Lipids: Biochemistry, Biotechnology and Health

449 Pages·2016·20.12 MB·English

by  Michael I. Gurr

Lipids

Lipids:
Biochemistry,
Biotechnology
and Health
SIXTHEDITION
(formerlyLipidBiochemistry:AnIntroduction,Editions1–5)
BY
Michael I. Gurr
John L. Harwood
Keith N. Frayn
Denis J. Murphy
Robert H. Michell
Thiseditionfirstpublished20162016byJohnWiley&SonsLtd
Firstedition1971MichaelI.GurrandA.T.James;Secondedition1975MichaelI.GurrandA.T.James;Thirdedition1980MichaelI.Gurrand
A.T.James;Fourthedition1991MichaelI.GurrandJohnL.Harwood;Fifthedition2002MichaelI.Gurr,JohnL.HarwoodandKeithN.Frayn;
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LibraryofCongressCataloging-in-PublicationData
Names:Gurr,M.I.(MichaelIan),author.|Harwood,JohnL.,author.|Frayn
K.N.(KeithN.),author.|Murphy,DenisJ.,author|Michell,R.H.,author.
Lipidbiochemistry.Precededby(work):
Title:Lipids:Biochemistry,BiotechnologyandHealth/byMichaelI.Gurr,John
L.Harwood,KeithN.Frayn,DenisJ.Murphy,andRobertH.Michell.
Description:6thedition.|Chichester,WestSussex;Hoboken,NJ:John
Wiley&SonsInc.,2016.|PrecededbyLipidbiochemistry/byMichaelI.
Gurr,JohnL.Harwood,andKeithN.Frayn.5thed.2002.|Includes
bibliographicalreferencesandindex.
Identifiers:LCCN2016000533(print)|LCCN2016002203(ebook)|ISBN
9781118501139(pbk.)|ISBN9781118501085(AdobePDF)|ISBN
9781118501108(ePub)
Subjects:|MESH:Lipids
Classification:LCCQP751(print)|LCCQP751(ebook)|NLMQU85|DDC
572/.57–dc23
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Coverimages:Leftpanel:Anarterypartiallyoccludedbyanatheroscleroticplaque(Section10.5.1). Theredstainisformacrophagesthatare
presentintheplaqueandbecomefoamcells.Thegreenstainisforsmoothmusclecellsinthearterialwallandcappingtheplaque. Photocourtesy
ofThomasS.DaviesandSusanChazi,CardiffUniversity,UKfromworkfundedbytheBritishHeartFoundation.
Middlepanel:Anenterocytefromhumanjejunumdisplayingmultiplelipiddropletsafewhoursafterconsumingafattymeal(Section7.1.3).
Thefigurealsoshowsmitochondria(dark)andthemicrovilli(brushborder). ElectronmicrographcourtesyofDrMDeniseRobertson,University
ofSurrey,UKfromworkfundedbytheBiotechnologyandBiologicalSciencesResearchCouncil(BBSRC). Reproduced,withpermissionfrom
BMJPublishingGroupLtd,fromMDRobertson,MParkes,BFWarrenetal.(2003)Mobilizationofenterocytefatstoresbyoralglucoseinman.
Gut6:833–8.
Rightpanel:DistributionofdifferentmolecularspeciesofphosphatidylcholinewithindevelopingoilseedrapeembryosasrevealedbyMALDI-MS
imaging(Section9.3.1). Redshowshighconcentrationsandgreenlow. PhotocourtesyofHelenWoodfieldandDrewSturteventfromwork
fundedbytheBBSRCinProf.KentChapman’slaboratoryattheUniversityofNorthTexas,USA.
