Lecture 2 : Lipids

Lipids are compounds, present in

plants and animals, that are soluble in
non polar solvent, such as chloroform
or eter, but not soluble in water.
2
3
Five (5) types of lipids:
Energy-storage lipids: triacylglycerols
Membrane lipids: phospholipids
Emulsification lipids: bile
Messenger lipids: steroid hormones
Protective lipids: biological waxes
4
FATTY ACIDS:
Saturated
Unsaturated
GLYCERIDES:
Neutral
Phosphoglycerides
COMPLEX LIPID:
Lipoproteins
Glycolipids
NONGLYCERIDES:
Sphingolipids
Steroid
Waxes
5
Fatty acids: a component of
many lipids
Different types of fatty acids:
Saturated fatty acid



Biosynthesized fatty acids are further classified as:
Long-chain: contain 12-26 carbons
Medium-chain: contain 6-10 carbons
Short-chain: contain 4-6 carbons

Unsaturated fatty acid
Monounsaturated fatty acid: exp (20:1).
Polyunsaturated fatty acids (PUFA): exp (20:3).

Monocarboxylic acids.


6
Physical properties
of fatty acids
the length and degree of
unsaturation.


Solubility in H
2
O
Chain Length
Melting Point
chain > > solubility < <


unsaturation > > melting point < < as due to
the lack of compact packing as a result of kinks
introduced by the double bonds
melting point > >

7
D.B.
0
1
2 3
4
melting
temperature
All unsaturated
fats are oils at room
temperature
16:0


60

16:1

1

18:0

63

18:1

16

18:2

-5

18:3

-11

20:0

75

F. A. M. P. (
0
C)

20:4

-50


1 D.B.
Cis D.B.
2 D.B.
8
Some fatty acids and their common names:
14:0 myristic acid; CH
3
(CH
2
)
12
-COOH

16:0 palmitic acid; CH
3
(CH
2
)
14
-COOH

18:0 stearic acid; CH
3
(CH
2
)
16
-COOH

18:1 cisD
9
oleic acid CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
-COOH

Double bonds in fatty
acids usually have the
cis configuration.
Most naturally
occurring fatty acids
have an even number
of carbon atoms.
C
O
O

1
2
3
4

fatty acid with a cis-D
9

double bond
9
18:2 cisD
9,12
linoleic acid
CH
3
(CH
2
)
4
CH=CHCH
2
CH=CH(CH
2
)
7
-COOH
is used to synthesize arachidonic acid, which regulates blood
pressure, clotting et


18:3 cisD
9,12,15
a-linonenic acid
CH
3
CH
2
CH=CHCH
2
CH=CHCH
2
CH=CH(CH
2
)
7
-COOH
is used to synthesize eicosapentaenoic acid (EPA) and docosahexanoic acid
(DHA) which are required for normal brain function and development (an
omega-3)





20:4 cisD
5,8,11,14
arachidonic acid
20:5 cisD
5,8,11,14,17
eicosapentaenoic acid(an omega-3)
10
11
Waxes
12
ester of fatty acids and

O
C
30
H
61
O C C
15
H
31

O
C
16
H
33
O C C
15
H
31
Important in fruits:
1. Natural protective layer in fruits, vegetables, etc.
2. Added in some cases for appearance and protection.
Beeswax (myricyl palmitate),Spermaceti (cetyl palmitate)

O
||
R - C - O - R
1



Waxes :
long chain alcohol
13
C-OH
CH
C-OH
H
H
H
H
HO-
glycerol
Monoacylglycerol/monoglyceride
H-O-C-CH
2
C-R
1
O
Diacylglycerol/
diglyceride
R
2
-CH
2
-C-OH
O
H-O-C-CH
2
C-R
3
O
Triacylglycerol = Triglyceride
14
15
16
The chemical reactions of triacylglycerols are similar
to those of alkenes and esters.
Hydrogenation of double bonds in unsaturated fatty
acids by H
2
(compare to alkenes).
Chemical Properties of Triacylglycerols
Hydrolysis of ester bonds by water
in the presence of an acid, a base,
or an enzyme (compare to esters).
TAG :
* energy reservoirs * insulator
* digested in the small intestine by
the enzyme pancreatic lipase
* saponification : formation of soaps
Monoacylglycerols are absorbed through
the intestinal cells, re-converted to TG
and assembled into lipoproteins
17
Triglycerides
Stored as droplets of
adipose tissue in body
fat.
Fat stored in this cell
18
Hydrogenated Fats
Hydrogenation of
vegetable oils to
margarine or
shortening, not only
convert unsaturated
bond to saturated, but
also may converts some
of cis unsaturated
bonds to trans
configuration

Diet high in trans fatty
acids risks heart
disease, cancer.

cis trans
*
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PYROLYSIS
Hydrogenation: addition of two hydrogen atoms
over a double bond. Some food products are
partially hydrogenated
O O
// //
CH
2
- O - C - R
1
3

CH
2
- O - C - R


O
//
CH - O - C - R
2
O


O //
// CH
2
= CH - C - H
CH
2
- O - C - R
3

D
fatty acids
acrolein
-o
2


20
- COOH
( fatty acid)

- C = C - + O
2
- C - C - - CHO
- C=O
O - O
(Peroxide)
H
2
O
Oxidation
Oxidation: addition of oxygen (derived from air),
lead to oxidize the double bonds present in a
fatty acid to produce carboxylic acid, and other
carbonyl compound (keton, aldehyd) through
peroxide intermediate.
21
Rancidification
O
//
Fat R - CH
2
- CH
2
- C - O - H
O O
// //
R - C - CH
2
- C - O - H R - C - C + CO
2

