???????? (Lipids and Lipid Biochemistry)

1
???????
Lipids and Lipid Biochemistry
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Biological Lipids

• ???????????????,???????????,?????????????(water
  insoluble)(????,fat-soluble),?????????????????????
  ????,??????

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Functions of Biological Lipids

• Supply and storage forms of energy
• Biomembrane about 50 lipids????????
• ??????????,???????????????????????????????????????
  ?????????
• ????????????????????????

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Functions of Lipids I

• ???????,?9 kcal/g??????????????25-30??????
• ??????????????????
• ?????????????????????,????????????????????????,??
  ????????????
• ???????????????????,???????,??????????????????????
  ???????????

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Functions of Lipids II

• ????????????,??????????????????????
• ????????????,??????????????????????,???????????
  ?????????????????,?????????,?????????????,????????
  ???????????????????????????,?????????????

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Functions of Lipids III

• ?????????????????????????????????????????????????
  ??????????????????D??????????????????????????,??
  ????????????????????????
• ????????????????????????????????????????

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Classification of Lipids

• ???????????,??
• ????(?)(Simple lipids),????????
• ????(Compound Lipids),????(????????)???(?????????)
  
• ?????(Isoprenes),??????????????

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Fatty Acids

• ???4-36????,??????????????????????????????????????
  
• ??????(Linoleic acid)????(Linolenic
  acid)??????(Arachidonic acid)????????(Essential
  fatty acids)?

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Chemical Structure of Fatty Acids
1 Carbon
Acid Group
Polar End - Hydrophilic End
Non-polar End - Hydrophobic End
(Fat-soluble tail)
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Saturated Fatty Acids
Octanoic Acid??
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Unsaturated Fatty Acids
3 - Octenoic Acid 3-???
3, 6 - Octadienoic Acid 3,6-????
Short hand 81 (?3) 82 (?3, 6)
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cis and trans Fatty Acids
(??)
cis 9 - Octadecenoic Acid (oleic)
(???)
trans 9 - Octadecenoic Acid (elaidic acid)
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Polyunsaturated Fatty Acids

• Linoleic acid cis, cis, 9, 12 - Octadecadienoic
  acid(???)
• Linolenic acid cis, cis, cis, 9, 12, 15 -
  Octadecatrienoic acid (???)
• Arachidonic acid cis, cis, cis, cis, 5, 8, 11,
  14 - Eicosatetraenoic acid (?????)

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Naturally-occurring Fatty Acids
1?cis form (??) 2?Not conjugated --- isolated
double bond.(???,??????) 3?Even numbered fatty
acids(???)
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Classification of Fatty Acids Present as
Glycerides in Food Fats
 
I. Saturated Fatty Acids
 
Butyric
Butanoic
CH3(CH2)2COOH
butterfat
Caproic
Hexanoic
CH3(CH2)4COOH
butterfat, coconut and palm nut oils
Caprylic
Octanoic
CH3(CH2)6COOH
coconut and palm nut oils, butterfat
Capric
Decanoic
CH3(CH2)8COOH
coconut and palm nut oils, butterfat
Lauric
Dodecanoic
CH3(CH2)10COOH
coconut and palm nut oils, butterfat
???
Myristic
Tetradecanoic
CH3(CH2)12COOH
coconut and Palm nut oil, most animal and plant
fats
????
???(???)
Palmitic
Hexadecanoic
CH3(CH2)14COOH
practically all animal and plant fats
Stearic
Octadecanoic
CH3(CH2)16COOH
animal fats and minor component of plant fats
???
???
Arachidic
Eicosanoic
CH3(CH2)18COOH
peanut oil
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II. Unsaturated Fatty Acids
 
