LIPIDS

BIO 2210 INTRODUCTORY BIOCHEMISTY

2017
Leanna Kalicharan, BSc., MSc.
Department of Biology
Faculty of Natural Sciences
University of Guyana
LIPIDS

INTRODUCTION TO BIOLOGICAL
LIPIDS & FATTY ACIDS
 Introduction
BIOLOGICAL LIPIDS are chemically diverse
compounds.

Defining feature is their INSOLUBILITY IN WATER:

water insoluble compounds.

Lipids contain the elements carbon, hydrogen

and oxygen.
 Lipids
Definition:
Lipids are organic compounds formed
mainly from alcohol and fatty acids
combined together by ester linkage.

O
H2O O
R CH2 OH HO C R R CH2 O C R
+
Fatty alcohol Fatty acid Esterase (lipase) ester (lipid)
 FUNCTIONS of LIPIDS
Energy storage: Fat & oils are principal
stored forms of energy in many organism;

Structure of cell membranes: Phospholipids

and sterols make up about the mass of
biological membranes;

Precursors of hormones (steroids and

prostaglandins).
 Biological Importance of Lipids
1. They are more palatable and storable to
unlimited amount compared to
carbohydrates.
2. They have a high-energy value (25% of
body needs) and they provide more
energy/gram than carbohydrates and
proteins but carbohydrates are the
preferable source of energy.
3. Supply the essential fatty acids that
cannot be synthesized by the body.
 Biological Importance of Lipids

4. Supply the body with fat-soluble vitamins

(A, D, E and K).

5. They are important constituents of the

nervous system.

6. Tissue fat is an essential constituent of

cell membrane and nervous system. It is
mainly phospholipids in nature that are not
affected by starvation.
 Classes (groups) of Lipids
Fatty acids Free fatty acids; for example: Stearic acid
and Oleic acid

Phospholipids the membrane lipids

Three types of phospholipids:

Glycerophospholipids

Sphingolipids

Sterols

Steroids have specific and essential biological activities; for

example: major male & female sex hormones
 Introduction Fatty acids
Fats and oils used (almost universally) as stored forms of
energy in living organisms are highly reduced

compounds and are derivatives of fatty acids.

They are soluble in non-polar solvents such as petroleum
ether, benzene, chloroform.
 Fatty acids
Fatty acids are Carboxylic acids with long hydrocarbon chains of 4
36 carbons
General structure:

CH3 (CH2)n COOH n = 0 : CH3COOH n = 1 : propionic acid

n is almost always even

Nomenclature for these compounds specifies the chain length and

number of double bonds, separated by colon.
For example: the 16-Carbon saturated palmitic acids is abbreviated
16:0 and 18-Carbon Oleic acid with one double bone is 18:1.
 Fatty acids

Fatty acids can be classified either as:

o Saturated or
o Unsaturated
 Fatty acids
Saturated fatty acids
The chain is fully saturated: it contains no
double bond, and unbranched.

Unsaturated fatty acids

The chain contains one or many double
bonds.
Fatty acids
 Unsaturated Fatty acids
There are 2 types of unsaturated fatty acids:
1. Monounsaturated fatty acids have one C=C double bond.
Double bond typically occurs between C-9 and C-10 on the
hydrocarbon chain.
2. Polyunsaturated fatty acids have many C=C double bonds that
generally occurs between C-12 and C-15.

The physical properties of fatty acids and of compounds that contain

them are largely determined by the length and degree of unsaturation
of the hydrocarbon chain.
 Fatty acids Physical
properties
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 the solubility in water.
The carboxylic acid group is polar and accounts
for the slight solubility of short-chain fatty acids in
water.
 Fatty acids Physical
properties
The melting points of fatty acids and of compounds that
contain them are strongly influenced by the length and
degree of unsaturation of the hydrocarbon chain.

