Lipids

• Lipids are a heterogeneous group of naturally

occurring organic compounds
• Are soluble in nonpolar organic solvents and
are insoluble in water.
• The solubility of lipids in nonpolar organic
solvents is mainly due to their hydrocarbon
component.
• This hydrocarbon portion of the compound is
also responsible for its oily nature called
“oiliness” or “fattiness”.
• The word lipid comes from the Greek lipos,
which means ”fat”.
• Classification of Lipids
• Chemists have divided this large family into
two major classes: complex lipids and simple
lipids
• Complex lipids
• Complex lipids are those that are easily
hydrolyzed to simpler constituents.
• Complex lipids are those that are easily
hydrolyzed to simpler constituents.
• Most complex lipids are esters of long-chain
carboxylic acids called fatty acids.
• The two major groups of fatty acid esters are
waxes and glycerides.
• Waxes are esters of long-chain alcohols, and
glycerides are esters of glycerol.
• Simple Lipids
• Simple lipids are those that are not easily
hydrolyzed by aqueous acid or base.
• This is inverse of its name because many so-
called ―simple lipids are quite complex
molecules.
• We will consider three important groups of
simple lipids:
• steroids, prostaglandins, and terpene.
• Some examples
• Glycerides
• Glycerides are simply the esters of fatty acid
and triol glycerol.
• There are two types of Glycerides.
• a) Triglycerides b) Phosphoglycerides
• a) Triglycerides or Triacylglycerol
• The most common glycerides are triglycerides
(triacylglycerols),
• in which all three of the glycerol groups have
been esterified by fatty acids.
• For example, tristearin (Figure above) is a
component of beef fat in which all three
groups of glycerol are esterified by stearic acid
CH3(CH2)16COOH.
• Triglycerides or Triacylglycerols are the oils of
plants and the fats of animal origin.
• They include such common substances as
peanut oil, soybean oil, corn oil, sunflower oil
and butter.
• Triacylglycerols that are liquids at room
temperature are generally called oils; those
that are solids are called fats.
• Most naturally occurring triglycerides are
mixed triglycerides, containing two or three
different fatty acids.
• Fats and oils are commonly used for long-term
energy storage in plants and animals.
• Fat is a more efficient source of long-term
energy than carbohydrates because
metabolism of a gram of fat releases over
twice as much energy as a gram of sugar or
starch.
• Fatty Acids
• The fatty acids of common triglycerides are
long, unbranched carboxylic acids with about
12 to 20 carbon atoms.
• Most fatty acids contain even numbers of
carbon atoms because they are derived from
two-carbon acetic acid units.
• saturated carbon chains, while others have one
or more carbon–carbon double bonds.
• Table below shows the structures of some
common fatty acids derived from fats and oils.
• Fatty acids can be saturated with hydrogen (and
therefore have no carbon–carbon double
bonds) or unsaturated (have carbon–carbon
double bonds).
• Fatty acids with more than one double bond
are called polyunsaturated fatty acids.
• Double bonds in naturally occurring unsaturated
fatty acids are never conjugated—they are
always separated by one methylene group.
• Essential Fatty Acids
• Human body is unable to synthesize all fatty
acids.
• Those fatty acids that are not synthesized in the
body but required for normal body growth and
maintenance are called as essential fatty acids.
• These fatty acids are to be supplied through
diet.
• Linoleic and linolenic acids are essential fatty
acids.
• Other longer chain fatty acids can be
synthesized
• by the body from dietary linoleic and linolenic
acids.
• For example Arachidonic acid is essential but it
can be synthesized by the body from linolenic
acid. It is also present in the meat.
• Rancidity of Fats:
• Development of bad odour and taste in fat or
oil upon storage is called rancidity.
• Rancidity can be of two types.
• It may be due to hydrolysis of ester bonds
(hydrolytic rancidity).
• due to oxidation of unsaturated fatty acids
(oxidative rancidity).
• Reduction of Fatty Acid Chains
(Hydrogenation) Addition of Hydrogen to the
double bonds of Fatty acid chains is called
hydrogenation.
• In this process the oils are converted into fats
so this process is called hardening of oils and
involves catalytic reduction of some or all
carbon-carbon double bonds.
• Margarine and other butter substitutes are
produced by partial hydrogenation of
polyunsaturated oils derived from corn,
cottonseed, peanut, and soybean oils.
• To the hardened oils following additives are
added:
• β-carotene to give the final product a yellow
color and make it look like butter
• Salt and about 15% milk by volume to form
the final emulsion.
• Vitamins A and D.
• Acetoin and diacetyl are often added to give
it a taste of butter.
• Phospholipids:
• Phospholipids are lipids that contain groups
derived from phosphoric acid.
• The most common phospholipids are
phosphoglycerides or Phosphoacylglycerols,
which are closely related to common fats and
oils.
• A phosphoglyceride generally has a
phosphoric acid group in place of one of the
fatty acids of a triglyceride.