A. Monoethenoic Acids
Oleic
Cis 9-octadecenoic
C17H33COOH
plant and animal fats
??
Elaidic
Trans 9-Octadecenoic
C17H33COOH
animal fats
???
B. Diethenoic Acids
peanut, linseed, and cottonseed oils
Linoleic
9,12-Octadecadienoic
C17H31COOH
???
C. Triethenoid Acids
Linolenic
9,12,15-Octadecatrienoic
C17H29COOH
linseed and other seed oils
???
peanut seed fats
Eleostearic
9,11,13-Octadecatrienoic
C17H29COOH
???
D. Tetraethenoid Acids
Moroctic
???
4,8,12,15-Octadecatetraenoic
C17H27COOH
fish oils
?????
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Common and Systematic Names of Fatty Acids
 
 
A. Monoethenoic Acids
Oleic
Cis 9-octadecenoic
C17H33COOH
plant and animal fats
Elaidic
Trans 9-Octadecenoic
C17H33COOH
animal fats
B. Diethenoic Acids
Linoleic
9,12-Octadecadienoic
C17H31COOH
peanut, linseed, and cottonseed oils
C. Triethenoid Acids
Linolenic
9,12,15-Octadecatrienoic
C17H29COOH
linseed and other seed oils
Eleostearic
9,11,13-Octadecatrienoic
C17H29COOH
peanut seed fats
D. Tetraethenoid Acids
4,8,12,15-Octadecatetraenoic
Moroctic
C17H27COOH
fish oils
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Essential Fatty Acids

• ????????,????????,????????????????????????????????
  ?????????????????????????????????
• ???????????????????????DHA?????,????????????????
  ??????????????,????????,??????????????
• ???????????????????

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?-???Linolenic Acid

• ????????????????,???????????,
  ???????,???????????????DHA?EPA(
  ???)??????????????,?????????????????????????????
  ?????????????,??a-?????????,??????????????????????
  ?????????????????????????????????????????

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Bioactive Fatty Acids

• EPA (eicosapentaenoic acid),??????(?5,8,11,14,17)?
  DHA(docosahexenoic acid),???????(?4,7,10,13,16,19)
  , ?3????????,????????????????????DHA?EPA?
• DHA??????????????????????????DHA??????,???????????
  
•  ????????????,?????????????,DHA?????????????,??6??
  ?,??????DHA???????????????????  

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??????????
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Melting Points and Solubility in Water of Fatty
Acids
Melting Point
Solubility in Water
Chain Length
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???????????????
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Effects of Double Bonds on the Melting Points
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???????????
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????(Fat and Oil)

• ????
• (Triacylglycerols, TG)

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????Triacylglycerols, TG

• ???????????????????,??????????????????????????????
  ?????(?????monoacylglycerol, MAG),?2?????????????
  ?(?????diacylglycerol, DAG)?
• ??????????????????????(simple glycerides),????????
  ??????(mixed glycerides)?

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• Glycerol and Triacylglycerol

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Fat and Oils
Mostly Triglycerides
Glycerol 3 Fatty Acids Triglycerides
?????,?????????????????CoA?
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Glycerides
Monoglyceride
Diglyceride (a- monostearin)
(a, a ' - distearin)
Triglyceride (b - palmityl distearin)
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a - oleodipalmitin 1 - oleodipalmitin
a - Linoleyldiolein 1 - Linoleyldiolein
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????(Fats and Oils)

• ????????????,?????????????,???????????,??????????
  ?????????,????(oil),??????????????????,?????(fat),
  ????????,?????????

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????

• ????????????????????,??????????,????????????????
  ???(adipcytes?fat cells)?????????????????,????????
  ??????????????
• ?????????????,?????????(??),???????????????????
  ?????????????????15-20 kg???,?????????,??,????????
  ????????????

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? ?

• ?????,???????????????,??????????????????,????????
  ?????????????????????,?????(??)????????????,??????
  ??

