Lipids

• By definition, lipids are water-insoluble

biomolecules that are highly soluble in
organic solvents such as chloroform
• The biological functions of the lipids are as
diverse as their chemistry.
• Fats and oils are the principal stored forms
of lipids in many organisms.
• Phospholipids and sterols are major
structural elements of biological membranes.
• Lipids have a variety of biological roles:
• They serve as fuel molecules.
• Highly concentrated energy stores.
• Signal molecules.
• Messengers in signal-transduction pathways
• Components of membranes.
• Enzyme cofactors
• Electron carriers.
• Light-absorbing pigments,
• Hydrophobic anchors for proteins,
• Chaperones help membrane proteins fold
• Emulsifying agents in the digestive tract,
• Here we introduces representative lipids of
each type, organized according to their
functional roles, with emphasis on their
chemical structure and physical properties
 Storage Lipids
• The fats and oils are principal stored forms
of lipids.
• Lipids 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 thus 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.
• The most commonly occurring fatty acids have
even numbers of carbon atoms in an
unbranched chain of 12 to 24 carbons.
• Nomenclature: fatty acid names are based
on their parent hydrocarbon.
• The systematic name for a fatty acid is
derived from the name of its parent
hydrocarbon by the substitution of -oic for
the final -e.
• For example, the C18 saturated fatty acid is
called octadecanoic acid because the parent
hydrocarbon is octadecane
• A C18 fatty acid with one double bond is
called octadecenoic acid.
• With two double bonds it is octadecadienoic
acid.
• With three double bonds, octadecatrienoic
acid.
• The notation 18:0 denotes a C18 fatty acid
with no double bonds, whereas 18:2 signifies
that there are two double bonds.
• The 16-carbon saturated palmitic acid is
abbreviated 16:0 and the 18-carbon oleic
acid, with one double bond, is 18:1.
• The positions of any double bonds are
specified by superscript numbers following ∆
(delta).
• A 20-carbon fatty acid with one double bond
between C-9 and C-10 (C-1 being the
carboxyl carbon) and another between C-12
and C-13 is designated 20:2(∆9,12).
• 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 (∆9).
• The other double bonds of polyunsaturated
fatty acids are generally 12 and 15.
• But Arachidonic acid is an exception to this
generalization.
• The double bonds of polyunsaturated fatty
acids are almost never conjugated thus
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.
• Fatty acid carbon atoms are numbered
starting at the carboxyl terminus shown
below.
• Carbon atoms 2 and 3 are often referred to
as alpha (α) and beta (β) respectively.
• The methyl carbon atom at the distal end of
the chain is called the omega (ω) carbon
atom.
• The position of a double bond is represented
by the symbol delta (∆) followed by a
superscript number
• For example, cis-∆9 means that there is a cis
double bond between carbon atoms 9 and 10
• Trans-∆2 means that there is a trans double
bond between carbon atoms 2 and 3.
• Fatty acids are ionized at physiological pH,
and so it is appropriate to refer to them
according to their carboxylate form: for
example, palmitate or hexadecanoate
Structures of palmitate is a 16-carbon, saturated fatty
acid, and oleate is an 18-carbon fatty acid with a
single cis double bond
• Two conventions for naming fatty acids.
• (a) Standard nomenclature assigns the
number 1 to the carboxyl carbon (C-1), and α
to the carbon next to it.
• (b) For polyunsaturated fatty acids (PUFAs),
an alternative convention numbers the
carbons in the opposite direction, assigning
the number 1 to the methyl carbon at the
• other end of the chain; this carbon is also
designated ω (omega; the last letter in the
Greek alphabet).
• The positions of the double bonds are
indicated relative to the ω carbon.
Two ways of numbering fatty acids
Some naturally occuring fatty acids in animals
• 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 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) carbon and is
given the number 1 as shown in slide
above.
• 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
 Physical properties of 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.
• Unsaturated fatty acids have lower melting
points than do saturated fatty acids of the
same length.
• For example, the melting point of stearic
acid is 69.68C, whereas that of oleic acid
(which contains one cis double bond) is
13.48C.
• The melting points of polyunsaturated fatty
acids of the C18 series are even lower.
• Chain length also affects the melting point, as
illustrated by the fact that the melting
temperature of palmitic acid (C16) is 6.5
degrees lower than that of stearic acid (C18).
• Thus, short chain length and unsaturation
enhance the fluidity of fatty acids and of their
derivatives.
• The nonpolar 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.
• Melting points are also 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 are solids or wax-
like whereas unsaturated fatty acids of these
lengths are oily liquids. Because.....
• In the fully saturated compounds, free rotation
around each carbon–carbon bond gives the
hydrocarbon chain great flexibility.
• The most stable conformation is the fully
extended form, in which the steric hindrance
of neighboring atoms is minimized.
• These molecules can pack together tightly in
nearly crystalline arrays, with atoms all along
their lengths in van der Waals contact with the
atoms of neighboring 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
• Triacylglycerols are fatty acid esters of
glycerol.
• They are the simplest lipids constructed
from fatty acids are the and are also referred
to as triglycerides, fats, or neutral fats.
• Triacylglycerols are composed of three fatty
acids each in ester linkage with a single
glycerol as shown below
Triacylyglycerol
• 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 as one shown above. They contain two
or three different fatty acids.
