Biochemistry
LIPIDS
BY :
AGUNG RAHMADANI
DEPARTMENT OF PHARMACY
UNIVERSITY OF MULAWARMAN
SAMARINDA
2016
Lipids ???
Lipids are a class of biological molecules
defined by low solubility in water and high
solubility in nonpolar solvents.
As molecules that are largely hydrocarbon in
nature, lipids represent highly reduced forms of
carbon and, upon oxidation in metabolism, yield
large amounts of energy. Lipids are thus the
molecules of choice for metabolic energy torage.
2
Functions Of Lipids
Lipids are the constituents of cell membrane and regulate membrane
permeability.
They protect internal organs, serve as insulating materials and give
shape and smoothness to the body.
They serve as a source of fat soluble vitamins.
Essential fatty acids are useful for transport of cholesterol, formation
of lipoproteins, etc.
Phospholipids in mitochondria are responsible for transport of
electron transport chain components.
Accumulation of fat in liver is prevented by phospholipids.
Phospholipids help in removal of cholesterol from the body by
participating in reverse cholesterol transport.
Cholesterol is a constituent of membrane structure and it synthesizes
bile acids, hormones and vitamin D. It is the principal sterol of higher
animals, abundant in nerve tissues and gallstones.
Classification Of Lipids
LIPIDS are broadly classified into simple lipids, complex lipids, derived
lipids and miscellaneous lipids based on their chemical composition.
1.
2.
3.
4.
SIMPLE LIPIDS: These lipids are the esters of fatty acids with
alcohols. They are of two types: Waxes and Triacylglycerides
COMPOUND/COMPLEX LIPIDS: These lipids are esters of fatty
acids with alcohols with additional groups such as phosphate,
nitrogenous base, etc. They are again divided into 3 types:
Phospholipids, Glycero phosphlipids, Sphingophospholipids.
DERIVED LIPIDS: These lipids are obtained on hydrolysis of simple
and complex lipids. These lipids contain glycerol and other alcohols.
This class of lipids include steroid hormones, ketone bodies,
hydrocarbons, fatty acids, fatty alcohols, mono and diacylglycerides.
MISCELLANEOUS LIPIDS: These include compounds, which contain
characteristics of lipids. They include squalene, terpenes,
hydrocarbons, carotenoids, etc.
Classification Scheme
Lipids
1.
2.
Complex
Simple
Wax esters
Triglycerides
1.
2.
Phospholipids
Glycerophospholipids
1.Phosphatidylcholine (PC)
2.Phosphatidylethanolamine (PE)
3.Phosphatidylinositol (PI)
Glycolipids
1.Cerebrosides
2.Gangliosides
3.
4.
Derived
Fatty acids
Sterols
Diglycerides
monoglycerides
Sphingolipids
1.Ceramides
2.Sphingomyelin
Triglycerides
The fats and oils found in animals and
plants are triglycerides
Triglycerides are:
esters of fatty acids and glycerols
simple lipids
important as the storage form of fat in the
human body
Triglycerides
They are esters of glycerol with various
fatty acids. Since the 3 hydroxyl groups
of glycerol are esterified, the neutral fats
are also called Triglycerides.
Triglycerides
Triglycerides are a combination of three 3 fatty
acid molecules with a glycerol molecule.
Triglycerides
Glycerol, which is also called
glycerin, is an alcohol with
three hydroxyl groups.
HO
CH2
As with the waxes, the fatty
acids can react with the
hydroxyl groups to form esters.
HO
CH
Since there are three hydroxyl
groups, three fatty acids can
react to form three esters.
HO
CH2
glycerol
Triglycerides
For triglycerides, all three hydroxyls of the
glycerol have a fatty acid residue attached to
O
it.
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C
CH2
O
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C O
CH
O
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C O
fatty acid
residues
CH2
glycerol
residue
10
11
Waxes
Waxes
wax is monoester formed from the reaction of
long-chain monohydroxy alcohol with fatty acid
molecule.
The block diagram:
Example
Biological role: They serve as protective coatings on
leaves, stems, and fruit of plants and the skin and fur of
animals.
Waxes
Differences between neutral lipids and waxes
Waxes
1.Digestibility:
Indigestible (not
hydrolyzed by lipase).
Neutral lipids
Digestible (hydrolyzed by lipase).
2-Type of alcohol:
Long-chain monohydric
alcohol + one fatty acid.
Glycerol (trihydric) + 3 fatty acids
3-Type of fatty
acids:
Fatty acid mainly palmitic
or stearic acid.
