heng savoeun/2008 1 · 2019-01-24 · auto-oxidation and rancidity ... •-gal´kul( alcohols) •...
TRANSCRIPT
1Heng Savoeun/2008 1
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cMNgeCIg
Heng Savoeun/2008 2
1- CIv³m:UelKul
1- GamINUGasuIt ‘Amino Acid)
2- RbUetGuIn ‘Protein)
3- kabUGuIRdat ‘Carbohydrate)
4- lIBIt (Lipid )
5- nuyekøGuicGasuIt ‘Nucleic Acid)
2- Gg;suIm (Enzyme)
3- vItamIn ‘Vitamin)
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niymn&y
• lIBItKWCasarZatuEdlrlaykñúgZaturMlaysrIrag<
ó chloroform(CHCl3) GaestUn Gakul ebnsuIn‘benzene’
nigeGETr EtminrlaykñúgTwk
⇒ lk¡N;Biessrbs´vaKWkarbeg,ItCaRKab´xøaj´lÁit>enAkñúgmCÄdðanTwk
⇒ muxgarrbs´lIBItkñúgPavrs´ KWeZVICaGaharbMrugEdlpþlzamBlx¬s´
nigCasarZatud*sMxan´sMrab´ekasika
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cMENkfñak;lIBIt
Õ tamTMrg´KImI lIBItRtUv:nEckCa2Rkum KW
→lIBItsaMjúaM
→ lIBItgay
Heng Savoeun/2008 5
- GasuItxøaj´‘fatty acid’
- RTIGasuIlKøIesru¨l‘triacylglycerol)
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GasuItxøaj´‘fatty acid’
• GasuItxøaj´;
Ù GasuItxøaj´Eq¸t (Saturated fatty acids)
Ù GasuItxøaj´minEq¸t (Unsaturated fatty acid)
• - GasuItxøaj´mU"NUminEq¸t (Monounsaturated fatty acids)
• - GasuItxøaj´bU"lIminEq¸t (Polyunsaturated fatty acids )
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GasuItxøaj;Eq ¥t
• GasuItxøaj´Eq¸tKWCaGasuItsrIrag<EdlmanGatUmkabUnCaExSEvgnigKμanExñg
CH3-(CH2)n-COOH GatUmkabUnticCag14 nig
eRcInCag20manedaykMr
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TMrg;GasuItxøaj;Eq¥t
Heng Savoeun/2008 8
• GasuItxøaj´PaKeRcInmanGatUmkabUnCacMnYnKU
eRJHZmμtaGasuItxøaj´ekIteLIgedaysarRbtikmμ
sMeyaKbUkGatUmkabUnmþgBIr
GasuItxøaj´manknÞúyCa
ExSGuIRdUkabUnEdlP¢ab´
eTAnwgkabuksuIl
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GasuItxøaj;minEq¥t
• mansm¬&nÆBIrCan´mYyrWeRcInkñúgmUelKul . Ésm¬&nÆbICan´kñúgGasuItxøaj´ KWkMrman
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stearate KWCa
GasuItxøaj´EqÁt
TMrg;suItxøaj;;minEq¥tEdlmankabUn18
oleate nig linolenate KWCaGasuItxøaj´minEqÁt
Heng Savoeun/2008 10
• GasuItxøaj´EqÁt rwg
• GasuItxøaj´minEqÁt rav
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Cis nig trans isomers
• sm¬&nÆBIrCan´enAkñúgmU¨elKulGasuItxøaj´ GacmanlTÆPaB KW cis nig trans
isomers . bu¨Enþ TMrg´ trans kRm
Heng Savoeun/2008 11
12Heng Savoeun/2008 12
- TMrg'KImI linolenic acid (18:3Δ9c,12c,15c)
- GñkKImI; rab´BI carbonyl carbon (blue numbering)
- GñksrIr; rab´BI n (ω) carbon (red numbering)
karehAeQμaH
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GuksuItkm μÉkÉg nigkareLIgxa
Auto-oxidation and rancidity
► kareLIgxa
• GasuItxøaj´kñúgsItuNØPaBbnÞb´ rgnUvbNþrKImI EdlehAza GuksuItkmμÉkÉg
• GasuItxøaj´ RtUvbMEbkeTACa - GuIRdUkabUn‘ hydrocarbons) • - extUn ( ketones)• - GaedGuIt (aldehydes)• - eGbuksuIt ( epoxides) • - Gal´kul( alcohols)
• Heavy metals present at low levels in fats and oils promote auto-oxidation. Fats and oils often are treated with chelating agents such as citric acid.
