BLUK122-Dijkstra September28,2007 19:12 Trans Fatty Acids i BLUK122-Dijkstra September28,2007 19:12 Trans Fatty Acids Edited by Albert J. Dijkstra Richard J. Hamilton Wolf Hamm iii BLUK122-Dijkstra September28,2007 19:12 (cid:2)C 2008byBlackwellPublishingLtd BlackwellPublishingeditorialoffices: BlackwellPublishingLtd,9600GarsingtonRoad,OxfordOX42DQ,UK Tel:+44(0)1865776868 BlackwellPublishingProfessional,2121StateAvenue,Ames,Iowa50014-8300,USA Tel:+15152920140 BlackwellPublishingAsiaPtyLtd,550SwanstonStreet,Carlton,Victoria3053,Australia Tel:+61(0)383591011 TherightoftheAuthortobeidentifiedastheAuthorofthisWorkhasbeenassertedinaccordancewiththeCopyright, DesignsandPatentsAct1988. Allrightsreserved.Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmitted,inanyformor byanymeans,electronic,mechanical,photocopying,recordingorotherwise,exceptaspermittedbytheUKCopyright, DesignsandPatentsAct1988,withoutthepriorpermissionofthepublisher. 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ForfurtherinformationonBlackwellPublishing,visitourwebsite:www.blackwellpublishing.com iv BLUK122-Dijkstra September28,2007 19:12 Contents Contributors ix Preface xi 1 Fattyacids:structure,occurrence,nomenclature,biosynthesis andproperties 1 RichardJ.Hamilton 1.1 Introduction 1 1.2 Fattyacidnomenclature 2 1.2.1 Saturatedacids 2 1.2.2 Monounsaturatedacids 4 1.2.3 Diunsaturatedacids 7 1.2.4 Triunsaturatedacids 7 1.3 Occurrence 7 1.4 Fattyacidbiosynthesis 12 1.4.1 Saturatedfattyacids 12 1.4.2 Monoenoicfattyacids 12 1.4.3 Polyunsaturatedfattyacids 14 1.5 Propertiesoftransfattyacids 15 1.5.1 Meltingpoints 17 1.5.2 Ultravioletspectra 18 1.5.3 Infraredspectra 20 1.5.4 Nuclearmagneticresonancespectroscopy 22 1.6 Labellingandlegislation 23 2 Transfattyacidsintake:epidemiologyandhealthimplications 25 GeokLinKhorandNorhaizanMohdEsa 2.1 Introduction 25 2.2 Foodsourcesoftransfattyacids 26 2.3 Transfattyacidsintake 30 2.4 Transfattyacidsinhumanmilk 39 2.5 Transfattyacidsintakeandhealthimplications 40 2.5.1 Coronaryheartdisease 40 2.5.2 Diabetes 43 2.5.3 Cancer 44 2.6 Concludingremarks 45 BLUK122-Dijkstra September28,2007 19:12 vi Contents 3 Conjugatedlinoleicacideffectsonbodycompositionandclinical biomarkersofdiseaseinanimalsandman:metabolicandcellmechanisms 54 KlausW.J.Wahle,MarieGoua,SimonaD’UrsoandStevenD.Heys 3.1 Generalintroduction:conjugatedlinoleicacidsandhealth 54 3.2 Structure,dietaryoriginsandconsumptionofCLAsinman 55 3.2.1 Structure 55 3.2.2 OriginsofCLAsinthehumandiet 56 3.2.3 DietaryconsumptionofCLAsinman 59 3.3 CLAsincancerpreventionandtreatment 59 3.3.1 Epidemiologyofdietaryfatsandcancerrisk 60 3.3.2 CLAsandbreastcancer 60 3.3.3 CLAsandprostatecancer 62 3.3.4 CLAsingastrointestinalcancer 64 3.3.5 CLAsandothercancers(hepatic,pancreaticanddermal) 66 3.4 CellularmechanismsofCLAs’anti-cancereffects 67 3.4.1 Inhibitionofangiogenesis 72 3.4.2 Attenuationofcancermetastasis 73 3.4.3 Reductionofcancercachexia 74 3.5 EffectofCLAsonbodycompositionandenergymetabolismin animalsandmen 75 3.5.1 Bodycompositioninanimals 75 3.5.2 Bodycompositioninman 76 3.5.3 Possiblemechanismsunderlyingreportedchangesinbody composition 78 3.5.4 EfficacyofdifferentCLAisomersinregulatingbodycomposition 78 3.6 OtherreportedhealthbenefitsofCLAs 79 3.6.1 Effectsoninsulinresistanceanddiabetes 80 3.6.2 Modulationofimmunefunctions 81 3.6.3 EffectsofCLAsonbiomarkersofcardiovasculardisease 87 3.7 ReportedadversehealtheffectsofCLAsinvivoandinvitro 90 3.8 Conclusions 91 4 Analysisoftransmono-andpolyunsaturatedfattyacids 102 Jean-LouisSe´be´dioandW.M.NimalRatnayake 4.1 Introduction 102 4.2 Isomericfattyacidsinthehumandiet 102 4.3 GaschromatographyandFouriertransforminfraredspectroscopy 106 4.4 DirectGCanalysis 106 4.4.1 Analysisofmonounsaturatedisomers 106 4.4.2 Isomersoflinoleicand(cid:2)-linolenicacids 111 