LIPID

Lipids
• Lipids have low solubility in water;
• Lipids are amphipathic (polar and nonpolar);
• Lipids are a principle component of biological
membranes;
• highly reduced forms of carbon; yield large
amount of energy upon oxidation in
metabolism;
 Roles of Lipids
 Structural elements (phospholipids, cholesterol)
 Energy storage (fatty acids, triacylglycerols)
 Hormones ( sex hormones e.g. Estrogen,
testosteron)

 Enzyme cofactors (coenzyme A)

 Electron carriers (coenzyme Q, plastpquinone)
 Light-absorbing pigments (carotenoids)
 Emulsifying agents (bile salts)
 Intracellular messengers (phosphatidyl inositol)
 Fatty Acids as Stored Energy

• Fatty acids are the body’s principal form

of stored energy
• Heart and muscle mostly use FA as
main energy source for their activities
• Brain only use glucose and keton bodies
(beta hidroxy butyric acids/BHBA)
• Carbon almost completely reduced as
CH2
 Lipids, Fats in Living Organism
• Basically are in the Triacylglycerols (Triglycerides)
forms
Some different fats and classification
L-Glycerol-3-phosphate,
the backbone of phospholipids
 Triacylglycerols (triglycerides)
• Triglycerols consist of a glycerol esterified with three fatty acids
• If all fatty acid chains are the same, the molecule is called
triacylglycerol (e.g., tristearin)
• Fats are largest subgroup of lipids
– Made up of fatty acids and glycerol

Chapter 15 10
 Phospholipids

2 Classes of phospholipids (PL)

(i) glycerolphospholipids – glycerol backbone
(ii) sphingomyelin – spingosine backbone
Glycerolphospholipids
- essential for membrane structure
- most abundant membrane lipids
Sphingolipids
- Component of a certain membrane
- Sphingosine, fatty acid and glycoside
 Sphingolipids

• Sphingosine forms the backbone of sphingolipids (rather than

glycerol);

• Sphingosines are important components of biological membranes;

• Ceramide = sphingosine + fatty acid (via an amide linkage);

• Sphingomyelins = ceramide + phospholipids (via 1-hydroxyl

group)

• Glycosphingolipids = ceramide + b-linked sugar at the 1-hydroxyl

moiety.
Sphingolipids
 Examples of Sphingolipids

• Sphingosine Ceramide O H3 C
H2O OH H OH O P O CH2 CH2 N CH3
H OH H OH H
C C CH2 C C CH2 H OH H O CH3
H NH C C CH2
H NH3
H H H NH Cholin
O H
R-COOH O Sphingomyelin
R
fatty acid R
 Fig 9.11

(a) Sphingosine
(b) Ceramides
(c) Sphingomyelin

Prentice Hall c2002 Chapter 9 16

Similarities between phosphatidylcholine
and sphingomelin
 Steroids

• Based on a core structure consisting of three 6-

membered rings and one 5-membered ring, all
fused together;
• Cholesterol is the most common steroid in animals
and precursor for all other steroids in animals;
• Steroid hormones serve many functions in animals
- including salt balance, metabolic function and
sexual function;
 Steroids
• Classified as isoprenoids - related to 5-carbon isoprene
(found in membranes of eukaryotes)
• Steroids contain four fused ring systems: 3-six carbon rings
(A,B,C) and a 5-carbon D ring
• Ring system is nearly planar
• Substituents point either down () or up ()

Fig 9.14
Isoprene
Prentice Hall c2002 Fig 9.15
Chapter 9 19
 Cholesterol
 Steroids:
(i) cholesterol and sterols of plants and fungi
(ii) steroid hormones
(iii) bile salts

 Roles of cholesterol in mammals

(i) structural component of plasma membrane and
modulates membrane fluidity
(ii) precursor of steroid hormones and bile acids

 Rarely found in plants, never in bacteria

 Steroid Examples OH

H3 C C D
C D CH CH3
A B
A CH2
B O
CH2
testosterone
Cyclopentanoperhydrophenanthrene CH2 synthesized in five
CH CH3 steps from cholesterol
CH2 OH

H3 C C D
C D
A B
A B
HO
HO
Cholesterol
Estradiol
Cholesterol
 Cholesterol
• Cholesterol modulates the fluidity of mammalian cell
membranes
• It is also a precursor of the steroid hormones and bile salts
• It is a sterol (has hydroxyl group at C-3)
• The fused ring system makes cholesterol less flexible than
most other lipids

Prentice Hall c2002 Chapter 9 23

 Cholesterol esters
• Cholesterol is converted to cholesteryl esters for cell storage
or transport in blood
• Fatty acid is esterified to C-3 OH of cholesterol
• Cholesterol esters are very water insoluble and must be
complexed with phospholipids or amphipathic proteins for
transport

