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JournalofChromatographyA,1218(2011)7438–7452ContentslistsavailableatScienceDirectJournalofChromatographyAjournalhomepage:éBernala,∗,AnaM.Aresa,JaroslavPólb,SusanneK.Wiedmerc,∗∗aI.U.CINQUIMA,AnalyticalChemistryGroup,UniversityofValladolid,E.47071Valladolid,SpainbThermoFisherScientific,Sluneˇcná27,10000Praha10,CzechRepubliccLaboratoryofAnalyticalChemistry,DepartmentofChemistry,POB55,00014UniversityofHelsinki,FinlandarticleinfoArticlehistory:Availableonline11May2011Keywords:HILICMechanismStationaryphasesFoodApplicationsabstractTheuseofhydrophilicinteractionliquidchromatography(HILIC)infoodanalysisinthelastdecadeisreviewed.TheHILICmechanismisbrieflydiscussed,butmainemphasisisputontheuseofHILICforseparationofdifferentfoodmatrices.Thefoodmatricesaredividedintofoodofanimaloriginandrelatedproducts,vegetables,fruitsandrelatedcompounds,andotherfood-relatedmatrices.Alistonimportantapplicationsisprovidedforeachcategoryincludingexperimentalconditionsandabriefsummaryoftheresults.The100referencesincludedwillprovidethereaderacomprehensiveoverviewandinsightintoHILICapplicationstofoodanalysis.©2011ElsevierB.V.Allrightsreserved.Contents1.Introduction..........................................................................................................................................74382.HILICmechanism....................................................................................................................................74392.1.Typicalcolumnsandsolvents................................................................................................................74393.ApplicationofHILICinfoodmatrices................................................................................................................74393.1.Foodofanimaloriginandrelatedproducts..................................................................................................74413.2.Foodandbeveragesofplantorigin..........................................................................................................74463.3.Othermatrices................................................................................................................................74504.Conclusions..........................................................................................................................................7451References...........................................................................................................................................74511.IntroductionLookingbackonthehistoryofliquidchromatography,thepio-neerliquidchromatographicsystemshasbeenoperatedinnormalmode(NPLC),whichmeansthatthestationaryphasehasbeenpolarandelutionhasbeenaccomplishedbynon-polarorganicsol-vents.Suchstationaryphases,however,exhibitedheterogeneitythatresultedinpeaktailingandnon-linearretentionfactorswithvaryinganalyteconcentration.Later,thedevelopmentofstation-aryphasesforchromatography,drivenbypharmaceuticalstudiesofwater/octanolpartitioning,offeredreversedphase(RP)systems[1,2].Bondedoctadecylstationaryphasesallowedefficientsepa-rationofanalyteswithinbroadrangeofpolarityandfastcolumnequilibration.Thelackofretentionofhighlyhydrophiliccom-∗Correspondingauthor.Tel.:+34983186347;fax:+34983423013.∗∗Correspondingauthor.Tel.:+358919150264;fax:+358919150253.E-mailaddresses:jose.bernal@qa.uva.es(J.Bernal),susanne.wiedmer@helsinki.fi(S.K.Wiedmer).poundswithfunctionalgroupsallowingdipolarbondingonRPhasbeensupplementedbyseparationonionexchangechromatogra-phy[3]orionparingonRP[4].However,largegroupofstronglyhydrophiliccompoundswithoutthepossibilitytoreceivechargeinsolutionhasnotbeenabletoreceiveretentiononeitherstationaryphases.TheproblemhasbeenovercomeinGCbyderivatization,andrecently,inLCbydevelopinghydrophilicinteractionchro-matography(HILIC)[5].TheconceptofHILICisinawayreversed,wherepolarstationaryphaseretainspolaranalytesthatareelutedbymixtureoforganicsolvent(usuallyacetonitrile)andwater.HILICoperationmodeisfriendlyformassspectrometry(MS)analysiswithelectrosprayionization(ESI)sinceanalytesareionizedinaqueousorganicsolution,whichenhancesESIprocess[6].HILICseparationmechanismisoppositetothatofRPsystemsandthosetwotechniquescomplement[7].Thereforeithasbeenpopulartoemploythetwomechanismsintandemforpre-concentrationorseparationintwo-dimensions[8].EventhoughtheuseofHILIChasbeenextensivelygrowingdur-ingthelastdecade,itsmechanismisstilltodaypartlyunresolved,0021-9673/$–seefrontmatter©2011ElsevierB.V.Allrightsreserved.doi:10.1016/j.chroma.2011.05.004J.Bernaletal./J.Chromatogr.A1218(2011)7438–74527439andwediscussthisissuelaterinthetextinmoredetail.HILIChasbeenusedinallapplicationareasofliquidchromatographicsepara-tions,rangingfromanalysisofsmallmolecules[9],pharmaceuticals[10],metabolites[11],drugsofabuse[12],toxins[13],carbohy-drates[14],oligosaccharides[15],aminoacids[16],peptides[5],andproteins[17].ThisreviewsummarizesmostoftheworkcarriedoutonfoodanalysisusingHILIC

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