At room temperature (~ 25C), saturated fatty acids (12:0

to 24:0) have a waxy consistency. Whilst, unsaturated fatty
acids of these lengths are oily liquids.
 Fatty acids Physical
properties
A cis double bond forces a kink in the hydrocarbon chain.
Fatty acids with one or several kinks cannot pack together
as tightly as fully saturated fatty acids, and their
interactions with each other are therefore weaker.
Because it takes less thermal energy to disorder these
poorly ordered arrays of unsaturated fatty acids; they
have lower melting points than saturated fatty acids of
the same chain length.
 Fatty acids Physical
properties

The cis double bond (shaded) in oleic acid (oleate) does not permit rotation and
introduces a rigid bend (kink) in the hydrocarbon tail.
Common Fatty acids
n = 4 butyric acid (butanoic acid)
n = 6 caproic acid (hexanoic acid)
n = 8 caprylic acid (octanoic acid)
n = 10 capric acid (decanoic acid)
Common Fatty acids

n = 12: lauric acid (n-dodecanoic acid; C12:0)

n = 14: myristic acid (n-tetradecanoic acid; C14:0)
n = 16: palmitic acid (n-hexadecanoic acid; C16:0)
n = 18; stearic acid (n-octadecanoic acid; C18:0)
n = 20; arachidic (eicosanoic acid; C20:0)
n= 22; behenic acid
n = 24; lignoceric acid
n = 26; cerotic acid
Triacylglycerols also referred to as
Triglycerides
 Triacylglycerols also referred to
as Triglycerides
The simplest form of lipids constructed from fatty
acids.

They are referred to fats or neutral fats.

A triglyceride is a molecule composed of three

fatty acids each in an ester linkage with a single
glycerol.
Triacylglycerols also referred to
as Triglycerides

Glycerol and Triacylglycerols

 Triglycerides

The molecules join together through the process

of condensation losing a molecule of water
each time a link is made.

The link between the glycerol molecule & each

fatty acid is an Ester Link.

The fatty acids in a lipid molecule can differ in

length and can be saturated or unsaturated.
 Triglycerides
Because the polar hydroxyls of glycerol and the
polar carboxylates of the fatty acids are bound
in ester linkages, triacylglycerols are non-polar,
hydrophobic molecules, essentially insoluble in
water.
For example, this explains why oil-water mixture (oil and vinegar
salad dressing) have two phases. Because lipids have lower
specific gravities than water, the oil floats on the aqueous phase.
 Triglycerides
Triacylglycerols containing the same kind of
fatty acid in all three positions are called simple
triacylglycerols, and are named after the fatty
acid they contain.

Mixed triacylglycerols contain two or more

different fatty acids; to name these compounds
the name and positions of each fatty acid must
be specified.
Many food contains
Triacylglycerols
Most natural fats, such as those in vegetable oils, dairy products,
and animal fat, are complex mixtures of simple and mixed
triacylglycerols.

These contain a variety of fatty acids differing in chain length and

degree of saturation.

Vegetable oils such as corn and olive oil are composed largely of
triacylglycerols with unsaturated fatty acids, and thus are liquid at
room temperatures.

Triacylglycerols containing only saturated fatty acids (e.g. tristearin)

are major component of beef fat, are white, greasy solids at room
temperature.
Many food contains
Triacylglycerols Rancidity
When lipid-rich foods are exposed too long to
oxygen in air, they may spoil and become
rancid.

The unpleasant taste and smell associated with

rancidity result from oxidative cleavage of the
double bonds in unsaturated fatty acids to
produce aldehydes and carboxylic acids of
shorter chain length and therefore higher
volatility.
 Fatty acid reactions
salt formation
NaOH
RCO2H RCO2-Na+ (a soap)

ester formation

lipid peroxidation

-H20
R'OH + RCO2H RCO2R'

R' O2
R R R'
H H non-enzymatic
OOH
very reactive
 Hydrogenated fats
Hydrogenation leads to either
saturated fats and or trans fatty acids
The purpose of hydrogenation is to
make the oil/fat more stable to oxygen
and temperature variation (increase
shelf life)
Examples: Margarine
 Neutral lipids
Glycerides (fats and oils)
Glycerol