Background:Gettyimages/manuelaschewe-behnisch/eyeem
Setin8.5/12pt,MeridienLTStd-RomanbyThomsonDigital,Noida,India
1 2016
Contents
Preface,xv 2.1.3 Unsaturatedfattyacids,14
Acknowledgements,xvii 2.1.3.1 Monounsaturated(monoenoic)
fattyacids,14
Abouttheauthors,xix
2.1.3.2 Polyunsaturated(polyenoic)
Aboutthecompanionwebsite,xxi
fattyacids,15
2.1.4 Cyclicfattyacids,17
1 Lipids:definitions,naming,methodsandaguideto 2.1.5 Oxyfattyacids,17
thecontentsofthisbook,1
2.1.6 Fattyaldehydesandalcohols,18
1.1 Introduction,1 2.1.7 Somepropertiesoffattyacids,18
1.2 Definitions,1 2.1.8 Quantitativeandqualitativefattyacid
1.3 Structuralchemistryandnomenclature,1 analysis,19
1.3.1 Nomenclature,general,1 2.1.8.1 Generalprinciples,19
1.3.2 Nomenclature,fattyacids,2 2.1.8.2 Determinationofthestructure
1.3.3 Isomerisminunsaturatedfattyacids,2 ofanunknownacid,20
1.3.4 Alternativenames,3 2.2 Storagelipids–triacylglycerolsandwax
1.3.5 Stereochemistry,3 esters,20
1.3.6 Abbreviationofcomplexlipidnames 2.2.1 Introduction,20
andotherbiochemicalterms,3 2.2.2 Thenamingandstructureofthe
acylglycerols(glycerides),20
1.4 Lipidomics,4
2.2.2.1 Introduction,20
1.4.1 Introduction,4
2.2.2.2 Allnaturaloilsarecomplex
1.4.2 Extractionoflipidsfromnatural
mixturesofmolecular
samples,4
species,22
1.4.3 Chromatographicmethodsfor
2.2.2.3 Generalcommentsabout
separatinglipids,4
storagetriacylglycerolsin
1.4.4 Modernlipidomicsemploysa
animalsandplants,24
combinationofliquidchromatography
2.2.3 Waxesters,25
orgaschromatographywithmass
spectrometrytoyielddetailedprofilesof 2.2.4 Surfacelipidsincludenotonlywax
naturallipids–the‘lipidome’,6 estersbutawidevarietyoflipid
molecules,25
1.5 Aguidetothecontentsofthisbook,8
2.3 Membranelipids,26
Keypoints,11
2.3.1 Generalintroduction,26
Furtherreading,12
2.3.2 Glycerolipids,27
2 Importantbiologicallipidsandtheirstructures,13
2.3.2.1 Phosphoglyceridesarethe
2.1 Structureandpropertiesoffattyacids,13
majorlipidcomponents
2.1.1 Saturatedfattyacids,13 ofmostbiological
2.1.2 Branched-chainfattyacids,13 membranes,27
v
Contents
vi
2.3.2.2 Phosphonolipidsconstitutea 3.1.7 Thebiosynthesisofhydroxyfattyacids
rareclassoflipidsfoundina resultsinhydroxylgroupsindifferent
feworganisms,27 positionsalongthefattyacidchain,67
2.3.2.3 Glycosylglyceridesare 3.1.8 Thebiosynthesisofunsaturatedfatty
particularlyimportant acidsismainlybyoxidative
componentsofphotosynthetic desaturation,68
membranes,29 3.1.8.1 Monounsaturatedfatty
2.3.2.4 Betainelipidsareimportantin acids,68
someorganisms,31 3.1.8.2 Polyunsaturatedfattyacids,70
2.3.2.5 Ether-linkedlipidsandtheir 3.1.8.3 Formationofpolyunsaturated
bioactivespecies,31 fattyacidsinanimals,75
2.3.3 Sphingolipids,32 3.1.9 Biohydrogenationofunsaturatedfatty
2.3.4 Sterolsandhopanoids,36 acidstakesplaceinrumen
2.3.4.1 Majorsterols,36 microorganisms,75
2.3.4.2 Othersterolsandsteroids,39 3.1.10Thebiosynthesisofcyclicfattyacids
providedoneofthefirstexamplesofa
2.3.4.3 Hopanoidsandrelated
complexlipidsubstrateforfattyacid
lipids,39
modifications,77
2.3.5 Membranelipidsofthearchaea,40
3.1.11Controloffattyacidbiosynthesisin
Keypoints,42
differentorganisms,78
Furtherreading,42 3.1.11.1Substratesupplyfordenovo
3 Fattyacidmetabolism,44 fattyacidbiosynthesis,78
3.1 Thebiosynthesisoffattyacids,44 3.1.11.2Acetyl-CoAcarboxylaseandits