4.4.3 Resolutionofeicosenoicand(cid:2)-linolenicacidisomers 113 4.4.4 Effectofthetypeofcarriergasandflowrateoncisandtrans isomerresolutionandfattyacidquantification 114 4.4.5 Conjugatedfattyacids 116 4.5 Silvernitratethin-layerandhigh-performanceliquidchromatography separationofcisandtransisomers 123 BLUK122-Dijkstra September28,2007 19:12 Contents vii 4.5.1 Monounsaturatedfattyacidisomers 123 4.5.2 Conjugatedfattyacids 125 4.6 Utilisationofpre-fractionationstepspriortochromatographic analysis:thecaseofdairyfats 127 4.7 Conclusion 128 5 Controllingphysicalandchemicalpropertiesoffatblendsthroughtheir triglyceridecompositions 132 AlbertJ.Dijkstra 5.1 Introduction 132 5.2 Definingtriglyceridecompositions 133 5.3 Meltingpointsandsfc 135 5.4 Theeffectofoilprocessingontriglyceridegroups 136 5.4.1 Hydrogenation 136 5.4.2 Fractionation 138 5.4.3 Interesterification 139 5.4.4 Otheroiltreatments 141 5.5 Usingtriglyceridegroupsinproductdevelopment 143 6 Transisomercontrolinhydrogenationofedibleoils 147 AnnemarieBeers,RobAriaanszandDouglasOkonek 6.1 Introduction 147 6.1.1 Hydrogenationprocess 147 6.1.2 Historyofhydrogenation 147 6.1.3 Reasonsforhydrogenation 147 6.2 Isomerisation 148 6.2.1 Geometricandpositionalisomerisation 148 6.2.2 Controllingisomerisation 149 6.3 Reactionmechanism 149 6.3.1 ‘Half-hydrogenated’intermediate 149 6.3.2 Saturation,positionalandgeometricisomerisation 149 6.4 Industrialhydrogenation 150 6.4.1 Batchprocess 150 6.4.2 Reactortypesandfeatures 151 6.4.3 Reactionparameters 151 6.4.4 Influenceoffeedstockontrans 153 6.4.5 Influenceofreactionconditionsontrans 157 6.4.6 Influenceofcatalystontrans 158 6.4.7 Influenceofreactordesignontrans 160 6.4.8 Transisomercontrol 160 6.5 Newdevelopmentsinlowtranshydrogenation 162 6.5.1 Alternativereactionconditions 162 6.5.2 Alternativehydrogenationprocesses 163 6.5.3 Hydrogenationadditives 169 6.5.4 Alternatecatalysts 169 6.6 Summary 175 BLUK122-Dijkstra September28,2007 19:12 viii Contents 7 Fractionationandinteresterification 181 WimDeGreytandAlbertJ.Dijkstra 7.1 Introduction 181 7.2 Fractionation 182 7.2.1 Historical 182 7.2.2 Fatcrystallisationtheory 183 7.2.3 Fatcrystallisationpractice 185 7.2.4 Separationprocesses 185 7.2.5 Fractionationproducts 187 7.3 Interesterificaton 191 7.3.1 Historical 191 7.3.2 Interesterificationmechanism 192 7.3.3 Interesterificationpractice 196 7.3.4 Interesterificationproducts 198 8 Foodapplicationsoftransfattyacids 203 JohnPodmore 8.1 Introduction 203 8.2 Margarine 205 8.2.1 Tablemargarine 205 8.2.2 Cakemargarine 208 8.2.3 Pastrymargarine 209 8.3 Biscuitfats 210 8.3.1 Doughfats–shortdoughbiscuits 210 8.3.2 Doughfat–laminatedbiscuits 211 8.3.3 Creamfillingfat 211 8.4 Fatsforchocolateconfectionery 211 8.5 Fatsforsugarconfectionery 214 8.6 Vanaspati 215 8.7 Syntheticcreams 216 8.7.1 Whippedtoppings 216 8.7.2 Coffeewhiteners 216 8.8 Concludingremarks 217 9 Foodproductswithouttransfattyacids 219 PernilleGerstenbergKirkeby 9.1 Introduction 219 9.2 Fatphase 219 9.3 Margarineandrelatedproducts 222 9.4 Manufacturingprocess 225 9.5 Optimalprocessingconditions 230 9.6 Finalremarks 233 Index 235 Thecolourplatesectionfollowspage228 BLUK122-Dijkstra September28,2007 19:12 Contributors RobAriaansz WolfHamm BASFNederlandB.V. Harpenden,UK DeMeern,TheNetherlands ProfessorStevenD.Heys DrAnnemarieBeers DepartmentofSurgicalandNutritional BASFNederlandB.V. Oncology DeMeern,TheNetherlands MedicalSchool,AberdeenUniversity Aberdeen,UK DrWimDeGreyt DeSmetTechnologies&Services ProfessorGeokLinKhor Zaventem,Belgium DepartmentofNutritionandDietetics FacultyofMedicineandHealthSciences DrAlbertJ.Dijkstra UniversitiPutraMalaysia ConsultanttotheOilsandFatsIndustry Serdang,Malaysia StEutrope-de-Born,France DouglasOkonek SimonaD’Urso BASFCatalystsLLC DepartmentofZootechnologicalSciences Iselin,NJ,USA