LIPIDS

PRASETYASTUTI

LIPIDS

Insoluble in water
Soluble in non polar solvents : ether, CHCl3, benzene
The lipids include : fats, oils, steroids, waxes
Important dietary constituents because
- of their high energy value
- the fat - soluble vitamins
- the essential fatty acids contained in the fat of
natural foods
Serves as
1. an efficient source of energy directly and potentially
when stored in adipose tissue

Serves as
1. an efficient source of energy directly and potentially
when stored in adipose tissue
2. A thermal insulator in the sub cutaneous tissues and
around certain organs
3. Non polar lipids act as electrical insulator

Lipoprotein ( combination of fat and protein ) are:

- important cellular constituents
- occurring in the cell membrane in the mitochondria
within the
cytoplasm
- transporting lipids in the blood

CLASIFICATION
1. Simple lipids: ester of fatty acids with various alcohols
a. Fats : ester of fatty acids with glycerol

b.

Oil , a fat in the liquid state

Waxes : ester of fatty acids with higher molecular weight
monohydride alcohos

2. Complex lipids : ester of fatty acids containing groups in

addition to an alcohol and a fatty acids
a. Phospholipids : lipids containing fatty acids, alcohol , a
phosphoric acids residue frequently have nitrogen
containing bases and other substituent
- glychophospholipids : the alcohol is glycerol
- sphingophospholipids : the alcohol is sphingosine
b. Glycolipids : lipids containing a fatty acid, sphingosine,
carbohydrate

 C. Other complex lipids : sulfolipids, aminolipids , lipoproteins

3. Precursor and derived lipids
Include : fatty acids, glycerol, steroids, alcohols in addition to glycerol
and sterols, fatty aldehides and ketone bodies, hydrocarbons, lipidsoluble vitamins, and hormones

Acylglycerols (glycerides)
Cholesterol
Cholesteryl esters
-------------------------- neutral lipids because they are uncharged

 FATTY ACIDS

- are aliphatic carboxylic acids

- occur mainly as :
ester in natural fats and oils ( unesterified form)
Usually straight-chain derivatives and contain an even
number of carbon atoms because they are synthesized from
two-carbon units
free fatty acids
Saturated acids end in anoic ( octanoic acid)
Contain no double bonds
CH3 COOH : the first member of the series
- CH2 is progressively added between the terminal CH3
and COOH groups

 Unsaturated acids end in enoic ( octadecenoic acid (oleic acid)

Contain one or more double bonds
1. Monounsaturated : contain one double bond
2. Poly unsaturated : contain >/ 2 double bond
3. Eicosanoid
: derived from eicosa ( -20-C ) polyenoic fatty
acids
= Prostanoids :
Prostaglandin
Prostasiklin
Tromboxan
= Leukotrienes
= lipoxins

 Prostaglandins

Exist in every mammalian tissues

Acting as local hormones
Have important physiologic and pharmacologic activities.
Synthesized in vivo by cyclization of the center of the carbon chain of
20 carbon (eicosanoic) polyunsaturated fatty acids to form a
cyclopentane ring

 Physical and physiologic properties of fatty acids

- the melting points of even numbered- carbon fatty acids increase
with chain length and decrease according to unsaturation
Triacylglycerol contaning all saturated fatty acids of 12 carbons or
more is solid at body temperature
If all three fatty acid residues are 18 :2, it is liquid to below O o C

TRIACYLGLYCEROLS ( TRIGLYCERIDES)

- the main storage forms of fatty acids

-esters of the alcohol glycerol and fatty acids.
- in naturally occurring fats
- the propotion of triacylglycerol molecule containing the same fatty
acid residue in all three ester positions is very small.
- nearly all mixed acylglycerols
- if all three fatty acids represented by R were stearic acid : tristearin

 PHOSPHOLIPIDS
the main lipid constituents of membranes
include :
1. Phosphatidic acid and phosphatidylglycerol : intermediate
in synthesis of TG
2. Phosphatidylcholine ( lecithins)
- occur in cell membranes
- represent a large proportion of the bodys store of choline
(important in nervous transmission, as acetylcholine, and as
store of labile methyl groups
Dipalmitoyl lecithin :
- very effective surface-active agent
- major constituent of the surfactant preventing adherence,
due to surface tension

3. Phosphatidylethanolamine (cephalin)
4. Phosphatidylinositol
- is a precursor of second messengers
- inositol as the stereoisomer, myoinositol
- Phosphatidylinositol 4,5 bisphosphate
is an important constituent of cell membrane phospholipids
It is cleaved ---- diacylglycerol and inositol triphosphate ( act as
internal signals or second messengers)

5. Phosphatidylserine
6. Lysophospholipids
Intermediates in the metabolism of phosphoglycerols
Phosphoacylglycerols containing only one acyl radical
( lysophosphatidylcholin = lysolecithin, important in the metabolism and
interconversion of phospholipids

