LIPIDS

Prepared by:
De Torres, Angelica M.
ChE-4102

Structure and
Classification of Lipids
Lipids
is
an
organic
compound found in living
organisms that is insoluble
(or only sparingly soluble) in
water but soluble in nonpolar
organic solvents.

a fat

a biological
wax

Figure 19.1 The stuctural formula of

these types of lipids illustrate the great
stuctural diversity among lipids.

Two common method exists for

subclassifying lipids into families for the
purpose of study. One method uses
biochemical function of a lipid as the
basis for classification, and the other
method is based on whether or not a lipid
can be broken down into smaller units
through basic hydrolysis, that is, reaction
with water under basic conditions. A
hydrolysis reaction that occurs in basic
solution is called saponification reaction.

Based on biochemical function, lipids are

divided into five categories:

1. Energy- storage lipids (triacylglycerols)

2. Membrane lipids (phospholipids,
sphingoglycolipids, and cholesterol)
3. Emulsification lipids (bile acids)
4. Messenger acids (steroid hormones and
eicosanoids)
5. Protective-coating lipids (biological
waxes)

Based upon whether or not

saponification occurs when a lipid is placed
in basic aqueous solution, lipids are
divided into two categories:

1. Saponifiable lipids (triacylglycerols,

phospholipids, sphingoglycolipids, and
biological waxes)
2. Nonsaponifiable lipids (cholesterol,
steroid hormones, bile acids, and
eicosanoids)

Types of Fatty Acids

The most frequently encountered
lipid building block is the structural
unit called fatty acid. A fatty acid is a
naturally occurring monocarboxylic
acid. In terms of carbon chain length,
fatty acids are characterized as longchain fatty acids (C12 to C26), mediumchain fatty acids (C8 and C10), or shortchain fatty acids (C4 and C6).

Saturated and Unsaturated

Fatty Acids

Fatty acids are classified as

saturated fatty acids (SFAs),
monounsaturated fatty acids
(MUFAs),
or
polyunsaturated
fatty acids (PUFAs).
A saturated fatty acid is a fatty
acid with a carbon chain in which
all carbon-carbon bonds are
single bonds.

The sructural formula for the 16carbon SFA is

A monounsaturated fatty acid is a

fatty acid with a carbon chain in
which one carbon-carbon double
bond is present.

IUPAC: cis-9-octadecenoic acid

Common name: oleic acid

A polyunsaturated fatty acid is a fatty

acid with a carbon chain in which two
or more carbon-carbon double bonds
are present. Up to six double bonds
are found in biochemically important
PUFAs.

IUPAC name: cis,cis-9,12-octadecadienoic acid

Common name: linoleic acid

Unsaturated Fatty Acids and

Double-Bond Position
An omega-3 fatty acid is an
unsaturated fatty acid with its
endmost double bond three carbon
atoms away from its methyl end.
An omega-6 fatty acid is an
unsaturated fatty acid with its
endmost double bond six carbon
atoms away from its methyl end.

Physical Properties of Fatty

Acids
Water solubility for fatty acids is a direct

function of carbon chain length; solubility

decreases as carbon chain length
increases. The slight solubility of shortchain fatty acids is related to the polarity
of the carboxyl group present. In longerchain fatty acids, the nonpolar nature of
the
hydrocarbon
chain
completely
dominates solubility considerations.

 Melting points for fatty acids are

stongly influenced by both
carbon chain length and degree
of unsaturation (number of
double
bonds
present).
As
carbon chain length increases,
melting point increases. The
greater
the
degree
of
unsaturation, the greater the
reduction in melting points.

Energy-Storage Lipids:
Triacylglycerols
Lipids known as triacylglycerols also
function within the body as energystorage materials.Triacylglycerols are
concentrated primarily in special cells
(adipocytes) that are nearly filled with the
material.
Triacyglycerols are much more efficient at
storing energy than is glycogen because
large quantities of them can be packed
into a very small volume.

 Fatty acids are the carboxylic

acids involved in triacylglycerol
formation. In the esterification
reaction producing a
triacylglycerol, a single molecule
of glycerol reacts with three fatty
acid molecules; each of the three
hydroxyl group present is
esterified.

Two general ways to represent

the stucture of triacylglycerol

Figure 19.4 Structure of the simple triacylglycerol

produced from the triple esterification reaction
between glycerol and three molecules of stearic acid.

 A simple triacylglycerol is a
triester formed from the
esterification of glycerol with
three identical fatty acid
molecules.
A mixed triacylglycerol is a
triester formed from the
esterification of glycerol with
more than one kind of fatty acid
molecule.

Fats and Oils

Fats are naturally occurring mixtures
of triacylglycerol molecules in which
many different kinds of
triacylglycerol molecules are present
Oils are also naturally occurring
mixtures of triacylglycerol molecules
in which there are many different
kinds of triacylglycerol molecules
present.