Fig 9.17 Cholesteryl ester

Prentice Hall c2002 Chapter 9 24

Steroid hormones carry messages between tissues

Derivates of sterols;

Sex hormones and

hormones from adrenal
cortex;

Play important roles

in gene expression;

Prednisolone and
prednisone are steroid
drug with potent
antiinflammatory
activities.
 Waxes
• Waxes are nonpolar esters of long-chain fatty acids and
long chain monohydroxylic alcohols
• Waxes are very water insoluble and high melting
• They are widely distributed in nature as protective
waterproof coatings on leaves, fruits, animal skin, fur,
feathers and exoskeletons

Fig 9.18 Myricyl palmitate, a wax

Prentice Hall c2002 Chapter 9 26

 Waxes

O
- Esters of long chain fatty acids O

(C14-36) with long chain

(C16-30) alcohols
- High melting points (60-100C)
- Energy storage Oleoyl alcohol Stearic acid
(Plankton)
-Water repellant
(birds and plants)
 Terpenes

• Terpenes are a class of lipids from two or more

molecules of 2-methyl-1,2-butadiene, or
head
isoprene;
O
tail

2-methyl-1,3-butadiene
• Example of a terpene molecule:
CHO

all-trans-retinal

• All sterols (including cholesterol) and steroid

hormones are terpene-based molecules
 LIPID/FAT AND FATTY ACIDS

Lipids/fats are mainly composed of fatty acids

or in other word

Fatty acids are as main component of lipids/fats

29
 Fatty acids
(FAs) and nomenclature
Structure

 Basic formula: CH3(CH2)nCOOH

 Carboxylic acids with hydrocarbon chains of
4-24 carbons

Free FAs are found in trace quantities in cells

FAs are either:

(i) part of a lipid molecule
(ii) complexed to a carrier protein
(e.g. albumin on blood)
31
 Fatty Acids
• Fatty acids - R-COOH (R=hydrocarbon chain)
are components of triacylglycerols,
glycerophospholipids, sphingolipids

• Fatty acids differ from one another in:

(1) Length of the hydrocarbon tails
(2) Degree of unsaturation (double bond)
(3) Position of the double bonds in the chain

Nomenclature of fatty acids

• Most fatty acids have 12 to 20 carbons
• Most chains have an even number of carbons
• IUPAC nomenclature: carboxyl carbon is C-1
• Common nomenclature:  etc. from C-1
• Carbon farthest from carboxyl is 
32
Prentice Hall c2002 Chapter 9
Fig 9.2
 Length of free fatty acid chains
• Fatty acid chains differ by length, often categorized as short,
medium, or long.
• Short-chain fatty acids (SCFA) are fatty acids with aliphatic tails of
fewer than six carbons (i.e. butyric acid)
• Medium-chain fatty acid (MCFA) are fatty acids with aliphatic tails
of 6–12 carbons, which can form medium-chain triglycerides.
• Long-chain fatty acid (LCFA) are fatty acids with aliphatic tails
longer than 12 carbons.
• Very long chain fatty acid (VLCFA) are fatty acids with aliphatic
tails longer than 22 carbons (i.e. wax, terpenes)
 Bond in fatty acids
Saturated vs. Unsaturated Fats

• Saturated fats have no C=C bonds

– Saturated with hydrogen

• Unsaturated fats have C=C bonds

– May have more than one double bond
– Can add more hydrogen to fats
– React readily with iodine, bromine, and chlorine
Chapter 15 34
Saturated b. Unsaturated
Examples of Saturated Fatty Acids
 Examples of Unsaturated Fatty Acids
Name Chemical structure Δx C:D n−x
Myristoleic acid CH3(CH2)3CH=CH(CH2)7COOH cis-Δ9 14:1 n−5

Palmitoleic acid CH3(CH2)5CH=CH(CH2)7COOH cis-Δ9 16:1 n−7

Sapienic acid CH3(CH2)8CH=CH(CH2)4COOH cis-Δ6 16:1 n−10

Oleic acid CH3(CH2)7CH=CH(CH2)7COOH cis-Δ9 18:1 n−9
Elaidic acid CH3(CH2)7CH=CH(CH2)7COOH trans-Δ9 18:1 ?
Vaccenic acid CH3(CH2)5CH=CH(CH2)9COOH cis-Δ11 18:1 ?
Linoleic acid CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH cis,cis-Δ9,Δ12 18:2 n−6

Linoelaidic acid CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH trans,trans-Δ9,Δ12 18:2 ?