7. Plasmalogens
- constitute as much as 10% of phospholipids of brain and muscle
- structurally resemble phosphatidylethanolamine
8. Sphingomyelins
- are found in large quantities in brain and nerve tissue.
- on hydrolysis, yield a fatty acud, phosphoric acid, choline, and a
complex amino alcohol, sphingosine
-combination of sphingosine plus fatty acid is ceramide

Glycolipids (glycosphingolipids)
Are important in nerve tissues and in the cell membrane
Are widely distributed in every tissue of the body,
particularly in nervous tissue such as brain.
Occur particularly in the outer leaflet of the plasma
membrane, where they contribute to cell surface
carbohydrates

Glycosphingolipids :
the major glycolipids found in animal tissues
Contain ceramide and one or more sugars

Galactosylceramide :
a major glycosphingolipid of brain and other
nervous tissue
Can be converted to sulfogalactosyl ceramide
(sulfatide) is present in high amounts in myelin
Glucosylceramide :
Predominant simple glycosphingolipid of
extraneural tissues, in the brain in small amount
Gangliosides
Are complex glycosylceramide that contain in
addition one or more molecules of a siallic acid

 Neuraminic acid is the principal sialic acid found in human

tissues
Present in nervous tissues in high concentration
The simplest ganglioside found in tissues is Gm3
Gm3 contain ceramide, one molecule of glucose, one
molecule of galactose and one molecule of NeuAc

 STEROIDS
Cholesterol
Is widely distributed in all cells of the body, particularly in nervous
tissue
A major constituent of the plasma membrane & plasma lipoprotein
Often found as cholesteryl ester
Occurs in animal fat, not in plant fat
precursor :

The bile acids

Adrenocortical hormones
Sex hormones
D. vitamins
Cardiac glycosides
Sitosterols
Some alkaloids

ERGOSTEROL
A precursor vitamin D
Occurs in plants and yeast
When irradiated with UV light, it acquires antirachitic
properties consequent to the opening of ring B
COPROSTEROL/COPROSTANOL
Occurs in feces as a result of the reduction of the double
bond of cholesterol between C5 and C6 by bacteria in the
intestine

 POLYPRENOIDS
Not steroids
Are synthesized like cholesterol, from five carbon isoprene
units
Include:
* ubiquinone : a member of the respiratory chain in
mitochondria
* dolicol : the long chain alcohol
Take part in glycoprotein synthesis by transferring
carbohydrate residues to asparagine residues of the
polypeptide
* rubber
* camphor
* vit. A, D, E, K and beta carotene :

 LIPID PEROXIDATION
Is a source of free radicals ( ROO., RO. OH.)
Peroxidation lipids exposed to oxygen is responsible for
Deterioration of food (rancidity)
Damage to tissues in vivo ----
Cause : cancer
Inflammatory diseases
Atherosclerosis
aging

The whole process of lipid peroxidation:

1. Initiation
ROOH + metal (n)+ ----- ROOo + metal (n-1)+ + H+
Xo + RH
----- Ro + XH

2. Propagation
Ro + O 2
----- ROOo
ROOo + RH

----- ROOH + Ro

3. Termination
ROOo + ROOo ----- ROOR + O2
ROOo + Ro
Ro
+ Ro

----- ROOR
----- RR

 To control and reduce lipid peroxidation use antioxidants

- propyl gallate
Butylated hydroxyanisole (BHA)
Butylated hydroxytoluene (BHT)
Vitamin E (tocopherol) ---- lipid soluble
antioxidant at high PO2

Urate
Vitamin C
Bata carotene , antioxidant at low PO2

Antioxidants fall into two classes

1. Preventive antioxidants : reduce the rate of chain
initiation
: catalase, DTPA, EDTA
2. Chain breaking antioxidants ; interfere with chain
propagation
: phenol
Superoxide dismutase : which acts in the aqueous phase to
trap superoxide free radicals
Urat and Vitamin E : which acts in the lipid phase to trap
ROOo radicals
Peroxidation is also catalyzed by : heme compounds
And lipoxygenase

 Separated and identify lipids

I. Classic chemical procedures
Crystallization
Distillation
Solvent extraction

II. Chromatographic procedures

TLC : separation of the various lipid classes
GLC : separation of the individual fatty acids

Amphipathic
Lipids are insoluble in water( contain a predominance of
non polar= hydrocarbon)
Fatty acids, phospholipids, sphingolipid, bile salt,
cholesterol contain polar groups
Part of the molecule is hydrophobic, or water in soluble
and part is hydrophilic, or water soluble === amphipathic
They become oriented at oil- water interface with the polar
group in the water phase and nonpolar group in the oil
phase.
A bilayer of such amphipathic lipids has been regarded as
a basic structure in biologic membranes