regulationinanimals,79
3.1.1 Conversionoffattyacidsinto
metabolicallyactivethioestersisoftena 3.1.11.3Acetyl-CoAcarboxylase
prerequisitefortheirmetabolism,44 regulationinother
organisms,81
3.1.1.1 Acyl-CoAthioesterswerethe
firsttypesofactivatedfatty 3.1.11.4Regulationoffattyacid
acidstobediscovered,45 synthase,82
3.1.1.2 Acyl-acylcarrierproteinscan 3.1.11.5Controlofanimal
befoundasdistinctmetabolic desaturases,84
intermediatesinsome 3.2 Degradationoffattyacids,85
organisms,47 3.2.1 β-Oxidationisthemostcommontypeof
3.1.2 Thebiosynthesisoffattyacidscanbe biologicaloxidationoffattyacids,85
dividedintodenovosynthesisand 3.2.1.1 Cellularsiteofβ-oxidation,85
modificationreactions,47
3.2.1.2 Transportofacylgroupstothe
3.1.3 Denovobiosynthesis,48
siteofoxidation:theroleof
3.1.3.1 Acetyl-CoAcarboxylase,49 carnitine,85
3.1.3.2 Fattyacidsynthase,50 3.2.1.3 Controlofacyl-carnitineisvery
3.1.3.3 Chaintermination,62 important,87
3.1.4 Mitochondrialfattyacid 3.2.1.4 Enzymesofmitochondrial
synthase,63 β-oxidation,87
3.1.5 Elongation,63 3.2.1.5 Otherfattyacidscontaining
3.1.6 Branched-chainfattyacids,65 branched-chains,doublebonds
Contents
vii
andanoddnumberofcarbon 3.5.13Importantnewmetabolitesofthen-3
atomscanalsobeoxidized,88 PUFAs,eicosapentaenoicand
3.2.1.6 Regulationofmitochondrial docoasahexaenoicacidshaverecently
β-oxidation,89 beendiscovered,115
3.2.1.7 Fattyacidoxidationin 3.5.14Foreicosanoidbiosynthesis,an
E.coli,91 unesterifiedfattyacidisneeded,118
3.2.1.8 β-Oxidationinmicrobodies,91 3.5.15Essentialfattyacidactivityisrelatedto
3.2.2 α-Oxidationoffattyacidsisimportant doublebondstructureandtotheability
ofsuchacidstobeconvertedinto
whensubstratestructureprevents
β-oxidation,93 physiologicallyactiveeicosanoids,119
3.2.3 ω-Oxidationusesmixed-function Keypoints,120
oxidases,94 Furtherreading,121
3.3 Chemicalperoxidationisanimportant 4 Themetabolismofcomplexlipids,124
reactionparticularlyofpolyunsaturatedfatty
4.1 Thebiosynthesisoftriacylglycerols,124
acids,95
4.1.1 Theglycerol3-phosphatepathwayin
3.4 Peroxidationcatalysedbylipoxygenase
mammaliantissuesprovidesalink
enzymes,96
betweentriacylglyceroland
3.4.1 Lipoxygenasesareimportantfor phosphoglyceridemetabolism,124
stressresponsesanddevelopment
4.1.2 Thedihydroxyacetonephosphate
inplants,97
pathwayinmammaliantissuesisa
3.5 Essentialfattyacidsandthebiosynthesisof variationtothemainglycerol
eicosanoids,100 3-phosphatepathwayandprovidesan
3.5.1 Thepathwaysforprostaglandin importantroutetoetherlipids,127
biosynthesisarediscovered,101 4.1.3 Formationoftriacylglycerolsinplants
3.5.2 Prostaglandinbiosynthesisby involvesthecooperationofdifferent
cyclo-oxygenases,101 subcellularcompartments,128
3.5.3 Nonsteroidalanti-inflammatorydrugs 4.1.4 Somebacteriamakesignificantamounts
arecyclo-oxygenaseinhibitors,103 oftriacylglycerols,132
3.5.4 Cyclicendoperoxidescanbe 4.1.5 Themonoacylglycerolpathway,132
convertedintodifferenttypesof 4.2 Thecatabolismofacylglycerols,133
eicosanoids,104
4.2.1 Thenatureanddistributionof
3.5.5 Neweicosanoidsarediscovered,105 lipases,133
3.5.6 Thecyclo-oxygenaseproductsexerta 4.2.2 Animaltriacylglycerollipasesplayakey
rangeofactivities,106 roleinthedigestionoffoodandinthe
3.5.7 Prostanoidshavereceptorsthatmediate uptakeandreleaseoffattyacidsby
