Lipid

2019.04.01
 Outline
• The functions of lipids

• The structure of fatty acids and triacylglycerols

• Recognize the structure of membrane lipids

(including glycerophospholipids and sterols)
 Functions of lipids
• Biological lipids are a chemically diverse group of
compounds, which are insoluble in water.
• Fats and oils are the principal stored forms of energy
in many organisms.
• Phospholipids and sterols are major structural
elements of biological membranes.
• Other lipids, although present in relatively small
quantities, play crucial roles as enzyme cofactors,
electron carriers, etc.
 Storage lipids
• The fats and oils are
stored forms of energy.
• They are composed of
fatty acids and glycerol.
Storage lipids
 Fatty acids
• Fatty acids are carboxylic
acids with hydrocarbon
chains ranging from 4 to 36
carbons long (C4 to C36).
• In some fatty acids, this
chain is unbranched and
fully saturated(contains no
double bonds); in others the
chain contains one or more
double bonds.
• The most commonly
occurring fatty acids have
even numbers of carbon
atoms in an unbranched
chain of 12 to 24 carbons
 Cis fatty acids
• In nearly all naturally occurring unsaturated fatty
acids, the double bonds are in the cis configuration.
Trans fatty acids are produced by fermentation in the
rumen of dairy animals and are obtained from dairy
products and meat.
 Trans fatty acids
Trans fatty acids became widely produced industrially
starting in the 1950s for use in margarine, snack food,
packaged baked goods, and for frying fast food
Although trans fats are edible, consuming trans
fats has been shown to increase the risk of
coronary artery disease in part by raising levels
of low-density lipoprotein (LDL, often termed
"bad cholesterol"), lowering levels of high-
density lipoprotein (HDL, often termed "good
cholesterol"), increasing triglycerides in the
bloodstream and promoting systemic
inflammation.
Trans fatty acids
 polyunsaturated fatty acids (PUFAs)
• What are omega-3 (ω -3) fatty acids？omega-6 (ω -6) fatty acids?

• Because the physiological role of PUFAs is related more to the

position of the first double bond near the methyl end of the chain
than to the carboxyl end, the carbon most distant from the carboxyl
group—is called the ω (omega) carbon and is given the number 1. In
this convention, PUFAs with a double bond between C-3 and C-4 are
called omega-3 (ω -3) fatty acids, and those with a double bond
between C-6 and C-7 are omega-6 (ω -6) fatty acids
 ω-3 PUFA
Humans require omega-3 PUFA
ω-linolenic acid (ALA; 18:3,
found in vegetable oil) and must
obtain it in the diet. From ALA,
humans can synthesize two
other omega-3 PUFAs important
in cellular function:
eicosapentaenoic acid (EPA;
20:5),and docosahexaenoic acid
(DHA; 22:6).
 ω-3 PUFA
An imbalance of omega-6 and omega-3 PUFAs in the diet is
associated with an increased risk of cardiovascular disease. The
“Mediterranean diet,” which has been associated with lowered
cardiovascular risk, is richer in omega-3 PUFAs, obtained in leafy
vegetables (salads) and fish oils. The latter oils are especially rich in
EPA and DHA