• To name these compounds unambiguously, the
name and position of each fatty acid must be
specified.
• Because the polar hydroxyls of glycerol and
the polar carboxylates of the fatty acids are
bound in ester linkages, triacylglycerols are
nonpolar, hydrophobic molecules, essentially
insoluble in water.
• Triacylglycerols provide stored energy and
insulation.
• In vertebrates, specialized cells called
adipocytes, or fat cells, store large amounts
of triacylglycerols as fat droplets.
• Triacylglycerols are also stored as oils in the
seeds of many types of plants, providing
energy and biosynthetic precursors during
seed germination
• Triacylglycerols are preferred over
polysaccharides as storage forms because of
two significant advantages.
• First, the carbon atoms of fatty acids are
more reduced than those of sugars, and
oxidation of triacylglycerols yields more than
twice as much energy, gram for gram, as the
oxidation of carbohydrates.
• Second, because triacylglycerols are
hydrophobic and therefore unhydrated, the
organism that carries fat as fuel does not
have to carry the extra weight of water of
hydration that is associated with stored
polysaccharides
• 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 the huge fat reserves
accumulated before hibernation serve the dual
purposes of insulation and energy storage
 Waxes
• Waxes serve as energy stores and water
repellants.
• Biological waxes are esters of long-chain
(C14 to C36) saturated and unsaturated fatty
acids with long-chain (C16 to C30) alcohols.
• Their melting points (60 to 100 degrees C)
are generally higher than those of
triacylglycerols.
• Certain skin glands of vertebrates secrete
waxes to protect hair and skin and keep it
pliable, lubricated, and waterproof.
• Some birds secrete waxes from their preen
glands to keep their feathers water-
repellent.
• The shiny leaves of some plants coated with
a thick layer of waxes, which prevents
excessive evaporation of water and protects
against parasites
 Structural Lipids
• Briefly discuss lipids as membrane
constituents.
• Membrane lipids are amphipathic: one end of
the molecule is hydrophobic, the other
hydrophilic.
• Their hydrophobic interactions with each
other and their hydrophilic interactions with
water direct their packing into sheets called
membrane bilayers.
• The three major kinds of membrane lipids are
phospholipids, glycolipids, and cholesterol.
 Phospholipids
• Phospholipids are abundant in all biological
membranes.
• A phospholipid molecule is constructed from
four components: fatty acids, a platform to
which the fatty acids are attached, a
phosphate, and an alcohol attached to the
phosphate.
• The platform on which phospholipids are built
may be glycerol, a three-carbon alcohol, or
sphingosine, a more complex alcohol.
• Phospholipids derived from glycerol are
called phosphoglycerides.
• A phosphoglyceride consists of a glycerol
backbone to which are attached two fatty
acid chains and a phosphorylated alcohol.
• In phosphoglycerides, the hydroxyl groups at
C-1 and C-2 of glycerol are esterified to the
carboxyl groups of the two fatty acid chains.
• The C-3 hydroxyl group of the glycerol
backbone is esterified to phosphoric acid.
• When no further additions are made, the
resulting compound is phosphatidate -
diacylglycerol 3-phosphate - the simplest
phosphoglyceride.
• The major phosphoglycerides are derived
from phosphatidate by the formation of an
ester bond between the phosphate group of
phosphatidate and the hydroxyl group of one
of several alcohols
• The common alcohol moieties of
phosphoglycerides are the amino acid
serine, ethanolamine, choline, glycerol, and
inositol.
• Below is a phosphatidate
• Phospholipids/phosphoglycerides formed are
• Phosphatidylcholine
• Phosphatidylethanolamine
• Phosphatidylserine
• Phosphatidylinositol, and
• Diphosphatidylglycerol
• Sphingomyelin is a phospholipid found in
membranes that is not derived from glycerol.
• The backbone in sphingomyelin is sphingosine,
an amino alcohol that contains a long,
unsaturated hydrocarbon chain.
• In sphingomyelin, the amino group of the
sphingosine backbone is linked to a fatty acid
by an amide bond
• The second major class of membrane lipids,
glycolipids - sugar-containing lipids.
• The glycolipids in animal cells are derived
from sphingosine.
• Glycolipids differ from sphingomyelin in the
identity of the unit that is linked to the
primary hydroxyl group of the sphingosine
backbone.
• In glycolipids, one or more sugars (rather
than phosphorylcholine) are attached to this
group.
• The simplest glycolipid, called a cerebroside,
contains a single sugar residue, either
glucose or galactose.
• More-complex glycolipids, such as
gangliosides, contain a branched chain of as
many as seven sugar residues.
• Glycolipids are oriented in a completely
asymmetric fashion with the sugar residues
always on the extracellular side of the
membrane.
• Cholesterol, the third major type of
membrane lipid, has a structure that is quite
different from that of phospholipids.
• It is a steroid, built from four linked
hydrocarbon rings.
• A hydrocarbon tail is linked to the steroid at
one end, and a hydroxyl group is attached at
the other end.
• In membranes, the orientation of the
molecule is parallel to the fatty acid chains
of the phospholipids, and the hydroxyl group
interacts with the nearby phospholipid head
groups.
• Cholesterol is absent from prokaryotes but is
found to varying degrees in virtually all
animal membranes.