Ester of glycerol - mono glycerides, diglycerides

and triglycerides

Waxes simple esters of long chain alcohols

CH2OH OH

H OH OH

CH2OH OH

glycerol is a prochiral molecule

GLYCERIDES

O O O

O
O R O R O R

OH OH R O

OH O R O R

O O

MONOGLYCERIDE DIGLYCERIDE TRIGLYCERIDE

Function: storage of energy in compact form and cushioning

WAXES
Biological waxes are esters of long-chain
saturated and unsaturated fatty acids (having
14 to 36 carbon atoms) with long-chain alcohols
(having 16 to 30 carbon atoms)
O

H3C (CH2)14 C O CH2 (CH2)28-CH3

fatty acid
long chain alcohol
WAXES
Their melting points (60 to 100C) are generally
higher than those of triacylglycerols .

Waxes are the chief storage form of metabolic

fuel in marine organisms that constitute the
plankton.

They serve a diversity of other function related to

their water-repellent properties and their firm
consistency.
WAXES
Their melting points (60 to 100C) are generally
higher than those of triacylglycerols .

Waxes are the chief storage form of metabolic

fuel in marine organisms that constitute the
plankton.

They serve a diversity of other function related to

their water-repellent properties and their firm
consistency.
WAXES
Biological waxes has a variety of applications in
pharmaceuticals, cosmetic and other industries.
For example:
Lanolin (from lambs wool),
Beeswax,
Carnauba wax (from a Brazilian palm tree), and
Spermaceti oil (from whales)
are widely used in the manufacture of lotions,
ointments and polishes.
Spermaceti source

Carnauba wax source

Bees wax
Structural Lipids in
Membranes: Phospholipids
Lipids and proteins are 2 major components of
all membranes.
The 3 major lipid components of cell
membranes are:
Glycerophospholipids,
Sphingolipids and Phospholipids
Sterol - Cholesterol.
Structural Lipids in Membranes:
Glycerophospholipids
These are also called Phosphoglycerides.
They are all derivatives of phosphatidic acid.
Two fatty acids are ester-linked to glycerol at C-1 and
C-2, and a highly polar (charged) head group is
attached to C-3. O

O O R
fatty acids (hydrophobic tail)
glycerol O R'
O-
O O X
P

O
phosphate
 Structure of
Glycerophospholipids
 O

O O R
fatty acids (hydrophobic tail)
glycerol O R'
O-
O O X
P

O
phosphate

X = H (phosphatidic acid) - precursor to other phospholipids

+
X = CH2-CH2-N (CH3)3 phosphatidyl choline
- +
X = CH2-CH(COO )NH3 phosphatidyl serine
+
X = CH2-CH2-NH3 phosphatidyl ethanolamine
Structural Lipids in Membranes:
Glycerophospholipids
The fatty acids in glycerophospholipids can be of a
wide variety. They are different in different species, in
different tissues of the same species, and different in
same cell or tissue. O

O O R
fatty acids (hydrophobic tail)
glycerol O R'
O-
O O X
P

O
phosphate
Structural Lipids in Membranes:
Sphinogolipids
They are the second large class of membrane lipids.
They are all derivatives of sphingosine.
They have a polar head and two non-polar tails, but
unlike glycerophospholipids they contain no glycerol.

Sphingolipids are composed of molecule of the long-

chain amino alcohol sphingosine (or one of its
derivatives), one molecule of a long-chain fatty acid,
a polar head alcohol, and sometimes phosphoric
acid in diester linkage at the polar head group.
Structural Lipids in Membranes:
Sphinogolipids
Carbons C-1, C-2 and C- bear functional groups:
-OH,
-NH2
-OH
These are structurally homologous with the three hydroxyl
groups of glycerol in glycerophospholipids.
When a fatty acid is attached in amide linkage to the
NH2, the resulting compound is ceramide.
Ceramide is the fundamental structural unit common
to all sphingolipids.
Sphingolipids

Based on sphingosine instead of glycerol OH

OH

sphingosine NH2

R long chain hydrocarbon

HO

NH2 attach fatty acid here

OH attach polar head group here

Sphingolipids
Structural Lipids in Membranes:
Sphinogolipids
There are 3 subclasses of sphingolipids that are all
derivatives of ceramide.
Sphingomyelins,
Glycolipids (neutral/uncharged), and
Gangliosides.
Structural Lipids in Membranes:
Sphingolipids: Sphingomyelins
Contain phosphocholine or phosphoethanolamine as
their polar head group, and are therefore classified
as phospholipids.

