flight mass spectrometerUSEorganic solvent extraction under ultrasonic irradiationUV-VISultraviolet-visibleVNnet retention volumeVBDvacuum belt dryingVOCvolatile organic compoundChapter 1Chromatography of Aroma Substancesand Fragrances1.1 Theory and Practice of Chromatographic TechniquesThe base of any chromatographic separation methods is the partition of the analytesbetween a solid or semisolid stationary and a mobile phase consisting of gas orfluid.Because of the different physicochemical characteristics of the analytes,theydiffer in their capacity to bind to the stationary and mobile phases.Because of thedifferences between the binding energies,analytes show different mobility in thechromatographic system resulting in their separation.1.1.1 Preconcentration and Prepurification of AnalytesThe concentration of aroma substances,flavour compounds and fragrances is gen-erally low in the samples;moreover,they are present in complicated matricesfrequently containing both organic and inorganic components such as various foodsand food products,cosmetics,pharmaceutical preparations.The aim of the samplepreparation is the prepurification and/or preconcentration of the solutes to be anal-ysed and the possible decrease of the disturbing accompanying components whichcan deteriorate the efficacy of the analysis,reduce the theoretical plate number,modify separation factor,peak symmetry,reproducibility and repeatability.Samplepreparation often plays a decisive role in the success of any chromatographic analy-sis.The conventional method of sample preparation is the shake flash extraction andits modern variant,the Soxhlet extraction.These liquid extraction or liquidliquidextraction(LLE)techniques are generally very efficient but time-consuming,andthe considerable amount of organic solvent can endanger the health of the labora-tory staff and can increase environmental pollution.The extracting solvent has tocomply with some requirements.First of all,it cannot be toxic neither to humansnor to any living organism;it has to be selective as much as possible dissolvingmaximally the analytes and minimally the other components present in the sample.Because of the complexity of both the composition of aroma substances and that ofother undesirable compounds in the sample,the objective to find and use the idealsolvent can be only approximately fulfilled.1T.Cserhti,Chromatography of Aroma Compounds and Fragrances,DOI 10.1007/978-3-642-01656-1_1,C?Springer-Verlag Berlin Heidelberg 201021Chromatography of Aroma Substances and FragrancesIn order to overcome the disadvantages of the LLE method mentioned above,a considerable number of up-to-date extraction methods were developed andsuccessfully applied for the preconcentration and prepurification of aroma sub-stances and fragrances in various accompanying matrices.Solid-phase extraction(SPE)can be applied for the preconcentration and pre-purification of both liquid samples and for the liquid extract of solid samples.The liquid containing the compounds to be analysed is passed through a glass orplastic cartridge filled with a sorbent with high adsorption capacity.The analyteswill remain in the cartridge adsorbed on the surface of the sorbent.After finishingthe adsorption step,the sorbent is washed to remove the majority of coadsorbedcomponents.Then a strong sorbent is applied for the removal of the molecules of interest.Themain requirements for an efficient SPE method are the highest possible selectivityand adsorption capacity of the sorbent.The selection of the sorbent depends on theoretical consideration.Nonpolaranalytes can be retained on nonpolar sorbents while analytes with polar substruc-tures can adsorb on sorbent containing adsorption centres of opposite polarity.Thevolume of sorbing commercially varies between 1 and 50 ml.Solid-phase microextraction(SPME)uses a short thin solid rod(generally 1 cmlong and 0.1 m outer diameter),sometimes coated with a polar or nonpolarpolymer.The SPME fibre is attached to a metal rod.Before analysis the fibre iswithdrawn into a protective sheath.The sample is placed in a vial and the vialis closed with a cap containing a septum.The sheath is pushed through the sep-tum,the plunger is lowered forcing the adsorptive fibre into the vial.The fibre canbe immersed in the liquid sample or let in contact with the headspace over thesolid or liquid sample.Analytes are adsorbed into the fibre.After reaching equi-librium between the adsorbed and nonadsorbed fractions of analytes,the fibre iswithdrawn into the sheath and the sheath is pulled out of the vial,and inserted inthe septum of the injector of gas chromatograph(GC).After thermal desorption theanalytes are separated in the GC column.The adsorption characteristics of poly-mers(polydimethylsiloxane,polyacrylate,carbowax/divinyl benzene,etc.)havebeen vigorously investigated and their application in solution of various separationproblems was proposed.As the equilibrium between the adsorbed and nonabsorbedanalytes may be different even for molecules of very similar chemical structure,theefficacy of SPME shows high differences depending on both the character of theadsorbent and that of the analytes.A careful calibration of each components of the sample is a prerequisite forthe precise quantitation of the data using SPME.The method has been extensivelyapplied for the determination of furan in baby-food(Bianchi et al.,2006),volatileoak compounds(Carrillo et al.,2006)and volatile phenols in wine(Mejias et al.,2003),sorbic and benzoic acids in beverages(Dong and Wang,2006),aroma activecompounds in orange essence oil(Hognadottir and Rouseff,2003),organophos-phorus insecticides in strawberry and cherry juices(Lambropoulou and Albanis,2002),headspace flavour compounds of banana(Liu and Yang,2002),volatilecompounds in fruit juices and nectars(Riu-Aumatell et al.,2004)and aromavolatiles from orange juices(Rouseff et al.,2001).1.1Theory and Practice of Chromatographic Techniques3Supercritical fluid extraction(SFE)is a solvent-free alternative to the extractionmethods discussed above.It applies inexpensive and environmental-friendly mobilephase(carbon dioxide or carbon dioxide mixed with organic solvents).The extrac-tion time is shorter and the extract can be used directly for GC,TLC and