LIPIDS

DEFINITION

• The lipids are a heterogeneous

group of compounds, including fats,
oils, steroids, waxes, and related
compounds, that are related more
by their physical than by their
chemical properties.
Property

(1)relatively insoluble in water and

(2) soluble in nonpolar solvents such

as ether and chloroform.
• stored in adipose tissue
• Nonpolar lipids act as electrical
insulators,
• allowing rapid propagation of
depolarization waves along
myelinated nerves
• Combinations of lipid and protein
(lipoproteins) serve as the means
of transporting lipids in the blood.
LIPIDS ARE CLASSIFIED AS
SIMPLE
OR COMPLEX
CLASSIFICATION OF LIPIDS

I. Simple Lipids

II. Complex Lipids

III. Derived Lipids

IV. Miscellaneous
Simple lipids:

• Esters of fatty acids with various alcohols.

• a. Fats: Esters of fatty acids with glycerol.
Oils are fats in the liquid state.
• b. Waxes: Esters of fatty acids with higher
molecular weight monohydric alcohols.
• Neutral fats (Triacylglycerol, TG): These are
triesters of fatty acids with glycerol.
Complex lipids:

• Esters of fatty acids containing groups in

addition to an alcohol and a fatty acid.
• a. Phospholipids: Lipids containing, in addition to
fatty acids and an alcohol, a phosphoric acid
residue. They frequently have nitrogen
containing bases and other substituents, eg, in
glycerophospholipids the alcohol is glycerol and
in sphingophospholipids the alcohol is
sphingosine.
Examples:

• phosphatidyl choline (Lecithin), phosphatidyl

ethanolamine (Cephalin), phosphatidyl inositols
(Lipositols), phosphatidyl serine, plasmalogens,
sphingomyelins, etc.
 Glycolipids (glycosphingolipids):

• Lipids containing a fatty acid, sphingosine, and

carbohydrate.
Lipids containing carbohydrate moiety are called glycolipids.
They contain a special alcohol called sphingosine or sphingol
and nitrogenous base in addition to fatty acids but does not
contain phosphoric acid or glycerol.
These are of two types:
• Cerebrosides
• Gangliosides
Other complex lipids:

• Lipids such as sulfolipids and aminolipids

(proteolipids). Lipoproteins may also be
placed in this category.
 Miscellaneous

• Aliphatic hydrocarbons include iso-octadecane

found in liver fat and certain hydrocarbons found in
bees wax and plant waxes.
• Carotenoids
• Squalene is a hydrocarbon found in shark and
mammalian liver and in human sebum.
• Vitamins E and K.
Precursor and derived lipids:

• These include fatty acids, glycerol, steroids,

other alcohols, fatty aldehydes, ketone
bodies, hydrocarbons, lipid-soluble vitamins,
and hormones. Because they are uncharged,
acylglycerols (glycerides), cholesterol, and
cholesteryl esters are termed neutral lipids.
Importance of Lipid

• They are important dietary constituents not only because of

their high energy value but also because of the fat-soluble
vitamins and the essential fatty acids contained in the fat of
natural foods.
• Fat is stored in adipose tissue, where it also serves as a thermal
insulator in the subcutaneous tissues and around certain organs.
• Nonpolar lipids act as electrical insulators, allowing rapid
propagation of depolarization waves along myelinated nerves.
Importance of Lipid

• Combinations of lipid and protein

(lipoproteins) are important cellular
constituents, occurring both in the cell
membrane and in the mitochondria, and
serving also as the means of transporting
lipids in the blood.
FATTY ACIDS

• FATTY ACIDS ARE ALIPHATIC CARBOXYLIC ACIDS

Fatty acids Found in the

occur in the unesterified form
body mainly as as free fatty acids,
esters in a transport form in
natural fats the plasma
and oils,
Natural Fatty acids

• Fatty acids that occur in natural fats

usually contain an even number of
carbon atoms.
• The chain may be saturated (containing
no double bonds) or unsaturated
(containing one or more double bonds)
Fatty Acids Are Named after
Corresponding Hydrocarbons
Saturated Fatty Acids Contain No Double
Bonds
Unsaturated Fatty Acids Contain One or
More Double Bonds

1. Monounsaturated (monoethenoid, monoenoic) acids,

containing one double bond.

2. Polyunsaturated (polyethenoid, polyenoic) acids, con

taining two or more double bonds.