They are present in plasma membranes of animal

cells; the myelin sheath which surrounds and insulates
the axons of myelinated neutrons is a good source of
sphingomyelins.
 Sphingomyelin (a
ceramide)
HO R
O

NH R' usually palmitic acid

O-
O O
P N(CH3)+

O
phosphatidyl choline (also can be ethanolamine)
It is a ubiquitous component of animal cell membranes, where it is by far
the most abundant sphingolipid. It can comprise as much as 50% of the
lipids in certain tissues, though it is usually lower in concentration than
phosphatidylcholine
Structural Lipids in Membranes:
Glycolipids and gangliosides
Neutral glycolipids and gangliosides have one or
more sugars in their head group, connected
directly to the OH at C-1 of the ceramide; they
do not contain phosphate.
HO R
O

NH R'

O SUGAR polar head is a sugar

beta linkage
Structural Lipids in Membranes:
Glycolipids and gangliosides
These sugar-containing sphingolipids are
sometimes called glycosphingolipids.

Neutral glycolipids contain one to six sugar units,

which may be D-glucose, D-galactose, or N-
acetyl-D-galactosamine.

These glycosphingolipids occur largely in the

outer face of the plasma membrane.
Structural Lipids in Membranes:
Gangliosides
The most complex sphingolipids, contain very large
polar heads made of several sugar units.

Gangliosides make up about 6% of the membrane

lipids in the gray matter of the human brain, and they
are present in lesser amounts in membranes of most
non-neural animal tissues.
Structural Lipids in Membranes:
Sterols
Sterols are structural lipids present in the membranes
of most eukaryotic cells.
Their characteristic structure is the steroid nucleus
consisting of four fused rings, three with 6 carbons
and one with 5.
H3 C
CH3

CH3 H
hydrophobic
O
H H

OH drawn this way R O

usually palmitate

hydrophillic
Structural Lipids in Membranes:
Sterols
Cholesterol is the major sterol in animal tissues.

It is amphipathic, with a polar head group (the OH

group at C-3) and the a non-polar hydrocarbon
body (the steroid nucleus and the hydrocarbon side
chain at C-17) about as long as 16-carbon fatty acid
in its extended form.

Stigmasterol is the sterol found in plants, and

ergosterol in fungi.
Structural Lipids in Membranes:
Sterols
In addition to their roles as membrane constituents,
the sterols serve as precursors for a variety of products
with specific biological activities.

Bile acids (in which the side chain at C-17) is

hydrophilic, act detergents in the intestine,
emulsifying dietary fats to make them more readily
accessible to digestive lipases.

Also, a variety of steroid hormones are produced

from cholesterol by oxidation of the side chain at C-
17.
Amphipathic Lipids Aggregate

We have noted that glycerophospholipids,

sphingolipids and sterols are virtually insoluble in
water.

When mixed with water, these amphipathic

compounds form microscopic lipid aggregates in a
phase separate from their aqueous surroundings.

Typically, lipid molecules cluster together with their

hydrophobic mioties in contact with each other and
their hydrophilic groups interacting with the
surrounding water.
Amphipathic Lipids Aggregate

Depending on the precise conditions, and the nature

of the lipids used, three types of lipid aggregates can
form when amphipathic lipids are mixed with water.

Micelles: are relatively small, spherical structures

involving a few dozen to few thousand molecules
arranged so that their hydrophobic regions
aggregate in the interior, excluding water and their
hydrophilic head groups are at the surface, in
contact with water.
Amphipathic Lipids Aggregate

Amphipathic lipid aggregates that form in water.

(a) In spherical micelles (b) In a bilayer (c) Liposome
Amphipathic Lipids Aggregate

Bilayer: two lipid monolayers combine to form a two-

dimensional sheet. Bilayer formation occurs most
readily when the cross-sectional areas of the head
group and side chain(s) are similar, as in
glycerophospholipids and sphingolipids.

