Chapter 5

LIPIDS
 Course Learning
Outcome
• CLO1
Apply the fundamental structures
and functions of lipids
 Objective
• Structure & chemistry of fatty acids,
triacylglycerols, & glycerophospholipids
• Sphingolipids
• Waxes
• Terpenes
• Steroids
• Biological signals
• Lipidomics
 Lipids
• Lipids can be either

(a) Hydrophobic (b) Amphipathic

Contain only non-polar Contain both polar &
groups non-polar groups
Highly reduced carbon

• Solubility of lipids
(a) low solubility in water
(b) high solubility in nonpolar solvents
eg. benzene
• Hydrophobic nature of lipid molecules allow
membranes to act as effective barrier to
polar molecules
 Type of Lipids
1
Fatty Acids
• Composition of a fatty acid (f.a)
(a) a terminal carboxyl (COOH) group (as “head”)
(b) a long hydrocarbon chain (as “tail”)
• Fatty acid can be either free or bound state
– Fatty acids are esterified to glycerol or other
backbone structures
Head

Tail

Fatty acid
in bound form Fatty acid
(stearoyl) in free form
(stearic acid /
stearate)
Fatty Acid

Number of Carbon
• Most fatty acids have even number of carbon atoms
(usually 14 to 24)
Fatty Acid
Saturated &
Fatty acid
Unsaturated
(a) Saturated (b) Unsaturated
Property All C-C bonds are 1 or more double
single bonds bonds in the
hydrocarbon chain
Example Stearic acid (18:0) Oleic acid (18:1)
Saturated Fatty Acids Unsaturated Fatty Acids
Fatty Acid

Mono- & Poly-Unsaturated

• Unsaturated fatty acids can be either:
2 Types (a) Monounsaturated (b) Polyunsaturated
Double bond 1 More than 1
Example Oleic acid (18:1) Linoleic acid (18:2)
 Type of Lipids
2
Triacylgylcerols Also called
triglycerides

Structure Consists of a glycerol backbone esterified with

3 fatty acids
Location TAGs are found in adipose tissue of animals
Function Serve as energy storage in animals & provide
good insulation
Solubility Insoluble in water
Soluble in benzene, chloroform
TAG  triacylglycerol

3 esterified
fatty acids

Glycerol
backbone
Triacylglycerol

Triacylglycerols
2 Types (a) Simple (b) Mixed
Structure All 3 fatty acids are Contains 2 or 3 different
same fatty acids
Example Tristearoylglycerol 1-myristoyl-2-stearoyl-3-
(or tristearin) palmitoleoylglycerol

Simple Mixed
triacylglycerol triacylglycerol
 Type of Lipids
3 Glycerophospholipids
• Consists of a 1,2-diacylglycerol that has a phosphate group
esterified at C3 of glycerol backbone
• A variety of polar groups are esterified to phosphoric acid
moiety → eg. choline, ethanolamine, serine, inositol,
glycerol
• Essential components of cell membrane
1,2-diacylglycerol
Also known as “Head” group
phosphoglyceride
or glycerol 1 phosphate
phosphatide C1 group at C3

C2
C3
Polar
2 esterified fatty acids
at C1 & C2
group
Glycerol
backbone
 Types of Glycerol
Glycerophospholipid

Phosphatides Polar Entity

Name
(esterified to phosphate
moiety at C3 of glycerol )
Phosphoryl-Choline 2 most common
Phosphatidylcholine constituents of
(common name – lecithin) biological
membrane
Phosphatidylethanolamine Phosphoryl-Ethanolamine

Phosphatidylserine Phosphoryl-Serine

Phosphatidylinositol Phosphoryl-Inositol

Phosphatidylglycerol Phosphoryl-Glycerol

Phosphatidic acid / Phosphoryl group only

phosphatide
Phosphatide  glycerol-3-phosphate with
2 fatty acids at C1 & C2
Glycerophospholipid

Phosphatidic acid
Ether Glycerophospholipid

Platelet Activating Factor

(PAF)
C1 C2 C3
choline

Position Group Group Name

C1 Alkyl 16-C chain
C2 Acyl Acetate (2C)
C3 “Head” Phosphorylcholine
• more water soluble
 Objective
• Structure & chemistry of fatty acids,
triacylglycerols, & glycerophospholipids
• Sphingolipids
• Waxes
• Terpenes
• Steroids
• Biological signals
• Lipidomics
 Type of Lipids
4 Sphingolipids Found in
biological
Backbone: sphingosine membrane

C3 C2 C1

Fatty
Fatty acid joined acid
to a sphingosine
(18C amino alcohol)
via an amide
linkage
 Sphingomyelin
Sphingolipid

C3 C2 C1 Phosphoryl choline

Amide
linkage Phosphorus-containing
Sphingolipid
Found in the nervous tissue
of animals
Formed by esterification of
a phosphorylcholine /
Sphingosine
phosphorylethanolamine to
(Backbone) 1-OH of a ceramide
Fatty acid
Sphingolipid

Glycosphingolipids Ceramide-based
lipids
Component (s) in Glycosphingolipid
1 or more sugar residues in
Ceramide a -glycosidic linkage at
1-OH moiety