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Mechanisms of Oxidation
• •+•• +
RH R HR O2 ROO
• + + •ROO R1H ROOH R1
• •+
+ +• •
RO R ROR• •+
• •+
R R RR
ROO ROO ROOR O2
ROO R ROOR
A. epþIm - karbeg,Itra¨DIkal´ alkyl esrI
B. dal - Rbtikmμbnþénra¨DIkal´ peroxy
C. bJ©b´ - karbeg,ItplitplKμanra¨DIkal´
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General Mechanisms of Autoxidation
14 13 12 11 10 9
- H
CH2 CH CH CH2 CH CH CH2 R(CH2)3CH3
INITIATION
12 11 10 9
•
+ O2
(C H2)4C H3 C H C H C H C H C H2 RC H
•
12 11 10 9
+ H •
(CH2)4CH3 CH CH CH CH CH2 RCH
O
OPROPAGATION
•
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12 11 10
HYDROPEROXIDE DECOMPOSION - OH
CH CH CH CH CH CH2 R(CH2)4CH3
O
O
H
•
•
12 11 10 9(C H
2)4
C H3 C H C H C H C H C H
2RC H
O
+ HTERMINATION
•
(PENTANE)
•
C H 3 (C H 2)3 C H 2
C H 3 (C H 2)3 C H 3
OC
HC H C H C H C H C H 2 R+ 12 11 10 9
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Peroxide Decomposition
OH+
•
•
• +
or
R CO
H R1+ •
•+
R' OH ROH•• +
+
R'
R'H+
+ •
R C R1
H
OOH
R C R1
H
O
R C R1
O
R'H
R C R1
H
OH
R1 C H1
O
R
R'
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RTIGasuIlKøIesru:l (triacylglycerol)
• xøaj´ nigeRbgekIteLIgBIRTIGasuIlKøIesrul ‘ehAza triglycerides)
• RTIGasuIlKøIesrul púSMeLIgBIGasuItxøaj´ nigKøIesrul
glycerol triacylglycerol
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karbegáItxøaj;
karsMeyaKRTIesþrIn BIKøIesrul nigesþrIcGasuIt
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eRbgqa nigxøaj;
• RTIGasuIlKøIesru¨lEdlcMeJHsItuNØPaBkñúgbnÞb´enArwgehAzaxøaj´
ehIyebIvarav ehAzaeRbgqa
• eRbgmanGasuItxøaj´minEqÁt‘oleic acid sMbUréRkElg’ nigPaKeRcIn
manenAkñúgruk¡Cati dUcCa eRbgsENþk eRbglá
• xøaj´stV‘animal fat’ RtUv:nbeg,IteLIgBIRTIKøIesrItEdlmanGasuIt
xøaj´EqÁt nigcMnYnGatUmkabUnKt´KUr
• eRbgRtI‘fish oils’manpleZ[bx¬s´énGasuItxøaj´minEqÁteRcIn
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xøaj; nigfamBl
• RTIGasuIlKøIesrul KWCazamBlbMrugkñúgxøÜnstV EdlRtUv:nsnSMTukeday
KμanmUelKulTwkkñúgCalikaxøaj´
• Calikaxøaj´sæitenARsTab´xageRkaménEs|k PaKeRcInRtg´k|aleJH
• cMeJHbursmanxøaj´cMnYn21PaKryénTMgn´ ÉRsþIman26PaKry
• brimaNxøaj´enH GaceGaymnusSenAraMuér:n2-3ExedayGt´Gahar
• cMENkKøIkUEsnkñúgxøÜneyIgvijGacp<t´p<g´zamBl:nmindl´1ézáeT
- xøaj´ 9 kcal/g
- RbUetGuInç kabUGuIRdat, 4 kcal/g
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karbMEbkGaharxøaj;
• edaysarkarminrlaykñúgTwkenH Rbdab´rMlayGaharminGacRsUbyk
xøaj´edayRtg´>:neLIy
• vaRtUveZVIRbtikmμbMEbkCamuneRkamGMeBIénGg´suIm lipase rbs´rslMEBg
kñúgeJHev[ntUcedaybg,eTACaKøIesrul nigGasuItxøaj´
• plitplénGuIRdUlIs RtUvRsUbedayRsTab´eJHev[ntUc ehIybnÞab´mk
vak*RtUvpSMeLIgvij rYcRtUv:ndwknaMedayRbUetGuIneTAkñúgQam nigpþl´
eGayCalikaxøaj´
• GasuItxøaj´RtUvbJ¢ÚneTAekasikadéTeT[tEdlvaTTYlrgnUvRbtikmμ
GuIRdUlIs nigGuksuItkmμ rhUtdl´køayCaTwknigósμ&nkabUnic
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sabU‘ (Soap)
P 511 Ch 17
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mU:elKulsabU‘(Soap Molecule)
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etIsabU‘rMlayxøaj;dUcemþcHow soap dissolves grease