Long and short chain fatty acids.
4-Acrolein test:
test
Negative.
Positive.
5-Rancidability:
Never get rancid.
Rancidible.
6-Nature at room
temperature.
temperature
Hard solid.
Soft solid or liquid.
7-Saponification
Nonsaponifiable.
Saponifiable.
8-Nutritive value:
value
No nutritive value.
Nutritive.
9-Example:
Bee & carnuba waxes.
Butter and vegetable oils.
Waxes
Fatty Acids
Definition:
Definition
Fatty
acids are aliphatic monocarboxylic acids that are mostly
obtained from the hydrolysis of
natural fats and oils.
Have the general formula R-(CH2)nCOOH and mostly have straight chain
(a few exceptions have branched and
heterocyclic chains). In this formula
"n" is mostly an even number of
carbon atoms (2-34) with a few
exceptions that have an odd number.
According to presence or absence of
double bonds they are classified into:
A-Saturated Fatty Acids
They contain no double bonds with 2-24
or more carbons.
They are solid at room temperature
except if they are short chained.
They may be even or odd numbered.
They
have the following molecular
formula, CnH2n+1COOH.
16
Saturated fatty acid
Fatty acid chains that contain only carbon-carbon
single bonds are referred to as saturated.
Palmitic acid:
B-Unsaturated Fatty Acids
They contain double bond
monounsaturated
they contain one double bonds .
(CnH2n-1 COOH)
polyunsaturated
they contain more the one double bond
(CnH2n-more than 1 COOH).
Unsaturated fatty acid
Those
molecules that contain one or
more double bonds are said to be
unsaturated.
There are mono- and polyunsaturated
fatty acids.
Oleic acid:
Structure of fatty acids
The figure was adopted from: J.Koolman, K.H.Rhm / Color Atlas of Biochemistry, 2 nd edition
Physical Properties of Fatty Acids
The
physical properties of fatty acids are largely determined
by the length and degree of unsaturation of the hydrocarbon
chain.
The
longer the chain and the fewer the double bonds, the
lower is the solubility in water, and higher is the melting
point.
Addition of double bonds decreases the melting point
whereas, increasing the chain length increases the melting
point. For example; 4:0 MP -7.9 C, 12:0 MP 44.2 C, 16:0 MP
62.7 C, 18:1 MP 10.5 C, 18:2 MP -5.0 C, 18:3 MP -11 C.
The Packing of Fatty Acids
isomerism
A double bond in Fatty acid chain permits
two types of geometrical isomers, cis and
trans.
Cis isomers have a curved configuration.
Trans isomers have a linear configuration.
Due to curve configuration cis unsaturated
fatty acids have a lower melting point as
compared to there trans counterpart.
Most of the natural unsaturated fatty acids
have cis double bonds.
Positional Isomers
Saturated
M.P.(69.6 C)
Trans, similar to
linear structure
M.P. (42.0 C)
COOH
COOH
Linear structure
CH3
Positional Isomers
Saturated
Linear structure
M.P.(69.6 C)
COOH
Cis one curved
structure
M.P. (10.5 C)
COOH
CH3
CH3
Positional Isomers
Saturated
Linear structure
M.P.(69.6 C)
COOH
Cis Two curved
structure
M.P. (-5.0 C)
COOH
CH3
CH3
Physical properties of fat and
oils:
1.
2.
3.
4.
Freshly prepared fats and oils are
colorless, odorless and tasteless. Any
color, or taste is due to association
with other foreign substances, e.g., the
yellow color of body fat or milk fat is
due to carotene pigments (cow milk).
Fats have specific gravity less than 1
and, therefore, they float on water.
Fats are insoluble in water, but soluble
in organic solvents as ether and
benzene.
Melting points of fats are usually low, but
higher than the solidification point,
Complex Lipids
* Phospholipids: They are esters of phosphoric
acids. There are two main types of phospholipids in
cellular membranes:
Glycerophospolipids: They are also known as
Phosphatidylcholine (lecithin). They are built from long chain
fatty acid, glycerol and phosphoric acids.
Spingolipids: They do not contain glycerol. Instead, they
contain sphingosine, a long-chain unsaturated amino alcohol.
Only one fatty acid is attached to the sphingisine.
Sphingomylins are found in brain and nervous tissue and in
the myelin sheath, the protective coat of nerves.
3-phosphoglycerol (building block for phosphoglycerides)
Glycerophospholipids
General structure of a glycerophospholipid.