Additional generalization and comparisons

between fats and oils follow.
1. Fats are composed largely of triacylglycerol in
which saturated fatty acids predominate,
although some unsaturated fatty acids are
present. Such triacylglycerols can pack
closely together because of the linearity of
their fatty acid chains. Oils contain
triacylglycerols with larger amounts of monoand polyunsaturated fatty acids than those in
fats. Such triacylglycerols cannot pack as
tightly together because of bends in their
fatty acid chains.

a fat

an oil

2. Fats are generally obtained from

animals; hence the term animal fat.
Although fats are solids at room
temperature, the warmer body
temperature of the living animal
keeps the fat somewhat liquid
(semi-solid) and thus allows for
movement. Oils typically come from
plants, although there are also fish
oils. A fish would have some serious
problems if its triacylglycerols
solidified when it encountered

Good Fats Versus Bad Fats

Fat is used as a substitute for the term triacylglycerol.
Thus a dietary fat can be either a fat or an oil.
Saturated fats are bad fat, monounsaturated fats
are good fat, and polyunsaturated fats can be both
good fat and bad fat.
Studies indicate that saturated fat can increase heart
disease risk,that monounsaturated fat can decrease
both heart disease and breast cancer risk, and that
polyunsaturated fat can reduce heart disease risk but
promote the risk of certain types of cancers.
Dietary fats are high in good monounsaturated
fatty acids include olive, avocado, and canola oils.

Omega-3 and Omega-6 Fatty

Acids

The Inuit diet is high in U.S. diet is high in

omega-6 fatty acids
omega-3 fatty acids
(from plant oils.)
(from fish).

 Cold-water fish, also called fatty fish

because of the extra amounts of fat
they have for insulation against the
cold, contain more omega-3 acids
than leaner, warm-water fish.
Fatty fish include albacore tuna,
salmon, and mackerel. Leaner, warmwater fish, which include cod, catfish,
halibut, sole, and snapper, do not
appear to offer as great a positive
effect on heart health as do their
fatter counterparts.

Essential Fatty Acids

An essential fatty acid is a fatty acid needed in the
human body that must be obtained from dietary
sources because it cannot be synthesized within the
body, in adequate amounts, from other substances.
There are two essential fatty acids: linoleic acid and
linolenic acid. Linoleic acid is the primary member
of the omega-6 acid family, and linolenic acid is the
primary member of omega-3 acid family.
These two acids (1) are needed for proper
membrane structure and (2) serve as starting
materials for the production of several nutritionally
important longer-chain omega-6 and omega-3 acids.

Linoleic acid is the starting material for the biosynthesis

of arachidonic acid.
Linoleic acid (18:2)
arachidonic acid (20:4)
Omega-6 fatty acids
Arachidonic acid is the major starting material for
eicosanoids substances that help regulate blood
pressure, clotting, and several other important body
functions.
Linolenic acid is the starting material for the
biosynthesis of two additional omega-3 fatty acids.
Linolenic acid (18:3)
EPA (20:5)
DHA (22:6)
Omega-3 fatty acids
EPA (eicosapentaenoic acid) and DHA
(docosahexaenoic acid) are important constituents of
the communication membranes of the brain and are
necessary for normal brain development. EPA and DHA

Chemical Reactions of
Triacylglcerols

Hydrolysis
Triacylglycerol hydrolysis
requires the presence of an
acid or base. Under acidic
conditions, the hydrolysis
products are glycerol and fatty
acids. Under basic conditions,
the hydrolysis products are
glycerols and fatty acid salts.

 In situations where
all three fatty acids
are removed, the
hydrolysis process
is referred to as
complete
hydrolysis.

If one or more of
the fatty acid
residues remains
attached to the
glycerol, the
hydrolysis process
is called partial
hydrolysis.

 Saponification
Reaction carried out in an
alkaline (basic) solution.
For fats and oils, the
products of saponification
are glycerol and fatty
acid salts.

 The overall reaction of triacylglycerol

saponification can be thought of as
occurring two steps. The first step is the
hydrolysis of the ester linkages to produce
glycerol and three fatty acid molecules:
Fat or oil + 3H20
3 fatty acids + glycerol
The second step involves a reaction
between the fatty acid molecules and the
base (usually NaOH) in the alkaline
solution. This is an acid-base reaction that
produces water plus salts:
3 fatty acids + 3NaOH
3 fatty acid salts +
3H2O

 Hydrogenation
Chemical reaction that involves
hydrogen addition across carbon-carbon
multiple bonds, which increases the
degree of saturation as some double
bonds are converted to single bonds.
Many food products are produced via
partial hydrogenation. In partial
hydrogenation, some, but not all, of the
double bonds present are converted into
single bonds. In this manner, liquids
(usually plant oils) are converted into
semi-solid materials.

 Oxidation
The carbon-carbon double
bonds present in the fatty acid
residues of a triacylglycerol
are subject to oxidation with
molecular oxygen (from air) as
the oxidizing agent.

Thank You