Principles of Biochemistry

L. Moran, R. Horton, G. Scrimgeour, M. Perry

Chapter 9
Lipids

Dr. Reem Arafa

Prof. of Biomedical Sciences
Biochemistry
BMS 204
Spring 2020
Structural and Functional Diversity
of Lipids
 Lipids’ structure (General)
• The simplest lipids are the fatty acids that have the
general formula R—COOH, where R represents a
hydrocarbon chain composed of various lengths of -CH2-
(methylene) units. They are components of many more
complex types of lipids, including
– triacylglycerols,
– glycerophospholipids, and
– sphingolipids.

• Steroids, lipid vitamins, and terpenes are related to the

five-carbon molecule isoprene and are therefore called
isoprenoids
 Lipids’ Function
1. Biological membranes contain a variety of amphipathic lipids
including glycerophospholipids and sphingolipids.
2. Triacylglycerols (fats and oils) function as intracellular storage
molecules for metabolic energy. Fats also provide animals with
thermal insulation and padding.
3. Waxes in cell walls, exoskeletons, and skins protect the surfaces of
some organisms.
4. Steroid hormones regulate and integrate a host of metabolic
activities in animals
5. Eicosanoids participate in the regulation of blood pressure, body
temperature, and smooth-muscle contraction in mammals.
6. Gangliosides and other glycosphingolipids are located at the cell
surface and can participate in cellular recognition.
 1. Fatty Acids

• Fatty acids differ from one another in:

– the length of their hydrocarbon tails,
– the number of carbon–carbon double bonds,
– the positions of the double bonds in the chains, and
– the number of branches.

• All fatty acids have a carboxyl group (-COOH) at their

“head.” The pKa of this group is about 4.5 to 5.0 so it is
ionized at physiological pH (-COO-).

• Fatty acids are a form of detergent because they are

amphipathic (long hydrophobic tail and a polar head)
• Double bonds in fatty acids
usually have the cis configuration.
• Most naturally occurring fatty
acids have an even number of
carbon atoms.
• A 18-C fatty acid with one cis
double bond between C atoms 9-
10 may be represented as 18:1
cis D9.
 1.1. Triacylglycerols

• Three fatty acyl residues esterified to

glycerol
• Very hydrophobic
• Fats and oils are mixtures of
triacylglycerols.
• They can be solids (fats) or liquids
(oils), depending on their fatty acid
compositions and on the temperature.

Formation of an ester:
O O
R'OH + HO-C-R" R'-O-C-R'' + H2O
 1.2. Glycerophospholipids
• The most abundant lipids in most membranes
• The simplest glycerophospholipids are the,
phosphatidates—they consist of two fatty acyl groups
esterified to C-1 and C-2 of glycerol 3-phosphate
• Glycerophospholipids are amphipathic molecules with a
polar head and long, nonpolar tails
• Phosphate group can be esterified by another compound
bearing an —OH group giving rise to different members
of this class
• Variety of phospholipases can be used to dissect
glycerophospholipid structures and determine the
identities of their individual fatty acids
 1.2. Glycerophospholipids
• Variety of phospholipases can be used to dissect
glycerophospholipid structures and determine the
identities of their individual fatty acids
 1.2.a. Plasmalogens
• Plasmalogens are another major type of
glycerophospholipids.

• They differ from phosphatidates because the

hydrocarbon substituent on the C-1 hydroxyl
group of glycerol is attached by a vinyl ether
linkage rather than an ester linkage

• Ethanolamine or choline is commonly esterified to

the phosphate group of plasmalogens.

• Plasmalogens account for about 23% of the

glycerophospholipids in the human central
nervous system and in the membranes of
peripheral nerve and muscle tissue.
• For your kind knowledge 
• Starting slide 19
 1.3. Sphingolipids
• The second most abundant lipids in
plant and animal membranes. In
mammals, sphingolipids are abundant in
CNS.

• The structural backbone of sphingolipids

is sphingosine (trans-4-sphingenine),
an unbranched C18 dialcohol with
hydroxyl groups at C-1 and C-3, an
amino group at C-2 and a trans double
bond between C-4 and C-5
 1.3. Sphingolipids
• Ceramide consists of a fatty acyl
group linked to the C-2 amino group
of sphingosine by an amide bond
• Ceramides are the metabolic
precursors of all sphingolipids. The
three major families of sphingolipids
are:
– sphingomyelins,
– cerebrosides, and
– gangliosides.
 1.3.a. Sphingomyelins
• Sphingomyelins: phosphocholine is attached
to the C-1 hydroxyl group of a ceramide

• zwitterion containing choline, phosphate, and

two long hydrophobic tails.

• Sphingomyelins are present in the plasma

membranes of most mammalian cells and are a
major component of the myelin sheaths that
surround certain nerve cells
 1.3.b. Cerebrosides
• Cerebrosides are glycosphingolipids that
contain one monosaccharide residue attached
by a β-glycosidic linkage to C-1 of ceramide.

• Galactocerebrosides, have a single β-D-

galactosyl residue as a polar head group

• Galactocerebrosides:15% of the lipids of

myelin sheaths.

• Many other mammalian tissues contain

glucocerebrosides, ceramides with a β-D-
glucosyl head group.
 1.3.c. Gangliosides
• Gangliosides are more complex glycosphingolipids in which
oligosaccharide chains containing N-acetylneuraminic acid
(NeuNAc) are attached to a ceramide.

• The structure of a representative ganglioside, GM2, is shown. The M

in GM2 stands for monosialo (i.e., one NeuNAc residue).

• Their structural diversity results from variations in the composition

and sequence of sugar residues
 2. Steroids
• Found in the membranes of eukaryotes e.g. cholesterol

• Steroids, along with lipid vitamins and terpenes, are

classified as isoprenoids because their structures are
related to the five-carbon molecule isoprene

• Contain four fused rings: three six-carbon rings

designated A, B, and C and a five carbon D ring. The
characteristic ring structure is derived from squalene
isoprene
 2.1. Cholesterol
• Cholesterol, an important
constituent of cell membranes,
has a rigid ring system and a
short branched hydrocarbon tail.

• Cholesterol is largely
hydrophobic.

• But it has one polar group, a

hydroxyl, making it amphipathic.

• Modulates the fluidity of

mammalian cell membranes
 3. Other important lipids
• Eicosanoids are oxygenated derivatives of C20
polyunsaturated fatty acids such as arachidonic acid.

• Arachidonic acid is a precursor of other eicosanoids.

• Eicosanoids participate in a variety of physiological

processes and can also mediate many potentially
pathological responses e.g. growth, inflammation,
immunity and messengers in the CNS

• Prostaglandins are eicosanoids that have a

cyclopentane ring.