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Lipid

Sylvia Rianissa Putri

Definition
Heterogenous group of compounds,
including fats, oils, steroids, waxes,
and related compounds, that are
related more by their physical than
their chemical properties.
Relatively insoluble in water
Soluble in nonpolar solvents

Classification
Simple: esters of fatty acids with various
alcohols
Fats: with glycerols including oils
Waxes: with higher molecular weight monohydric
alcohols.

Complex: esters of fatty acids containing groups


in addition to an alcohol and a fatty acid
Phospholipids: phosphoric acid residue, frequently
have nitrogen-containing bases and other
substituents
Glycerophospholipids
Sphingophospholipids

Glycolipids (glycosphingolipids): fatty


acid, sphingosine,carbohydrate
Other complex lipids:
Sulfolipids
Amino lipids
Lipoprotein

Precursor and derived lipids:


Fatty acids
Glycerol
Steroids
Other alcohols
Fatty aldehydes
Ketone bodies
Hydrocarbons
Lipid soluble vitamins
Hormones

Roles
Important constituent of diet
Energy source: high calorie
Vitamin solvent
Contains essential fatty acid (alpha-linolenic
acid, linoleic acid) and conditionally essential
(gamma-linolenic acid, docosahexaenoic acid)

Energy storage
Structural
Cell/organelle membrane
Electrical insulator (myelin)

Protective: biological wax


Cell communication/signalling
Hormone
Vitamin

Transport: lipoprotein

Fatty acids: a component of


many lipids
Monocarboxylic
acids.
Different
types of fatty acids:
Saturated fatty acid

Unsaturated fatty acid


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

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

Asam lemak terdapat sebagai

- ester dalam minyak & lemak alami


- asam lemak bebas (tdk teresterifikasi) bentuk
transport dalam darah

Yang terdapat dalam lemak alami biasanya dg


a. atom karbon rantai lurus
b. jumlah atom C genap
c. rantai dapat jenuh /tidak jenuh

Physical properties
of fatty acids
the length and degree
of unsaturation.
chain > >
solubility
< < point
melting
>>

Melting Point

Solubility in H2O
Chain Length

unsaturation > >


melting point <
< as due to the lack of compact packing
as a result of kinks introduced by the
10
double bonds

F. A.

Cis D.B.

M. P. (0C)

60
1
63
16
-5
-11
75
-50

16:0
16:1
18:0
18:1
18:2
18:3
20:0
20:4
melting

1 D.B.

temperature

2 D.B.

All unsaturated
fats are oils at room
temperature

D.B.

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Penamaan

asam lemak jenuh : akhiran anoat


asam lemak tdk jenuh : dg akhiran enoat
atom karbon no. 1 : atom karbon ggs karboksil
atom karbon no. 2 : atom karbon alfa
tanda : menunjukkan jumlah dan posisi ik
rangkap

Saturated fatty acids

Non polar end


Hydrophobic
end
Fat soluble
tail

8
7
CH3 CH2

O
Acid Group
R C OH Polar end
#1 Carbon

Hydrophilic end
Water soluble
head

5
3
4
6
CH2 CH2 CH2 CH2

Octanoic Acid

O
2
1
CH2 C OH

Unsaturated fatty acids

Unsaturated Fatty Acid


Rule: Double bonds in fatty acids are usually CIS
CH2

H H
C=C

CH2

Rule: Double bonds are always separated


by a -CH2- group
10

12
CH2

H H
C=C
11

H H
CH2 C=C CH2
3

Rule: Double bonds are always numbered 3 apart


Example 9,12 means a double bond on C9 and C12

The
Truly
Awful!

Trans Fatty Acids are to be avoided for health reasons

O
Double bonds in

fatty acids usually


3
1 O
4
2
have the cis
configuration.
fatty acid with a cis-9
Most naturally
double bond
occurring fatty
acids have an
Some
fatty
acids and
even
number
of their common names:
14:0myristic
acid; CH3(CH2)12-COOH
carbon atoms.