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?????????
Arabidopsis cotyledon
Cross section of guinea pig adipocytes
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??(???????)
??(?)
The sperm whales head is very large, accounting
for over one-third of its total body weight.
About 90 of the weight of the head is made up of
the spermaceti organ, a blubbery mass that
contains up to 18,000 kg of spermaceti oil, a
mixture of triacylglycerols and waxes containing
an abundance of unsaturated fatty acids.
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?????????
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????(Saponification)????(Saponification Value)

• ?????????????,????,???KOH?NaOH?????,??????????????
  ,??????????1g??????KOH?mg?????,???????????????????
  ?????????,???????3?56?1000/????
• ???????????(??)???????????????????

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Saponification
Saponification - hydrolysis of ester under
alkaline condition.
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??Racidity???Acid Value

• ???????????????,???????,??????????????????????,??
  ??????,???????1 g???????????KOH?mg?????,?????????

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Acid Value
Number of mgs of KOH required to neutralize the
Free Fatty Acids in 1 g of fat.
ml of KOH ? N ?56
AV
Weight of Sample
mg of KOH
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??(Halogenation)???(???, Iodine Number)

• ?????????????????,???????,???????100
  g?????????????,??????????????????

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Iodine Numbers of Triglycerides
Palmitoleic Acid
1
95
Oleic Acid
1
86
Linoleic Acid
2
173
Linolenic Acid
3
261
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??(Hydrogenation)

• Ni????,?????????????H2??????,?????,??????,??????

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?????(Acetylation)?????(Acetylation Number)

• ????-OH???????????????????????,????????1g????????
  ?????KOH?????KOH?mg????????

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?????????

• ???????,???????????,??????????-OH,?????????
• ??????????,????????????????????
• ?????????????,C1?C3???????,C2?????,??????

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????????(Amphipathic Lipids Aggregate)

• ????????????????,????????,???????????????????(?)?
  ????????????????????????????????????????????????,?
  ?????????????????????????,??????????(micelles)???
  ???(bilayer)????(liposome)?

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????????
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?(Waxes)-?????????

• ??????14-16C?????16-30C????,?????????
• ?????60-80?,????????
• ???????????????,?????????????????????????????????
  ?????????????????????????????????????????????????
  ?
• ?????????????????????,???????????????

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Waxes

• Fatty acids Long chain alcohol
• Important in fruits
• Natural protective layer in fruits, vegetables,
  etc.
• Added in some cases for appearance and
  protection.
• Beeswax (myricyl palmitate), Spermaceti (cetyl
  palmitate)

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• ? ? ?

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??????

• ???????????????,???????????????????????????
• ?????(Glycerophospholipids)
• ???(Sphingolipids)???????
• ???(Sterols)

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• ??????

Sterols
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????????(Phosphatidic acid, phosphatidate)????

• ???2?????????C1?C2?????????,??????????????(nonpo
  lar tail)??????????????C3?-OH??,??????(polar
  head)??????C3?-OH ??????????????,?????????????,???
  ????????????????????????

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???????(L-glycerol 3-phosphate)
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• ????(Glycerophopholipids)

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????
58
????????
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Phospholipids in Plasma Membrane
PE
PS
PC
PI
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???(Lecithin, Phosphatidylcholine)

• ?????????,?????????????????,????????(8-10)????Lek
  ithos,???egg yolk?
• ???????,???????????????????????????
• ?????????????,??????
• ???????????????????????????????????

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(No Transcript)
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???????????
63

• ????????????

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• ???????????????

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???????????

• ????????????????ether lipids,?????????????????
  ??,????????????,????C1-C2??????,?????(plasmalogens
  )????????????????????,????????????????,???????????
  ?????????????????????????????,??????????????

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????????????

• ???????platelet activating factor,
  PAF????????,1-O-??-2-O-???-Sn-??-?????,??????????
  ?,??????????PAF??????????,?????????????,??????????
  ??????????,??????????5-???????????????,???????????
  ??????????????????????????????????????????????????
  ???

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????(Plasmalogen)????????(Platelet-activating
factor, PAF)