Type of
1
Cerebroside
Glycosphingolipid
Ceramide
Ceramide
Component(s) Galactose / Glucose
Sphingolipid
Type 2
Sulfatide
Ceramide
Glyco- Component(s) Galactose
Sulfate
sphing (esterified at C3 of Gal)

olipids
3
Type
Ganglioside
Ceramide
Component(s) 3 or more
sugars
Sphingolipid

Glycosphingolipids
• Glycosphingolipids have important cellular functions
(a) glycosphingolipids at cell surfaces are used to
determine tissue & organ specificity
(b) cell-cell recognition & tissue immunity
(c) gangliosides that present in nerve endings are
important for nerve impulse transmission
• Accumulation of specific glycosphingolipids due to
absence of their specific degradation enzymes can
cause disease
• eg. Tay-Sachs disease
– accumulation of ganglioside GM2 in brain
– cause a red spot on retina, gradual
blindness, loss of weight in infants & children
 Objective
• Structure & chemistry of fatty acids,
triacylglycerols, & glycerophospholipids
• Sphingolipids
• Waxes
• Terpenes
• Steroids
• Biological signals
• Lipidomics
 Type of Lipids
5
Waxes
• Esters of long-chain alcohols with long-chain fatty acids

Saturated or unsaturated
Alcohols May include sterols
(eg. Cholesterol)
• Weakly polar head group  water insoluble
Fatty
• Long, acids
nonpolar Saturated
tail (hydrocarbon chains)
• Properties of waxes:
(i) water-repellant
(ii) glossy surface

Carnauba wax (palm frond)

Lanolin (wool wax)
 Objective
• Structure & chemistry of fatty acids,
triacylglycerols, & glycerophospholipids
• Sphingolipids
• Waxes
• Terpenes
• Steroids
• Biological signals
• Lipidomics
 Type of Lipids
6
Terpenes
• Combinations of 2 or more (≥ 2) molecules of
2-methyl-1,3-butadiene (isoprene) (C5)
• Isoprene units are usually linked head to tail to
form straight-chain or cyclic molecules
Terpene

Types of
Terpenes
Number Number of
Type of isoprene Detail
carbon unit
Monoterpene C10 2 All higher plants

Sesquiterpene C15 3 ----

Diterpene C20 4 ----

C30 6 Include squalene &

Triterpene lanosterol
(precursors of cholesterol
& other steroids)
C40 8 Include carotenoids,
Tetraterpene a class of photosynthetic
pigments
 Terpene

Monoterpenes are recognized by their flavors or odors

a carotenoid found in tomatoes

Precursors of cholesterol & steroids
 Objective
• Structure & chemistry of fatty acids,
triacylglycerols, & glycerophospholipids
• Sphingolipids
• Waxes
• Terpenes
• Steroids
• Biological signals
• Lipidomics
Terpene

Steroids (8-10 C alkyl

side-chain)

• Terpene-based lipids
• Have a common structural motif
of three 6-membered rings &
one 5-membered ring all fused
together
• eg. cholesterol

(i) OH group in sterol

(ii) carbonyl group in
other steroids
Steroid Hormones
Derived from
cholesterol

• Include bile acids & 5 families of hormones in animals:

Hormone Example Source Function
1 Androgen Testosterone Testicles Mediate development of sexual
2 Estrogen Estradiol Ovaries characteristics & sexual
function
3 Progestin Progesterone Ovaries Control menstrual cycle &
pregnancy
4 Glucocorticoid Cortisol Adrenal Control carbohydrate, protein, &
gland lipid metabolism
5 Mineralocorticoid Aldosterone Adrenal Regulate salt (Na+, K+, Cl-)
gland balances in tissues
 Derived from

Bile Acids
cholesterol

• Include cholic & deoxycholic acid

• Molecules secreted in bile from gallbladder
• Assist in the absorption of dietary lipids in the intestine
 Objective
• Structure & chemistry of fatty acids,
triacylglycerols, & glycerophospholipids
• Sphingolipids
• Waxes
• Terpenes
• Steroids
• Biological signals
• Lipidomics
 Biological Signals
• Glycerophospholipids & sphingolipids play
important roles as
(i) principal components of biological membranes
(ii) chemical signals
• Lipid signals act locally either
(i) within the cell where they are made, or
(ii) on nearby cells
• These lipid signals typically initiate a cascade of
reactions with multiple effects
• Lifetimes of these lipid signals are usually very short
• Creation & breakdown of lipid signals is carefully
regulated & timed
Phospholipase Enzyme that hydrolyze
the ester bond of
glycerophospholipid

Phospholipase Cleaved Group

A1 Fatty acids from C1
A2 Fatty acids from C2
C Polar head group
D
Biological Signals
 Objective
• Structure & chemistry of fatty acids,
triacylglycerols, & glycerophospholipids
• Sphingolipids
• Waxes
• Terpenes
• Steroids
• Biological signals
• Lipidomics
 Lipidomics
• Many human diseases involve disruption of lipid
metabolic enzymes & pathways
• New techniques have made possible global analysis of
lipids & their interacting protein partners in organs, cells,
& organelles – an approach termed lipidomics
• Typical cells contain over a thousand different lipids
• Complete understanding of lipid function will require
determination of which lipids are present & in what
concentrations
• Cellular lipidomics provides a framework for
understanding myriad roles of lipids