• They can be further classified as below:
• phosphatidic acid:
• They are similar to triacylglycerols except that
terminal OH group of glycerol is esterified with
phosphoric acid rather than with a fatty acid,
forming a phosphatidic acid.
• Cephalin and Lecithin:
• Many phospholipids contain an additional
alcohol esterified to the phosphoric acid group.
• Phosphatidylethanolamines also called
cephalins are esters of ethanolamine, and
phosphatidylcholines also called as Lecithins
are esters of choline.
• Both cephalins and lecithins are widely found
in plant and animal tissues and membranes.
• Lecithins are used as emulsifying agents and
added as to foods such as mayonnaise to
prevent the aqueous and fat components
from separating.
• Phosphoacylglycerols or phosphoglycerides
form membranes by arranging themselves in a
lipid bilayer.
• The polar heads of the phosphoacylglycerols
are on the outside of the bilayer, and the fatty
acid chains form the interior of the bilayer.
• Sphingomyelins: In sphingomyelins, the
primary OH group of sphingosine is bonded to
phosphocholine or phosphoethanolamine,
similar to the bonding in lecithins and
cephalins.
• Cerebrosides: In cerebrosides, the primary OH
group of sphingosine is bonded to a sugar
residue through apha linkage.
• Sphingomyelins are phospholipids because
they contain a phosphate group.
• Simple Lipids
• Simple lipids are those that are not easily
hydrolyzed by aqueous acid or base. We will
consider three important groups of simple
lipids: steroids, prostaglandins, and terpene.
• Steroids Steroids are complicated polycyclic
molecules found in all plants and animals.
• They are classified as simple lipids because
they do not undergo hydrolysis like fats, oils,
and waxes do. Steroids include a wide variety
of compounds, including hormones,
emulsifiers, and components of membranes.
• Hormones are chemical messengers—organic
compounds synthesized in glands and
delivered by the bloodstream to target tissues
in order to stimulate or inhibit some process.
• Many hormones are steroids. Because steroids
are nonpolar compounds, they are lipids.
Their nonpolar character allows them to cross
cell membranes, so they can leave the cells in
which they are synthesized and enter their
target cells.
• Structure of steroids: All steroids contain a
tetracyclic ring system.
• The four rings are designated A, B, C, and D. A,
B, and C are six-membered rings and D is a
five-membered ring. The carbons in the
steroid ring system are numbered as shown
• We have seen that rings can be trans fused or cis
fused and that trans fused rings are more stable.
In steroids, the B, C, and D rings are all trans
fused. In most naturally occurring steroids, the A
and B rings are also trans fused.
• Cholesterol: It is the most abundant member of
the steroid family in animals and is the precursor
of all other steroids. Cholesterol is biosynthesized
from squalene which is a triterpene.
• Cholesterol is an important component of cell
membranes. Its ring structure makes it more
rigid than other membrane lipids. Because
cholesterol has eight asymmetric carbons, 256
stereoisomers are possible, but only one exists
in nature (Figure below).
• Eicosanoids Eicosanoids are a class of molecules derived
from 20-carbon (―eicosa‖ is Greek for 20) polyunsaturated
fatty acids, most frequently Arachidonic acid. The
eicosanoids include the prostaglandins, thromboxanes,
leukotrienes and lipoxins. These molecules almost always
act on the cells that produce them or on neighboring cells,
that is, over short distances and time periods, and,
therefore, can be classified as autocrine/paracrine
hormones. They are widely distributed in the cells and
tissues of the body and have wideranging biological actions.
The eicosanoids play important roles in endocrine systems.
• Prostaglandins Prostaglandins are fatty acid
derivatives that are even more powerful
biochemical regulators than steroids. They are
called prostaglandins because they were first
isolated from secretions of the prostate gland.
They were later found to be present in all
body tissues and fluids, usually in minute
quantities
• Functions: Prostaglandins affect many body
systems, including the nervous system,
smooth muscle, blood, and the reproductive
system. They play important roles in regulating
such diverse functions as blood pressure,
blood clotting, the allergic inflammatory
response and the activity of the digestive
system.
• Structure: Prostaglandins have a cyclopentane
ring with two long side chains trans to each
other, with one side chain ending in a
carboxylic acid. Most prostaglandins have 20
carbon atoms, numbered as follows:
• GLYCOLIPIDS A carbohydrate, usually an
oligosaccharide, that is covalently linked to a
lipid molecule, such as those found in the cell
membrane are called Glycolipids. An example
of a glycolipid is a glycosphingolipid. It is
comprised of a carbohydrate and a sphingolipid
linked together by a glycosidic bond. Hydrolysis
of the glycosphingolipid, thus, yields sugar, fatty
acid, and sphingosine (or dihydrospingosine).
• The glycosphingolipids are part of the cell
membrane and are involved in cell-cell interactions.
Human blood types (A, B, AB, O) are based on the
glycolipids on the surface of erythrocytes.
• The oligosaccharide component of the glycolipid
determines the blood group antigen. For example,
blood type A has N-acetylgalactosamine, blood
type B has a galactose. Blood type AB has both
antigens whereas blood type O lacks these
antigens.