theiractions,107 tissues,134
3.5.8 Prostaglandinsandothereicosanoids 4.2.3 Plantlipasesbreakdownthelipids
arerapidlycatabolized,108 storedinseedsinaspecialized
3.5.9 Insteadofcyclo-oxygenation, organelle,theglyoxysome,135
arachidonatecanbelipoxygenatedor 4.3 Theintegrationandcontrolofanimal
epoxygenated,108 acylglycerolmetabolism,136
3.5.10Controlofleukotrieneformation,108 4.3.1 Fueleconomy:theinterconversionof
3.5.11Physiologicalactionofleukotrienes,110 differenttypesoffuelsishormonally
3.5.12CytochromeP450oxygenations,112 regulatedtomaintainnormalblood
Contents
viii
glucoseconcentrationsandensure 4.5.9 Differencesbetweenphosphoglyceride
storageofexcessdietaryenergyin biosynthesisindifferentorganisms,154
triacylglycerols,136 4.5.10Plasmalogenbiosynthesis,154
4.3.2 Thecontrolofacylglycerolbiosynthesis 4.5.11Plateletactivatingfactor:abiologically
isimportant,notonlyforfueleconomy activephosphoglyceride,156
butformembraneformation,requiring
4.6 Degradationofphospholipids,157
closeintegrationofstorageand
4.6.1 Generalfeaturesofphospholipase
structurallipidmetabolism,137
reactions,157
4.3.3 Mobilizationoffattyacidsfromthefat
4.6.2 PhospholipaseAactivityisusedto
storesisregulatedbyhormonalbalance,
removeasinglefattyacidfromintact
whichinturnisresponsiveto
phosphoglycerides,158
nutritionalandphysiologicalstates,140
4.6.3 PhospholipaseBand
4.3.4 Regulationoftriacylglycerol
lysophospholipases,161
biosynthesisinoilseeds,143
4.6.4 PhospholipasesCandDremovewater-
4.4 Waxesters,143
solublemoieties,161
4.4.1 Occurrenceandcharacteristics,143
4.6.5 Phospholipidsmayalsobecatabolized
4.4.2 Biosynthesisofwaxestersinvolvesthe bynonspecificenzymes,162
condensationofalong-chainfatty
4.6.6 Endocannabinoidmetabolism,162
alcoholwithfattyacyl-CoA,145
4.7 Metabolismofglycosylglycerides,163
4.4.3 Digestionandutilizationofwaxestersis
poorlyunderstood,145 4.7.1 Biosynthesisofgalactosylglycerides
takesplaceinchloroplast
4.4.4 Surfacelipidsincludewaxestersanda
envelopes,163
widevarietyofotherlipids,146
4.7.2 Catabolismofgalactosylglycerides,164
4.5 Phosphoglyceridebiosynthesis,146
4.7.3 Metabolismoftheplant
4.5.1 Tracerstudiesrevolutionizedconcepts
sulpholipid,164
aboutphospholipids,146
4.8 Metabolismofsphingolipids,165
4.5.2 Formationoftheparentcompound,
phosphatidate,isdemonstrated,147 4.8.1 Biosynthesisofthesphingosinebase
andceramide,165
4.5.3 Anovelcofactorforphospholipid
biosynthesiswasfoundby 4.8.2 Cerebrosidebiosynthesis,166
accident,147 4.8.3 Formationofcomplex
4.5.4 Thecorereactionsofglycerolipid glycosphingolipids,167
biosynthesisarethoseoftheKennedy 4.8.4 Gangliosidebiosynthesis,167
pathway,147 4.8.5 Sulphatedsphingolipids,169
4.5.5 Thezwitterionicphosphoglycerides 4.8.6 Sphingomyelinisbothasphingolipid
canbemadeusingcytidine andaphospholipid,170
diphospho-bases,149
4.8.7 Catabolismofthesphingolipids,170
4.5.6 CDP-diacylglycerolisanimportant
4.8.8 Sphingolipidmetabolisminplantsand
intermediateforphosphoglyceride
yeast,172
formationinallorganisms,150
4.9 Cholesterolbiosynthesis,173
4.5.7 Phosphatidylserineformationin
4.9.1 Acetyl-CoAisthestartingmaterialfor
mammals,152
polyisoprenoid(terpenoid)aswellas
4.5.8 AllphospholipidformationinE.coliis
fattyacidbiosynthesis,174
viaCDP-diacylglycerol,152