10| Lipids

2013 W. H. Freeman and Company

Lipids
Water insoluble compounds
Soluble in non-polar solvents such as petroleum
ether, benzene, chloroform
Chemically most lipids are derivatives of fatty acids,
generally ester of fatty acids.

Lipids
Biological roles
Energy storage (in seeds and adipose tissue)
Structural component of cell membranes
Insulation against low temperature (in penguins, seals,
walruses and polar bears
Buoyancy in spermaceti whale
Protection against water loss (wax coated plant leaves)
Water repellent (wax of birds feathers)
Enzyme cofactors and electron carriers (lipoate and
lipoamide)
Hydrophobic anchor of proteins
Precursors of hormones (steroids and prostaglandins)
Intracellular messengers

Spermaceti source

Carnauba wax source

Bees wax

Bees
wax

Classification of Lipids

Fatty acids: are long chain linear (unbranched) hydrocarbon

carboxylic acids
Triacylglycerides: are fatty acid esters of glycerol
Phospholipids: are lipids that contain one or more
phosphate groups
Glycolipids: have a carbohydrates component
Eicosanoids: are a family of derivatives of Arachidonic acid
Steroids: have a basic structure of a
perhydrocyclopentanophenanthrene ring system
Lipoproteins: are complexes of lipids and proteins that
circulate in the blood.

Fatty Acids

Saturated fatty acid

Unsaturated fatty acid

Nomenclature of fatty acid

Fatty Acids
Long chain linear hydrocarbons carboxylic acids
Usually have an even number of C atoms (usually 12 to 20)
The carbons are numbered starting from the carboxylic C.
They are amphipathic; they have a polar end and rest of the
molecule is nonpolar
Fatty acids may be saturated (no double bonds) or unsaturated
(one or more double bonds)
All naturally occurring double bonds have a cis-configuration
Two or more double bonds exist as non-conjugated double bonds
Melting point of fatty acids increases with increase in the length
of
C-chain.
Saturated fatty acids have higher melting points than unsaturated
fatty acids
In vertebrates, free fatty acids circulate in the blood bound noncovalently to a protein carrier, serum albumin. However, fatty
acids are present in blood mostly as carboxylic acid derivatives
such as esters and amides.

Fatty acids

Fatty Acids

Fatty Acids

Fatty Acids

Saturation level affects packaging

Storage lipids

Triacylglycerol
Simplest lipids
Fatty acid esters of glycerol

Triacylglycerols
Generally referred to as fats or neutral fats or simple triglycerides.
Are fatty acid derivative of glycerol
All 3 hydroxyl groups of glycerol are esterified by fatty acids in
triacylglycerols. In contrast, monoacylglygerol and diacylglycerol
have only one and two OH gps of glycerol esterified by fatty acids.
If all three fatty acids of a triacylglycerol are the same, it is called
simple triacylglycerol. If a triacylglycerol has two or three different types
of fatty acids, it is called mixed triacylglycerol.
Because polar hydroxyls of glycerol and polar carboxylates of fatty acid
are bound in ester linkages, triacylglycerols are non-polar, hydrophobic
molecules essentially insoluble in water.
Have lower specific gravities than water.
Triacylglycerols are the storage form of fatty acids; stored in adipocytes
in animals and in seeds in plants; most dietary fats are triglycerides.
Adipocytes and seeds contain lipases, enzyme that catalyze hydrolysis
of stored triacylglycerols releasing fatty acid to be used as fuel.
Monoacylglycerols are absorbed through the intestinal cells,
reconverted to triacylglycerols and assembled into lipoproteins.

Vertebrates store lipids in

adipocytes

Plants store lipids in seeds

Why lipids are better than carbohydrates

as stored fuel?
(1) Since, C-atoms of fatty acids are more reduced than those of sugars,
oxidation of triacylglycerols yields more than twice the amount of
energy, on per gram basis, compared to the oxidation of sugars.
(2) Since triacylglycerols are hydrophobic and therefore unhydrated, the
organism that carries fat as fuels does not have to carry the extra
weight of water of hydration that has to be carried with carbohydrates
(2g per gram of polysaccharide).

Most foods contain triacylglycerols

Exam III
45
40
35
30
25
20
15
10
5
0

44.6%

32.0%
Average = 85

13.0%

10.2%

DF

Structural lipids

Structural lipids in membranes

Amphipathic with hydrophobic and hydrophilic ends
Interaction of hydrophobic ends with each other and hydrophilic ends with
aqueous environment results in the formation of bilayer membrane structure.

Phospholipids
Glycolipids
Archaebacterial ether lipids

Phospholipids
These are lipids that contain one or more phosphate groups
Phospholipids are the primary components of biomembranes.
Other lipids in biomembranes are glycolipids and cholesterol.
Phospholipids are subclassified based on if they are
derivative of glycerol or sphingosine
Glycerophospholipid: derivative of glycerol
Sphingolipid: derivative of sphingosine

Glycerophospholipid
L-Glycerol 3-phosphate, the backbone of phospholipids

Glycerophospholipid

Phosphate gp is in turn esterified to the polar head gp X e.g. serine, choline,

ethanolamine, glycerol or inositol.
The two fatty acids tend to be non-identical being different in length or
position of double bond.