cis,cis,cis-
α-Linolenic acid CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH 18:3 ?
Δ9,Δ12,Δ15
CH3(CH2)4CH=CHCH2CH=CHCH2CH=CHCH2CH=CH(CH2)3 cis,cis,cis,cis-
Arachidonic acid
Δ5Δ8,Δ11,Δ14
20:4 ?
COOHNIST
CH3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH= cis,cis,cis,cis,cis-
Eicosapentaenoic 20:5 n−3
acid CH(CH2)3COOH Δ5,Δ8,Δ11,Δ14,Δ17

Erucic acid CH3(CH2)7CH=CH(CH2)11COOH cis-Δ13 22:1 ?

cis,cis,cis,cis,cis,ci
CH3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH= s-
Docosahexaenoic
CHCH CH=CH(CH ) COOH Δ 4
,Δ7
,Δ10
,Δ13
,Δ16
,Δ
22:6 ?
acid 2 2 2
19
Some Naturally Occurring Fatty Acids

Chapter 15 38
 Structure and nomenclature of fatty acids
• Saturated - no C-C double bonds
• Unsaturated - at least one C-C double bond
• Monounsaturated - only one C-C double bond
• Polyunsaturated - two or more C-C double bonds

Double bonds in fatty acids

• Double bonds are generally cis
• Position of double bonds indicated by n, where n indicates
lower numbered carbon of each pair
• Short-hand notation example:

20:45,8,11,14
(total # carbons : # double bonds, double bond positions)
Prentice Hall c2002 Chapter 9 40
• double bonds are never conjugated and
are seperated by–CH2

(-CH=CH-CH2-CH=CH-)n

• Double bonds of Unsaturated FA:

9, 12, 15 ………
 Naming of fatty acids
C18

 10 9  
CH3-(CH2)7-CH=CH-CH2-CH2-CH2-CH2-CH2-CH2-CH2-COOH
Cis 9

18:0, stearic acid : octadecanoic acid

18:1 (9), oleic acid : octadecenoic acid

18:2 (9,12), linoleic acid : octadecadienoic acid

18:3 (9,12,15), -linolenic acid : octadecatrienoic acid

 Examples of Unsaturated Fatty Acids
Name Chemical structure Δx C:D n−x
Myristoleic acid CH3(CH2)3CH=CH(CH2)7COOH cis-Δ9 14:1 n−5

Palmitoleic acid CH3(CH2)5CH=CH(CH2)7COOH cis-Δ9 16:1 n−7

Sapienic acid CH3(CH2)8CH=CH(CH2)4COOH cis-Δ6 16:1 n−10

Oleic acid CH3(CH2)7CH=CH(CH2)7COOH cis-Δ9 18:1 n−9
Elaidic acid CH3(CH2)7CH=CH(CH2)7COOH trans-Δ9 18:1 n−9
Vaccenic acid CH3(CH2)5CH=CH(CH2)9COOH cis-Δ11 18:1 n−7

Linoleic acid CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH cis,cis-Δ9,Δ12 18:2 n−6

Linoelaidic acid CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH trans,trans-Δ9,Δ12 18:2 n−6

cis,cis,cis-
α-Linolenic acid CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH 18:3 n−3
Δ9,Δ12,Δ15
CH3(CH2)4CH=CHCH2CH=CHCH2CH=CHCH2CH=CH(CH2)3 cis,cis,cis,cis-
Arachidonic acid 20:4 n−6
COOHNIST Δ5Δ8,Δ11,Δ14

Eicosapentaenoic CH3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH= cis,cis,cis,cis,cis-

20:5 n−3
acid CH(CH2)3COOH Δ5,Δ8,Δ11,Δ14,Δ17

Erucic acid CH3(CH2)7CH=CH(CH2)11COOH cis-Δ13 22:1 n−9

cis,cis,cis,cis,cis,ci
Docosahexaenoic CH3 CH 2CH=CHCH 2 CH=CHCH 2 CH=CHCH2 CH=CHCH 2 CH= s-
22:6 n−3
acid CHCH2CH=CH(CH2)2COOH Δ4,Δ7,Δ10,Δ13,Δ16,Δ
19
 Iodine Number
• Iodine Number: number of grams of iodine
consumed by 100 g of fat

Chapter 15 44
 Fig. 9.3 Structures of three C18 fatty acids

(a) Stearate (octadecanoate)

(b) Oleate (cis-9-octadecenoate)
(c) Linolenate (all-cis-9,12,15-
octadecatrienoate)
• The cis double bonds produce
kinks in the tails of unsaturated
fatty acids

Prentice Hall c2002 Chapter 9 45

 Fig 9.4 Structures of stearate, oleate, linolenate

Prentice Hall c2002 Chapter 9 46