16:0 palmitic acid; CH3(CH2)14-COOH


18:0stearic acid; CH3(CH2)16-COOH
18:1 cis9 oleic acid CH3(CH2)7CH=CH(CH2)7-COOH
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18:2 cis 9,12 linoleic acid


CH3(CH2)4CH=CHCH2CH=CH(CH2)7-COOH

is used to synthesize arachidonic acid, which regulates blood


pressure, clotting et

18:3 cis 9,12,15 a-linonenic acid


CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7-COOH

is used to synthesize eicosapentaenoic acid (EPA) and docosahexanoic aci


(DHA) which are required for normal brain function and development (an
omega-3)

20:4 cis5,8,11,14
arachidonic acid
5,8,11,14,17
20:5 cis
eicosapentaenoic acid(an
omega-3)

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Oleic acid. n 9 (n minus 9) is equivalent to


9.

The
Good!

Penamaan

asam lemak jenuh : akhiran anoat


asam lemak tdk jenuh : dg akhiran enoat
atom karbon no. 1 : atom karbon ggs karboksil
atom karbon no. 2 : atom karbon alfa
tanda : menunjukkan jumlah dan posisi ik
rangkap

Oleic acid. n 9 (n minus 9) is equivalent


to 9.

Waxes

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Waxes :

ester of fatty acids and long chain alcohol

O
||
R - C - O - R1

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)

C30 H61

O
O C

C15 H31

C16 H33

O
O C

C15 H31

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O
O H C-OH
H-O-C-CH2C-R1
HO-CH O
R2-CH2-CH-O-C-CH2C-R3
OH
H C-OH
H
Monoacylglycerol/monoglyceride
Diacylglycerol/
diglyceride
H

Triacylglycerol
glycerol = Triglyceride

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Chemical Properties of Triacylglycerols


The chemical reactions of triacylglycerols are similar
to those of alkenes and esters.
Hydrogenation of double bonds in unsaturated fatty
acids by H2 (compare to alkenes).
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

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Triglycerides
Stored as droplets
of adipose tissue
in body fat.

Fat stored in this cell

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Hydrogenated Fats

Hydrogenation of
vegetable oils
converts some of
unsaturated bonds
to saturated,
trans
conformation.
Diet high in trans
fatty acids risks
heart disease,
cancer.

cis

trans
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PYROLYSIS

O
//
CH2 - O - C - R1
O
//
CH - O - C - R2
O
//
CH2 - O - C - R3

O
//
3 CH2 - O - C - R

fatty acids

-o2
CH2 = CH - C - H

O
//

acrolein

Hydrogenation: addition of two hydrogen atoms


over a double bond. Some food products are
partially hydrogenated
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Oxidation
- COOH
( fatty acid)
- C = C - + O2

H 2O

-C - C

O - O
(Peroxide)

- CHO
- C=O

Oxidation: addition of oxygen (ex: air) can


lead to oxidation of the double bonds present
in a fatty acid, which produces carboxylic
acids.
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Rancidification

Lipase
//

Fat

R - CH2 - CH2 - C - O - H

the decomposition
of fats and other
lipids by
hydrolysis and or
O
oxidation

//
R - C - CH2 - C - O - H
//
O
Keton

-Oksidase

//
R - C - C + CO2

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Glycerol esterified to
2 fatty acids.
Third position is
phosphate
Other end of
phosphate can
PHOSPHATE
combine with other
molecules to form
various derivatives
Amphipathic
OH
emulsifying agents Phosphatidyl
inositol
Production of cell
H
membrane
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H
OH
H
OH

OH
H
H

OH

Each glycerophospholipid / phosphoacylglycerol


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

O
R1

H2C
O

CH
H2C

glycerophospholipid

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R2

O
O

non-polar hydrocarbon tails


of fatty acids (R1, R2).