The hydrophobic portions in each monolayer

interact, excluding water.

The hydrophilic head groups interact with water at

the two surfaces of the bilayer.
Amphipathic Lipids Aggregate

Liposome: this is formed when a lipid bilayer folds

back on itself to form a hollow sphere or vesicle.

By forming vesicles, bilayer sheets lose their

hydrophobic edge regions, achieving maximal
stability in their aqueous environment.

These bilayer vesicles enclose water, creating a

separate aqueous compartment.
Lipids with specific Biological
activities
Thus far, the 2 classes of lipids are:
Storage lipids and
Structural lipids
These 2 classes of lipids are major cellular
components.
Membrane lipids represent about 5 to 10% of the
dry mass of most cells, while
Storage lipids represent more than 50% of the
mass of an adipocyte (fat cells).
Lipids with specific Biological
activities
The exceptions are:
Lipids play a passive role in the cell; fuels are acted
on by oxidative enzymes, and
Lipids in membranes form impermeable barriers that
separate cellular compartments.
Other active lipids serve as essential cofactors for
enzymes, as electron carriers, or as intracellular
signals.
Steroids

Steroids (the third group of lipids) includes hundred of

compounds that share four-ring steroid nucleus,
which are synthesized from five-carbon precursors
related to isoprene:
Steroids

The isoprenoids include vitamins A, D, E and K, first

recognized as fatty materials that are essential to the
normal growth of animals and numerous biological
pigments.

The major groups of steroid hormones are the male

and female sex hormones and the hormones of the
adrenal cortex, cortisol and aldosterone.

All of these hormones contain an intact steroid

nucleus.
Steroids
They are produced in one tissue and are carried in the
bloodstream to target tissues, where they bind to highly
specific receptor proteins and thus, trigger changes in
gene expression and metabolism.

Steroids derived from Cholesterol. Testosterone, the male sex hormone, is produced in the
testes. Estradiol, one of the female sex hormones, is produced in the ovaries and
placenta. Cortisol and aldosterone are produced in the cortex of the adrenal gland and
they regulate glucose metabolism and salt excretion, respectively.
Biological Cofactors: Fat-soluble
vitamins
Vitamins are compounds essential to the health of
humans and other vertebrate animals that cannot be
synthesized by these animals and must therefore be
obtained in the diet.

Nutritional studies have identified 2 general classes of

such compounds:
Those soluble in nonpolar organic solvents (fat-soluble
vitamins)
Those that can be extracted from foods with aqueous
solvents (water-soluble vitamins)
Biological Cofactors: Fat-soluble
vitamins
The fat-soluble group was resolved into four vitamins A, D,
E and K, all of which are isoprenoid compounds.
Isoprenoids are synthesized by the condensation of
isoprene units.

Vitamin A (retinol) is a pigment essential to vision. Vitamin

A itself does not occur in plants, but many plants contain
carotenoids, light absorbing pigments that can be
enzymatically converted into vitamin A by most animals.
Biological Cofactors: Fat-soluble
vitamins
Vitamin D is a derivative of cholesterol and the precursor
to a hormone essential in calcium and phosphate
metabolism in vertebrate animals. Vitamin D3, called
cholecalciferol, is normally formed in the skin in a
photochemical reaction driven by the ultraviolet
component of sunlight.

Vitamin E is a collective name for a group of closely

related lipids called tocopherols, all of which contain a
substituted aromatic ring and a long hydrocarbon side
chain. Tocopherols can undergo oxidation-reduction
reactions on the aromatic ring.
Biological Cofactors: Fat-soluble
vitamins
Vitamin E cont.
The vitamin activity of tocopherols likely results from
their ability to prevent oxidative damage to the lipids of
cellular membranes. Recall that reactions of
unsaturated fatty acids with oxygen that cause
rancidity in foods. If such reactions were to occur in
living cells, the resulting defects in membrane function
might cause cell death.
Tocopherols react with and destroy the most reactive
forms of oxygen, protecting unsaturated fatty acids
from oxidation.
Biological Cofactors: Fat-soluble
vitamins
Vitamin K is a lipid cofactor required for normal blood
clotting. The vitamin acts in the formation of prothrombin,
a blood plasma protein essential in blood-clot formation.
 Biological Membranes

Membranes define the external boundary of cells

and regulate the molecular traffic across the
boundary. They divide the internal space into
discrete compartments to segregate processes and
components.

