BCH 201

LIPIDS
 INTRODUCTION
 Lipids are diverse group of organic compounds including
fats, oil, hormones, and certain components of membranes
that are grouped together because they do not interact
appreciably with 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,
light-absorbing pigments, hydrophobic anchors for proteins,
“chaperones” to help membrane proteins fold, emulsifying
agents in the digestive tract, hormones, and intracellular
messengers.
 STORAGE LIPIDS
The fats and oils used almost universally as stored
forms of energy in living organisms are derivatives
of 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
A few contain three-carbon rings, hydroxyl
groups, or methyl-group branches
 NOMENCLATURE
A simplified nomenclature for unbranched fatty
acids specifies the chain length and number of
double bonds, separated by a colon.

For example, the 16-carbon saturated palmitic

acid is abbreviated 16:0, and the 18-carbon oleic
(octadecenoic) acid, with one double bond, is
18:1.
Each line segment of the zigzag in the structure represents a
single bond between adjacent carbons. The carboxyl carbon is
assigned the number 1 (C-1), and the carbon next to it is C-2.

The positions of any double bonds, designated Δ (delta), are

specified relative to C-1 by a superscript number indicating
the lower-numbered carbon in the double bond. By this
convention, oleic acid, with a double bond between C-9 and
C-10, is designated 18:1(Δ 9 ); a 20-carbon fatty acid with one
double bond between C-9 and C-10 and another between C-12
and C-13 is designated 20:2(Δ 9,12 ).
 KEY FEATURES
 The most commonly occurring fatty acids have even numbers of carbon atoms in an
unbranched chain of 12 to 24 carbons. The even number of carbons results from the
mode of synthesis of these compounds, which involves successive condensations of
two-carbon (acetate) units.

 There is also a common pattern in the location of double bonds; in most

monounsaturated fatty acids the double bond is between C-9 and C-10 (Δ9), and the
other double bonds of polyunsaturated fatty acids are generally Δ12 and Δ15.
(Arachidonic acid is an exception to this generalization. The double bonds of
polyunsaturated fatty acids are almost never conjugated (alternating single and double
bonds, as in —CH=CH—CH=CH—), but are separated by a methylene group:
CH=CH—CH2—CH=CH—. 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.
Some Naturally occurring fatty acids
 Polyunsaturated fatty acids (PUFAs)
• The family of polyunsaturated fatty acids
(PUFAs) with a double bond between the third
and fourth carbon from the methyl end of the chain
are of special importance in human nutrition.

• 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 that near the
carboxyl end, an alternative nomenclature is
sometimes used for these fatty acids.
• The carbon of the methyl group—that is, the carbon
most distant from the carboxyl group—is called the
ω (omega; the last letter in the Greek alphabet)
carbon and is given the number 1 (C-1); the
carboxyl carbon in this convention has the highest
number.
• The positions of the double bonds are indicated
relative to the ω carbon. 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.
• Shown below is eicosapentaenoic acid, which
can be designated as 20:5(Δ5,8,11,14,17) by the
standard nomenclature but is also referred to as
an omega-3 fatty acid, emphasizing the
biologically important double bond in the
omega-3 position.
 Essential fatty acids
• Humans require the omega-3 PUFA α-linolenic acid
(ALA; 18:3(Δ9,12,15), and omega-6 linoleic acid but do
not have the enzymatic capacity to synthesize it and
must therefore obtain it in the diet, thus this fatty acid
is referred to as essential fatty acids.

• From ALA, humans can synthesize two other omega-3

PUFAs important in cellular function:
eicosapentaenoic acid (EPA; 20:5(Δ5,8,11,14,17), and
docosahexaenoic acid (DHA; 22:6(Δ4,7,10,13,16,19).

• An imbalance of omega-6 and omega-3 PUFAs in the

diet is associated with an increased risk of
cardiovascular disease.
 The physical properties of the fatty acids
• The physical properties of the fatty acids, and of
compounds that contain them, are largely
determined by the length and degree of
unsaturation of the hydrocarbon chain.
• The non-polar hydrocarbon chain accounts for the
poor solubility of fatty acids in water.
• The longer the fatty acyl chain and the fewer the
double bonds, the lower is the solubility in water.
• The carboxylic acid group is polar (and ionized at
neutral pH) and accounts for the slight solubility of
short-chain fatty acids in water
The physical properties of the fatty acids
 Melting points are also strongly influenced by the length and
degree of unsaturation of the hydrocarbon chain. At room
temperature (25 °C), the saturated fatty acids from 12:0 to 24:0
have a waxy consistency, whereas unsaturated fatty acids of
these lengths are oily liquids.

• This difference in melting points is due to different degrees of

packing of the fatty acid molecules.

• In unsaturated fatty acids, a cis double bond forces a kink in

the hydrocarbon chain. Fatty acids with one or several such
kinks cannot pack together as tightly as fully saturated fatty
acids, and their interactions with each other are therefore
weaker. Because less thermal energy is needed to disorder
these poorly ordered arrays of unsaturated fatty acids, they
have markedly lower melting points than saturated fatty acids
of the same chain length.
 TRIACYLGLYCEROLS
 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.

 Those containing the same kind of fatty acid in all three

positions are called simple triacylglycerols and are
named after the fatty acid they contain.

 Simple triacylglycerols of 16:0, 18:0, and 18:1, for

example, are tripalmitin, tristearin, and triolein,
respectively. Most naturally occurring triacylglycerols
are mixed; they contain two or three different fatty
acids. To name these compounds unambiguously, the
name and position of each fatty acid must be specified.
 TRIACYLGLYCEROLS
Because the polar hydroxyls of glycerol and the polar carboxylates of the fatty acids are bound
inester linkages, triacylglycerols are nonpolar, hydrophobic molecules, essentially insoluble in
water
 Triacylglycerols provide stored energy and insulation
In most eukaryotic cells, triacylglycerols form a
separate phase of microscopic, oily droplets in the
aqueous cytosol, serving as depots of metabolic fuel.
 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.
Adipocytes and germinating seeds contain lipases,
enzymes that catalyze the hydrolysis of stored
triacylglycerols, releasing fatty acids for export to sites
where they are required as fuel.
 ADVANTAGES of USING TRIACYLGLYCEROLS AS
STORED FUELS
• There are two significant advantages to using
triacylglycerols as stored fuels, rather than polysaccharides
such as glycogen and starch:
I. The carbon atoms of fatty acids are more reduced than
those of sugars, so oxidation of triacylglycerols yields
more than twice as much energy, gram for gram, as the
oxidation of carbohydrates
II. because triacylglycerols are hydrophobic and therefore
unhydrated, the organism that carries stored fuel in the
form of fat does not have to carry the extra weight of
water of hydration that is associated with stored
polysaccharides (2 g per gram of polysaccharide).
• In some animals, triacylglycerols stored under the skin
serve not only as energy stores but as insulation against
low temperatures. Seals, walruses, penguins, and other
warm-blooded polar animals are amply padded with
triacylglycerols. In hibernating animals (bears, for
example), the huge fat reserves accumulated before
hibernation serve the dual purposes of insulation and
energy storage
 SUMMARY
 Lipids are water-insoluble cellular components, of diverse structure, that
can be extracted from tissues by non-polar 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.

 Because trans fatty acids in the diet are an important risk factor for
coronary heart disease, their use in prepared and processed foods has
become highly regulated.

 Waxes are esters of long-chain fatty acids and long-chain alcohols