3. Eicosanoids: These compounds, derived from eicosa (20

carbon) polyenoic fatty acids, comprise the prostanoids,
leukotrienes (LTs), and lipoxins (LXs). Prostanoids in clude
prostaglandins (PGs), prostacyclins (PGIs), and
thromboxanes (TXs)
Physical and Physiologic Properties of Fatty Acids
Reflect Chain Length and Degree of Unsaturation

• melting points
• even-numbered carbon fatty acids
in crease with chain length and
decrease according to unsaturation.
 Melting Point
•Increase with chain length: As the number of carbon atoms in a fatty
acid increases, the melting point also increases. This is because longer
hydrocarbon chains have more surface area, leading to stronger van der
Waals (London dispersion) forces between molecules, which require
more energy to break.
•Decrease with unsaturation: The melting point decreases as the
degree of unsaturation (number of double bonds) increases. Naturally
occurring unsaturated fatty acids typically have cis double bonds,
which create "kinks" or bends in the chain. These kinks prevent the
molecules from packing tightly together in a solid lattice, weakening
intermolecular attractions and lowering the temperature required to melt
them.
TRIACYLGLYCEROLS (TRIGLYCERIDES)*
ARE THE MAIN STORAGE FORMS OF
FATTY ACIDS
• The triacylglycerols are esters of the
trihydric alcohol glycerol and fatty acids.
• They are significant in the synthesis and
hydrolysis of triacylglycerols
Carbons 1 & 3 of Glycerol Are Not
Identical

sn (stereochemical numbering) system

Carbons 1 & 3 of Glycerol Are Not
Identical

• Enzymes readily distinguish between

them and are nearly always specific for
one or the other carbon; eg, glycerol is
always phosphorylated on sn-3 by
glycerol kinase to give glycerol 3-
phosphate and not glycerol 1-phosphate.
PHOSPHOLIPIDS ARE THE MAIN LIPID
CONSTITUENTS OF MEMBRANES
• derivatives of phosphatidic acid
• phosphate is esterified with the —OH of a
suitable alcohol
Phosphatidic acid is
important as an intermediate
in the synthesis of
triacylglycerols as well as
phosphoglycerols but is not
found in any great quantity
in tissues
Phosphatidylcholines (Lecithins) Occur in
Cell Membranes
Phosphatidylcholines

• Abundant phospholipids of the cell

membrane
• Large proportion of the body’s store of
choline.
• Choline is important in nervous
transmission, as acetylcholine, and as a
store of labile methyl groups.
Dipalmitoyl lecithin

• Dipalmitoyl lecithin is a very effective

surface-active agent and a major
constituent of the surfactant preventing
adherence, due to surface tension, of the
inner surfaces of the lungs. Its absence
from the lungs of premature infants
causes respiratory distress syndrome.
Phosphatidylethanolamine (cephalin)
and phosphatidylserine

Phosphatidylserine
also plays a role in
apoptosis
(programmed cell
death).
Phosphatidylinositol Is a Precursor of
Second Messengers

• The inositol is present in phosphatidylinositol

as the stereo isomer, myoinositol
Phosphatidylinositol 4,5-bisphosphate

• Phosphatidylinositol 4,5-bisphosphate is
an important constituent of cell membrane
phospholipids; upon stimulation by a
suitable hormone agonist, it is cleaved into
diacylglycerol and inositol tris phosphate,
both of which act as internal signals or
second messengers
Cardiolipin Is a Major Lipid of
Mitochondrial Membranes

• Phosphatidic acid is a precursor of

phosphatidylglycerol which, in turn, gives rise to
cardiolipin.
• Found only in mitochondria and is essential for
mitochondrial function.
• Mitochondrial dysfunction in aging and in pathological
conditions including heart failure, hy pothyroidism and
Barth syndrome (cardioskeletal myopathy).
Lysophospholipids Are Intermediates in
the Metabolism of Phosphoglycerols

important in the
metabolism and
interconversion of
phospholipids. It is also
found in oxidized
lipoproteins and has
been implicated in some
of their effects in
promoting
atherosclerosis
Plasmalogens Occur in Brain & Muscle

• These compounds constitute as much as

10% of the phospho lipids of brain and
muscle. Structurally, the plasmalogens re
semble phosphatidylethanolamine but
possess an ether link on the sn-1 carbon
instead of the ester link found in
acylglycerols.
Sphingomyelins Are Found in the
Nervous System

• Sphingomyelins are found in large

quantities in brain and nerve tissue. On
hydrolysis, the sphingomyelins yield a
fatty acid, phosphoric acid, choline, and
a complex amino alcohol, sphingosine
• No glycerol is present.
The com bination of
sphingosine plus fatty
acid is known as
ceramide, a structure
also found in the
glycosphingolipids
GLYCOLIPIDS (GLYCOSPHINGOLIPIDS) ARE IMPORTANT
IN NERVE TISSUES & IN THE CELL MEMBRANE

• cell surface carbohydrates.

• major glycolipids found in animal tissues are
glycosphingolipids. They contain ceramide and
one or more sugars.
• Galactosylceramide is a major glycosphingolipid
of brain and other nervous tissue, found in
relatively low amounts else where. It contains a
number of characteristic C24 fatty acids, eg,
cerebronic acid.