Membranes are tough but flexible, self-sealing and

selectively permeable to polar solutes. Their
flexibility permits shape changes that accompany
cell growth and movement.
 Biological Membranes

Membranes are composed of just two layers of

molecules and are therefore very thin. They can
be thought of as essentially two-dimensional.
 The molecular constituents of
membranes
Proteins and polar lipids account for almost all of the
mass of biological membranes.

The small amount of carbohydrate present in

generally part of glycoproteins and glycolipids.

The relative proportions of protein and lipid differ in

different membranes, reflecting the diversity of
biological roles.
The supramolecular architecture of
membranes
All biological membranes share certain fundamental
properties.

They are impermeable to most polar or charge

solutes, but permeable to nonpolar compounds.

They are 5 to 8 nm thick; appear trilaminar (three-

layered) when viewed in cross section with the
electron microscope.
 The supramolecular architecture of
membranes

The fluid mosaic model for membrane structure. The fatty acyl chains in the interior of the
membrane form a fluid, hydrophobic region. Integral membrane proteins float in this sea
of lipid, held by hydrophobic interactions with their nonpolar amino acid side chains.
The supramolecular architecture of
membranes
Amphipathic phospholipids and sterols form a lipid
bilayer, with the nonpolar regions of lipids facing
each other at the core of the bilayer and the polar
head groups facing outward.

In this lipid bilayer, globular proteins are embedded

at irregular intervals, held by hydrophobic
interactions between the membrane lipids and
hydrophobic domains in the proteins.
The supramolecular architecture of
membranes
The individual lipid and protein subunits in a
membrane form a fluid mosaic; its pattern, unlike a
mosaic of ceramic tile and mortar, is free to change
constantly.

The membrane mosaic is fluid because the

interactions among lipids and between lipids and
proteins, are noncovalent, leaving individual lipid and
protein molecules free to move laterally in the plane
of the membrane.
The supramolecular architecture of
membranes
Although the lipid bilayer structure itself is stable, the
individual phospholipid and sterol molecules have
great freedom of motion within the plane of the
membrane.

The interior of the bilayer is also fluid; individual

hydrocarbon chains of fatty acids are in constant
motion produced by rotation about the carbon-
carbon bonds of long acyl side chains.
The supramolecular architecture of
membranes
The degree of fluidity depends on lipid composition
and temperature.

At low temperature, relatively little lipid motion occurs

and the bilayer exists as a nearly crystalline array.

Above a temperature that is characteristic for each

membrane; lipids can undergo rapid motion.
The supramolecular architecture of
membranes
The temperature of the transition from crystalline solid
to fluid depends upon the lipid composition of the
membrane.

Saturated fatty acids pack well into crystalline array,

but kinks in unsaturated fatty acids interfere with this
packing, preventing the formation of a crystalline
solid state.

The higher the proportion of saturated fatty acids, the

higher is the solid-to-fluid transition temperature of the
membrane.
The supramolecular architecture of
membranes
The sterol content of a membrane also is an
important determinant of this transition temperature.

The rigid planar structure of the steroid nucleus,

inserted between fatty acyl side chains, has 2 effects
on fluidity.
Below the temperature of the solid-to-fluid
transition, sterol insertion prevents the highly
ordered packing of fatty acyl chains, and thus
fluidizes the membrane.
The supramolecular architecture of
membranes
Above the thermal transition point, the rigid ring
system of sterol reduces the freedom of
neighboring fatty acyl chains to move by rotation
about carbon-carbon bonds, and thus reduces
the fluidity in the core of the bilayer.

Sterols therefore tend to moderate the extremes

of solidity and fluidity of the membranes that
contain them.