P
O

O
O
R1

H2 C
O

CH
H2 C

R2

O
O

CH3

H2
CH

OH
Phosphatidic acid
Phosphatidyl

OH

Phosphatidylinositol

CH2
H

+
N CH3
CH3

OH
Phosphatidylcholine/lechitin
OH
H
It is
OH

H
a common
membrane lipid
H

H
H

OH

In addition to being a membrane lipid,


phosphatidylinositol has roles in cell
signaling.
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phosphatidyl choline =
lechitin

Lecithin, a
common food
additive, is a
phospholipid.
Embedded in
cell
membranes.

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Cell Membrane

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Phosphatidyl choline with fatty acids


as oleate and palmitate

O
CH3
+

H3C

CH3

O P

H2C

HC

(CH2)7 C
H
(CH2)14

C
H

(CH2)7 CH3

CH3

CH2

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Sphingolipids
Sphingosine instead of glycerol
Derivatized at ester C1
Fatty acids added at amine
Different types are found in
plasma membrane and myelin
sheaths
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The amino group of sphingosine can


form an amide bond with a fatty acid
carboxyl, to yield a ceramide
Ceramides usually include a polar head
Sphingomyelins
group, esterified to the terminal OH
are found
of the sphingosine
abundantly in the
CHCH
O
3 2OH
myelin sheath that
H2 H

O2
+
OH
N
H3C
O
P
O
C
C
surrounds the
H
H
nerve fibers
OH
OH
OH
H

CH3

OH

H
Sphingomyelin, a ceramide
H
C
CH
C
2
H
OH
with a phosphocholine or
A cerebroside is a head
phosphethanolamine
H2N
CH
OH
sphingolipid
(ceramide)
with a
group,
is a common
constituent
monosaccharide
such as
CH
O
C
of
plasma membranes
glucose or galactose
as polar
Sphingomyelin
Sphingolipids
head group.
R (CH 2 )12
/ceramide
sphingosine
CH 3

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Steroid Nucleus
Consists of:
3 cyclohexane rings.
1 cyclopentane ring.
no fatty acids.

steroid nucleus
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Cholesterol
is the most abundant steroid in the body.
has methyl CH3- groups, alkyl chain, and
-OH attached to the steroid nucleus.
CH3
CH3

CH3
CH3

CH3

HO

HO
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Precursor to Vitamin D

-important constituent of cell


membranes
-has a rigid ring system and
a short branched
hydrocarbon tail.
Precursor to Bile Acids:
- Act as detergents to
dissolve
dietary fats
- Fats can be broken
better by enzymes

HO

amphipathic.

Keeps the lipids in membrane


from aggregrating: Keeps the
membrane intact as a bilayer

hydrophobic

Precursor to steroid hormones


that regulate gene expression

A normal, open artery.

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An artery clogged by
cholesterol plaque

HO

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.
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53

.
The OH group of cholesterol forms hydrogen bonds
with polar phospholipid head groups.

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eukaryotic cell
High temperature
increase membrane fluidity

membrane fluidity
Low temperatur
decrease membrane fluidity

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Lipoproteins: LDL, HDL, Etc


combine lipids
with proteins &
phospholipids.
are soluble in
water because
the surface
consists of
polar lipids.
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Types of Lipoproteins
differ in density, composition, and
function.
include low-density lipoprotein (LDLs)
and high-density lipoprotein (HDLs).

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Transport of Lipoproteins in the


Body

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Good vs Bad Cholesterol


Related to lipoproteins (protein + lipid
complexes)
Dietary excess fat is packaged into
VLDL
Fat cells (adipose cells) take these up
convert to fatty acids
Some VLDL is converted to LDL
LDL is very rich in Cholesterol
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LDL
circulate in the blood
Build up in arteries; lead
to heart attack

level 130 mg/dL,


reflects an increased
risk of heart disease

HDL
cholesterol
lipoprotein,
that returns to the liver ;
removes cholesterol out of
the bloodstream;
believed to prevent heart
attacks
level < 40 mg/dL, is
thought to increase the
risk for heart disease.

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