Glycerophospholipids

Sphingolipid

Sphingosine is an amino alcohol, a derivative of glycerol which has

NH2 gp instead of -OH at C2 and has a -OH as well as a long chain
hydrocarbon on C3.
The NH2 forms an amide bond with a long chain fatty acid to form a
ceramide.
Sphigomyelin is formed when a phosphodiester bridge links the
C1 -OH of ceramide to ethanolamine or choline
Sphingomyelins are found abundantly in the myelin sheath that
surrounds the nerve fiber

Sphingolipid

Structural similarity of
phospholipids

Sphingolipid

Sphingolipid

Sphingolipid
Glycolipids

Glycolipids are lipids that contain carbohydrates

Cerebrosides have a monosaccharide attached to the
C1 -OH of ceramide
Gangliosides have an oligosaccharide attached to the
C1 -OH of ceramide
Cerebrosides and gangliosides are found in the brain
and nervous tissue
In biomembranes, glycolipids are oriented
asymmetrically with the sugar units always on the
extracellular side of the membrane
Carbohydrate moiety of certain sphingolipids define the
human blood gp.

Glycosphingolipids
are determinants
of blood groups

Galactolipids
Have one or two galactose residues connected by a glycosidic linkage to
C1 or C2 of glycerol.
Predominate in plant cells; constitute 70-80% of total membrane lipids of
vascular plants.
Abundant in thylakoids.

Sulfolipids
Also called sulfatides or cerebroside
sulfates
Contained in brain lipids
Sulfate esters of cerebrosides
Present in low levels in liver, lung, kidney,
spleen, skeletal muscle and heart
Function is not established

Degradation by Lipases
There are specific lipases for digesting specific hydrolysable bonds of lipids.

Lipid storage diseases

Also known as sphingolipidoses
Genetically acquired
Due to the deficiency or absence of a catabolic
enzyme
Examples:
Tay Sachs disease
Gauchers disease
Niemann-Pick disease
Sandhoffs disease
Fabrys disease

Lipid
storage
diseases

Tay-Sachs disease

Tay-Sachs disease
A fatal disease which is due to the deficiency of
hexosaminidase A activity
Accumulation of ganglioside GM2 in the brain of
infants
mental retardation, blindness, inability to swallow
a cherry red spot develops on the macula (back of
the the eyes)
Tay-Sachs children usually die by age 5 and often
sooner

Cholesterol

Sterols
Sterols are structural lipids present in the membranes of
most eukaryotic cells.
Sterol imparts stability to the fluid membrane structure.
The characteristic feature of sterols is the steroid nucleus,
consisting of four fused rings, three with 6 carbon and one
with 5-C.
The steroid nucleus is almost planar and relatively rigid.
Cholesterol, the major sterol in animal tissue is amphipathic
with a polar head gp (OH group at C-3) which provides the
polarity and a non-polar hydrocarbon group at the other end
which adds to its hydrophobic nature.
In biomembranes, the OH of cholesterol is aligned with
the head group (phosphate) of phospholipids.
Steroids are important metabolically (cholesterol), for
digestion (bile salts), as hormones (human sex hormones).

Lipids as Signals, Cofactors,

and Pigments

Lipids as second messengers

(Water soluble)

(Water insoluble)

Eicosanoids are like hormones

Eicosanoids are similar to hormones except that their site of action
is the same as site of synthesis.
They are derived from arachidonic acid, a 20C polyunsaturated
fatty acid.
Are involved in a variety of cellular functions such as in reproductive
functions; in the inflammation, fever and pain associated with injury
and pain; in the formation of blood clots; in the regulation of blood
pressure; in gastric acid secretion; and a variety of other processes.
There are three classes of eicosanoids:
(1) Prostaglandins
(2) Thromboxanes
(3) Leukotrines

Eicosanoids are derived from arachidonic Acid

Non-steroid anti-inflammatory drugs (NSAID)

SAID

Pain

Non-steroid antiinflammatory drugs

(NSAID)
COX1 and COX2 inhibitors

Non-steroid anti-inflammatory drugs (NSAID)

Non-steroid anti-inflammatory drugs (NSAID)

COX2 inhibitors

Functions of eicosanoids
Prostaglandins, particularly PGE1, block gastric
production and thus are gastric protection agents.
Misoprostol (Cytotec) is a stable PGE1 analog that is
used to prevent ulceration by long term NSAID
treatment.
PGE1 also has vasodilator effects
Alprostadil (PGE1) used to treat infants with congenital
heart defects
PGF2 causes constriction of the uterus.
PGE2 is applied locally to help induce labor.

Examples of drugs derived from prostaglandins

Steroid
hormones
Oxidized derivatives of sterols
Have sterol nucleus but lack thee
alkyl chain attached to the nucleus
Examples:
Male and female sex hormones,
hormones secreted by adrenal
cortex, cortisol, aldosterone
Prednisone and prednisolone
are steroid drugs with potent
anti-inflammatory activities (inhibits
synthesis of prostaglandins,
leukotrines and thromboxanes.

Vitamins
Fat soluble vitamins (A,D,E and K) are isoprenoid
compounds formed by condensation of multiple
isoprene units.

Electron carrier
Ubiquinone and plastoquinone are isoprenoids that
function as electron carrier.

Enzyme cofactor
Lipoate is an enzyme cofactor.

Lipoproteins
Cell surface recognition