//
O Keton
Lipase
-Oksidase
+
the decomposition
of fats and other
lipids by
hydrolysis and or
oxidation
Keton or acids produced from lipid oxidation /rancidification
process have low-molecular-mass and volatile. This volatile
compounds are reponsible for rancid odor and flavor in some
food products. Antioxidant is usually added to prevent lipid
oxidation which lead to rancidity.
22
Glycerol esterified with 2
fatty acids.
Third position is
phosphate
Other end of phosphate
can combine with other
molecules to form various
derivatives
Amphipathic emulsifying
agents
component of cell
membrane
PHOSPHATE
O H
H
O H
H
H
O H H
O H
H
H
O H
Phosphatidyl
inositol
23
polar
non-polar
"kink" due to
double bond
O P O
O

O
H
2
C
CH
H
2
C
O C R
1
O O C
O
R
2
X
glycerophospholipid

a polar region:
glycerol, carbonyl O
of fatty acids, P
i
, & the
polar head group (X)

non-polar hydrocarbon tails
of fatty acids (R
1
, R
2
).
Each glycerophospholipid / phosphoacylglycerol
possess:
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O P O
O
O
H
2
C
C H
H
2
C
O C R
1
O O C
O
R
2
H
H
Phosphatidic acid
Phosphatidyl
-
O H
H
O H
H
H
O H H
O H
H
H
O H
Phosphatidylinositol
Phosphatidylinositol has roles in cell signaling, as
well as component of cell membrane
C H
2
C H
2
N C H
3
C H
3
C H
3
+
Phosphatidylcholine/lechitin
It is a common membrane lipid
25
phosphatidyl choline = lechitin
Lecithin, a
common food
additive, is a
phospholipid,
Which
embedded in
cell
membranes.
26
Cell Membrane
27
Structure of Phosphatidyl choline with
2 fatty acids, oleate and palmitate
O
C H
3
N
+
CH
3
CH
3
O
(CH
2
)
14
CH
3
O
O
O
(CH
2
)
7
C
H
C
H
(CH
2
)
7
CH
3
CH
2
C H
C H
2
O P
O
O
28
Sphingolipids
Sphingosine instead of glycerol

Derivatization at ester C1

Fatty acids added at amine

Different types are found in
plasma membrane and myelin
sheaths

29
2
H
2
C
H
C
O H
C H
N C H
C
C H
2
C H
3
H
( )
1 2
sphingosine
Sphingolipids
/ceramide
H
O H
C
R
O
OH
The amino group of sphingosine can
form an amide bond with carboxylate
group of a fatty acid, to yield a
ceramide
Ceramides usually include a polar head
group, esterified to the terminal OH
of the sphingosine
P O O
O
H
2
C
H
2
C
N
+
C H
3
H
3
C
C H
3

OH
Sphingomyelin, a ceramide
with a phosphocholine or
phosphethanolamine head
group, is a common constituent
of plasma membranes
Sphingomyelin

Sphingomyelins
are found
abundantly in the
myelin sheath that
surrounds the
nerve fibers
P O O
O
H
2
C
H
2
C
N
+
C H
3
H
3
C
C H
3

O H
O
H
H
H
O H H
O H
C H
2
O H
H
A cerebroside is a
sphingolipid (ceramide) with a
monosaccharide such as
glucose or galactose as polar
head group.
30
Steroid Nucleus
Consists of:
3 cyclohexane rings.
1 cyclopentane ring.
no fatty acids.



steroid nucleus
31
CH
3
CH
3
CH
3
CH
3
HO
CH
3
Cholesterol
is the most abundant steroid in the body.
has methyl CH
3
- groups, alkyl chain, and -
OH attached to the steroid nucleus.
O H
32
Cholesterol:
-important constituent of cell
membranes
-has a rigid ring system and a
short branched hydrocarbon
tail.



O H
hydrophobic amphipathic.
Keeps the lipids in membrane
from aggregrating, eliminate of
excess cholesterol in intestinal
tract and artery.
- Precursor to Bile Acids:
- Crusial role in lipid
digestion
- break up large lipid to
smaller one, make it
can be broken easily
by enzymes
Precursor to steroid hormones that
regulate gene expression
Precursor to Vitamin D
A normal, open artery.
An artery clogged by
cholesterol plaque
33
Cholesterol inserts into bilayer membranes with its
hydroxyl group oriented toward the aqueous phase &
its hydrophobic ring system adjacent to fatty acid
chains of phospholipids.
O H
34


.
The OH group of cholesterol forms hydrogen bonds
with polar phospholipid head groups.
35
Lipoproteins: LDL, HDL, Etc
combine lipids
with proteins &
phospholipids.

are soluble in
water because its
surface consists of
polar lipids.
36
Types of Lipoproteins
differ in density, composition, and function.
include low-density lipoprotein (LDLs) and high-
density lipoprotein (HDLs).
37
Transport of Lipoproteins in the Body


38
LDL
circulate in the
blood
Build up in arteries;
lead to heart attack
HDL
level 130 mg/dL,
reflects an increased
risk of heart disease
level < 40 mg/dL, is
thought to increase the
risk for heart disease.
cholesterol lipoprotein,
that returns to the liver ;
removes cholesterol out of
the bloodstream;
believed to prevent heart
attacks