Fig 17.2
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lIBItsaMjúaM ‘complex Lipid’
1- KøIesrU:pUsVrlIBIt (glycerophospholipid)
2- sphingolipids
3- esþrU:GuIt (steroids)
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1- KøIesrU:pUsVrlIBIt (glycerophospholipid)
• glycerol 3-phosphate cg
sm¬&nÆeGEsÞenARtg´TItaMg C1
nigC2 CamYybg<MúGasuIlén
GasuItxøaj´
• cMENkpUsVatGaccgsm¬&nÆ
eGEsÞCamYynwgsmasZatu
epSgeT[t dUcCaGal´kulcMnYn 4
KW ethanolamine, choline,
L-serine nig inositol
Heng Savoeun/2008 27
• Phosphatidateman glycerol 3-phosphate nigbg<MúGasuIlBIr
• phosphatidate KWCaTMrg´gayrbs´KøIesrU¨pUsVrlIBIt
• phosphatidatemank|albU¨ElnigknÞúyminbU¨El
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phosphatidyl choline
•CYnkalRtUv:neKehAza lecithin
•CamUelKul amphiphileEdlman
knÞúyCa hydrophobic nig
k|alCa hydrophilic
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phospatidyl ethanolamine
• Ca cephalin
• CamU¨elKul amphiphile
EdlmanknÞúyCa hydrophobic
nigk|alCa hydrophilic
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phosphatidyl serine
• CamU¨elKul amphiphile
EdlmanknÞúy hydrophobic
nigk|al hydrophilic
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KøIesrU:pUsVrlIBIt
• phosphatidic acid manvtþman tictYcNas´kñúgPñasCIv;
• KøIesrUpUsVrlIBItEdlmanvtþmankñúgPñasCIv;KWk|alrbs´vaman alcohol
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Inositol
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2- sphingolipids
• sphingolipids man sphingosine CMnYsKøIesru¨l
• CaTUeTA sphingolipids rgRbtikmμemtabUlIsyWtCag phospholipids ehIyeZVI
eGayTMrg´ekasikamanesærPaBCag
• man sphingolipids cMnYn3EdlRtUvsMeyaKecjBI N-acyl-fatty acid
derivatives of sphingosine (RsLay sphingosine KW ceramide);
• Sphingomyelins
• Cerebrosides
• Gangliosides
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2-1- Sphingomyelins
Heng Savoeun/2008 33
Ù sphingomyelin éneRsam myelin
minRtUv:nrgemtabUlIseTkñúgxøÜnmnusS
Ù sphingomyelin manvtþmany¨ageRcIn
enAkñúgCalikaRbsaT
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2-2- Cerebrosides
Heng Savoeun/2008 34
• cerebrosidesrW glycosphingolipids
ó galacto-cerebrosides nig gluco-
cerebrosides• cerebroside manvtþmany"ageRcIn
kñúgCalikaRbsaT
• KøIkUlIBIt KWCalIBItsaMjaMmYyEdlmantYnaTIy¨agsMxan´kñúg
sarJg<kay
ó1 CaGñkTTYlxusRtUveTAelIlk¡N;énmuxgarBiessenA
elIPñasekasikaQamRkhm
ó2 Ca receptor sMrab´karcgsm¬&nÆénvIrusnigPñasekasika
35Heng Savoeun/2008 35
2-3- Gangliosides
ó1 CaGñkTTYlxusRtUveTAelI
lk¡N;énmuxgarBiessenA
elIPñasekasikaQamRkhm
ó2 Ca receptor sMrab´GrmUn
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3- esþrU:GuIt (steroids)
• esþrUGuIt rlaykñúgZaturMlaylIBIt
• vaRtUv:ncat´za lIBIt edaysarcriklk¡N;énPaBrlayrbs´va Rsed[g
• esþrUGuItTaMgGs´manrgVg´ cyclo-pentano phenanthrene Edl mankabUn17
CamUldðanRKw;énTMrg´rbs´va
Heng Savoeun/2008 36
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kUelesþru:l ‘cholesterol’
• kUelesþru¨l KWCaesþrU¨GuIt
• kñúgznikstV kUelesþrulCasarZatuepþIménBBYk steroid hormone
dUcCa androgen nig estrogen man«TÆiBlelIkarvivDÄ nigmuxgarePT
Heng Savoeun/2008 37