andNutrition FredericoIIUniversityofNapoli JohnPodmore Naples,Italy ConsultanttotheOilsandFatsIndustry Liverpool,UK DrNorhaizanMohdEsa DepartmentofNutritionandDietetics DrW.M.NimalRatnayake FacultyofMedicineandHealthSciences NutritionResearchDivision UniversitiPutraMalaysia FoodDirectorate Serdang,Malaysia HealthProductsandFoodBranch HealthCanada PernilleGerstenbergKirkeby Ottawa,Ontario,Canada GerstenbergSchroederA/S Brondby,Denmark ProfessorJean-LouisSe´be´dio DrMarieGoua INRA,Unite´ deNutritionHumaine TheRobertGordonUniversity MassSpectrometryPlatform SchoolofLifeSciences SaintGene`sChampanelle,France Aberdeen,UK ProfessorKlausW.J.Wahle ProfessorRichardJ.Hamilton TheRobertGordonUniversity ConsultantinOilsandFatsChemistry SchoolofLifeSciences Merseyside,UK Aberdeen,UK BLUK122-Dijkstra September28,2007 19:12 Preface Overthelastseveraldecades,agreatdealofworkhasbeencarriedoutontransfattyacids withinanumberofinterrelatedfields,suchasnutrition,health,foodscienceandindustrial processing.Inchapterswrittenbyleadingexperts,thisvolumeoffersaclearperspectiveof thecurrentpositionoftransfattyacidsincommerceandacademicresearch. Thebookisdesignedasanaidtoresearchersandprofessionalsinnutritionandhealthand thoseprovidinganalyticalservicestothefoodindustry.Readersseekingwaystoformulate oilblendswithouttransfattyacidsandthosewishingtoalterthecompositionofoilsandfats bymeansofinteresterification,fractionationandhydrogenationwillfindalargeamountof researchdescribedandmanyapplicationsoutlined.Theywillalsofindmethodsofadjusting the formulation of their products and their processing. The book is written in a reader- friendlystyle,whichwillpermitnewcomerstotheareatograspthewaysinwhichthefield isprogressing.Eachchaptercontainsmanyofthelatestreferencesandsignificantareasof research. Chapter1introducestransfattyacidsandputsthemintheirpropercontextinrelationto themanyothersaturatedandunsaturatedacidsfoundinnature.Itshowshowtransacidsare producedbothinindustryandbynaturalbiohydrogenationinanimalsandplants.Itoutlines someofthepropertiesoftransfattyacidsandcontraststhemwiththoseoftheircisisomers. Chapters 2 and 3 deal with the health implications and the epidemiology of trans fatty acids.IntakesoftransacidsintheUSA,CentralAmerica,Nigeria,Iran,India,China,Hong Kong,NewZealand,Australia,Hungary,theCzechRepublic,Poland,BulgariaandSpainare considered.Anumberofstudies,e.g.theZutphenElderly,theScottishHeartandHealth,the SevenCountries,theNursesHealthandtheEURAMICcasecontrol,havebeenreferenced. Theresultsareconsideredwithoutbiasandtheauthorsarenotafraidtopointoutwherefurther research is needed to confirm the original conclusions. In the consideration of conjugated linoleic acid (Chapter 3), the authors discuss the synthetic products that can be used for humanandanimalsupplementation. With the realization that not all trans fatty acids have the same biological effect came the realization that it is important to know more than just the total trans fatty acid content inafood.Chapter4explainshowdirectGC,GC-MS,AgNO -TLCandHPLCareusedto 3 determinethetransfattyacidcompositionofvariousfoodproducts.Somerecommendations forthebestanalysisofcis/transmonounsaturatedfattyacidsaregiven,whilsttheneedfor pre-fractionationinsomeinstancesishighlighted. Chapter5introducestheconceptoftriglyceridegroupsanddemonstratesthat,formost componentsusedinconstitutingfatblends,thetriglyceridegroupcompositioncanbecalcu- lated.Itillustrateshowhydrogenation,fractionationandinteresterificationcausethetriglyc- eridegroupcompositiontochangeanditalsohighlightshowproductdevelopmentcanbe facilitatedbyspecifyingfatblendsonthebasisoftheirtriglyceridegroupcomposition. Chapter6providesawidesurveyoftheindustrialhydrogenationprocessinthefieldof edibleoilprocessing,itsmechanismandhowprocessparametersaffectthetransfattyacid