Note the glycerol-3-phosphate backbone
Neuraminic Acid = Sialic Acid
Complex Lipids
Glycolipids: A lipid molecule that contains
carbohydrates, which is usually a simple
sugar like glucose or galactose
They are also called cerebrosides because
of their abundance in brain.
Galactolipids
Sulfolipids
Sulfolipids have a sulfonated glucose residue joined to a
diacylglycerol in glycosidic linkage. They also exist predominantly
in chloroplast.
Steroids
Steroids are a family of lipids found in plants
and animal
A steroid contains four fused carbon ring: 17 carbon
atoms make the structural unit of steroids known as
steroid nucleus.
Steroid nucleus is found in a number of extremely
important
biological
molecules:
cholesterol,
adrenocorticoid hormones, the sex hormone and bile
acids.
Steroids - overview
Sterols are steroid alcohols
-OH group in C-3 position and one or more double bonds
cholesterol, ergosterol (plants)
Bile acids are synthesized from cholesterol in the liver
cholic acid, chenodeoxycholic acid, lithocholic acid, deoxycholic acid
Steroid hormones regulate metabolism, growth and reproduction
progesterone, estrogene, testosterone, aldosterone, cortisol,
calcitriol
Cholesterol (membrane sterol)
Cholesterol is found only
in animal cells. A typical
animal cell membrane
contains
about
60%
phospholipids and 25%
cholesterol.
Cholesterol
free cholesterol
Cholesterol is a constituent of cellular membranes and it is present
in all animal tissues.
Cholesterol esters with FA are insoluble in the water.
Lipoproteins (LDL, HDL) are transporters of cholesterol in blood.
Figures were assumed from a book T. M. Devlin et al.: Textbook of Biochemistry With Clinical Correlations, 4th ed., Wiley Liss,
Inc., NewYork, 1997.
Steroid Hormones Made from Cholesterol
Multistep
Glucose Metabolism
Cholesterol
Anti-inflammatory
Salt Excretion
Synthesis of Vitamin-D
Regulate
Calcium
Metabolism
Steroid hormones
cholesterol is a metabolic precursor of all steroid
hormones in human body
number of C atoms is changing during synthesis of
hormones: from 27 to 21, 19 or 18
glucocorticoids (21 C)
mineralocorticoids (21 C)
sex hormones (progesterone 21 C, testosterone 19
C, estrogene 18 C)
Steroid hormones
Figure was adopted from: J.Koolman, K.H.Rhm / Color Atlas of Biochemistry, 2nd edition, Thieme 2005
Lipoproteins are used to
transport the water insoluble
lipids such as triglycerides,
phospholipids and
cholesterol, in the blood.
Lipoproteins contain lipids and
proteins.
They include:
Chylomicrons transport primarily
triglycerides from the digestive
track.
LDLs (low density lipoproteins)
transport cholesterol, triglycerides
and phospholipids from the liver to
other tissues.
HDLs (high density lipoproteins)
transport cholesterol and
phospholipids back to the liver.
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Lipoproteins
The HDL and LDL levels in the blood can be
used to assess ones risk for atherosclerosis.
High levels of HDL is considered good
This is why HDL is sometimes referred to as good
cholesterol
> 40 mg/dL is good.
High levels of LDL is considered bad
This is why LDL is sometimes referred to as bad
cholesterol
> 100 mg/dL is bad.
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Isoprenoids and steroids
isoprenoids (terpenes) are derived from an isoprene (2methyl-1,3-butadiene)
isoprene metabolism in plants is very complex
synthesis of many types of aromatic substances
(menthol, camphor, citronellal)
activated isoprene can be used in synthesis of fatsoluble vitamins (A, D, E, K)
isoprene is a precursor in synthesis of cholesterol (
steroid hormones, bile acids)
Examples of terpenes
menthol (C10)
phytol (C 20)
squalene (C 30)
-carotene (C40)
The figures were adopted from http://en.wikipedia.org
Retinal Comes from Carotene
Isoprene Vitamins
Mitochondrial and Chloroplast
Membrane Electron Carriers
Carotenoids
Bile acids
Are formed from cholesterol in the
liver and they are excreted into a
bile
primary bile acids:
cholic and chenodeoxycholic acid
secondary bile acids:
deoxycholic and lithocholic acid
Function: emulsification of lipids in
intestine digestion and resorption
Figure was assumed from book T. M. Devlin et al.: Textbook of Biochemistry With Clinical
Correlations, 4th ed., WileyLiss, Inc., NewYork, 1997.