The optimal dietary ratio of omega-6 to

omega-3 PUFAs is between 1:1 and 4:1,
but the ratio in the diets of most North
Americans is closer to 10:1 to 30:1,
leading to an increased frequency of
heart disease and stroke.
 Oil and fat
• Melting points are strongly influenced by the length and
degree of unsaturation of the hydrocarbon chain. At
room temperature, the saturated fatty acids from 12:0 to
24:0 have a waxy consistency , whereas unsaturated fatty
acids of these lengths are oily liquids.
• Vegetable oils such as corn (maize) and olive oil are
composed largely of triacylglycerols with unsaturated
fatty acids and thus are liquids at room temperature.
Triacylglycerols containing only saturated fatty acids,
such as tristearin, the major component of beef fat, are
white, greasy solids at room temperature.
Triacylglycerols Are Fatty Acid Esters of Glycerol
The simplest lipids constructed
from fatty acids are the
triacylglycerols, also referred to as
triglycerides, fats,
or neutral fats.
Triacylglycerols are composed of
three fatty acids each in ester
linkage with a single glycerol
Most naturally occurring
triacylglycerols are mixed; they
contain two or three different
fatty acids.
 Homework question
• Triacylglycerols Provide Stored Energy. In vertebrates,
specialized cells called adipocytes, or fat cells, store
large amounts of triacylglycerols as fat droplets that
nearly fill the cell. Triacylglycerols are also stored as
oils in the seeds of many types of plants, providing
energy and biosynthetic precursors during seed
germination.
• Why use triacylglycerols as stored fuels, rather than
polysaccharides such as glycogen and starch?
• What are partially hydrogenated oils? What are their
applications and the detrimental effects of these oils?
 Summary: storage lipids
• Lipids are water-insoluble cellular components, of
diverse structure, that can be extracted by nonpolar
solvents.
• Almost all fatty acids, the hydrocarbon components of
many lipids, have an even number of carbon atoms
(usually 12 to 24); they are either saturated or
unsaturated, with double bonds almost always in the cis
configuration.
• Triacylglycerols contain three fatty acid molecules
esterified to the three hydroxyl groups of glycerol. Simple
triacylglycerols contain only one type of fatty acid; mixed
triacylglycerols, two or three types. Triacylglycerols are
primarily storage fats; they are present in many foods.
 Membrane lipids
• Membrane lipids are amphipathic: one end of the
molecule is hydrophobic, the other hydrophilic.
• The double layer of lipids acts as a barrier to the passage
of polar molecules and ions.
• Their hydrophobic interactions with each other and their
hydrophilic interactions with water direct their packing
into sheets called membrane bilayers.
Some common membrane lipids
 Glycerophospholipids
Also called phosphoglycerides.
two fatty acids are attached in ester linkage to the first
and second carbons of glycerol, and a highly polar or
charged group is attached through a phosphodiester
linkage to the third carbon.
 Sterols
Sterols are structural
lipids present in the
membranes of most
eukaryotic cells. The
characteristic structure of
this fifth group of
membrane lipids is the
steroid nucleus,
consisting of four fused
rings, three with six
carbons and one with five.
 Cholesterol
Cholesterol is absent from prokaryotes but is found to
varying degrees in virtually all animal membranes. It
constitutes almost 25% of the membrane lipids in
certain nerve cells but is essentially absent from some
intracellular membranes.
Cholesterol
 Cholesterol
Cholesterol is an amphipathic molecule, meaning,
like phospholipids, it contains a hydrophilic and a
hydrophobic portion. Cholesterol's hydroxyl (OH)
group aligns with the phosphate heads of the
phospholipids. The remaining portion of it tucks
into the fatty acid portion of the membrane.
 Cholesterol
Because of the way cholesterol is shaped, part of the
steroid ring is closely attracted to part of the fatty acid
chain on the nearest phospholipid. This helps slightly
immobilize the outer surface of the membrane and make it
less soluble to very small water-soluble molecules that
could otherwise pass through more easily.

In animals, cholesterol is the key regulator of memebrane

fluidity.
Without cholesterol, cell membranes would be too fluid,
not firm enough, and too permeable to some molecules. In
other words, it keeps the membrane from turning to mush.
 Steroid hormones
Steroids are oxidized derivatives of sterols; they have
the sterol nucleus but lack the alkyl chain attached to
ring D of cholesterol, and they are more polar than
cholesterol. Steroid hormones move through the
bloodstream (on protein carriers) from their site of
production to target tissues, where they enter cells,
bind to highly specific receptor proteins in the nucleus,
and trigger changes in gene expression and thus
metabolism. Because hormones have very high affinity
for their receptors, very low concentrations of
hormones (nanomolar or less) are sufficient to produce
responses in target tissues.
 Summary: membrane lipids
• The polar lipids, with polar heads and nonpolar tails, are
major components of membranes. The most abundant
are the glycerophospholipids, which contain fatty acids
esterified to two of the hydroxyl groups of glycerol, and a
second alcohol, the head group, esterified to the third
hydroxyl of glycerol via a phosphodiester bond. Other
polar lipids are the sterols. Sterols have four fused rings
and a hydroxyl group.
• Cholesterol, the major sterol in animals, is both a
structural component of membranes and precursor to a
wide variety of steroids.