CYL456: Chemistry of Life An Introduction

Biomolecules

Lipids
Instructor: Yashveer Singh, PhD

General, Organic, and Biological Chemistry, HS Stoker,

Brooks/Cole
Timberlakes Chemistry: An Introduction to General, Organic, and
Biological Chemistry, KC Timberlake, Prentice Hall
3 November 2014

Lipids

A lipid is an organic compound found in living organism that is

either insoluble or only sparingly soluble in water
Lipids are used to store energy and carbon atoms. Fats also
surround and insulate vital body organs to provide protection from
mechanical shock and prevent excessive loss of heat energy. Lipids
are basic components of cell membranes and several cholesterol
derivatives function as hormones in the body

Fatty acids

Fatty acids are naturally occurring monocarboxylic acid, containing

even number of carbon atoms. Rarely found free in nature but as a
part of the structure of more complex lipids
Short chain (C4-6), medium chain (C8-10) or long chain (C1226)
Also classified as saturated, monounsaturated, and
polyunsaturated fatty acid
Most naturally occurring fatty acids are cis-

Biologically important fatty acids

-6 and -3 fatty acids

Humans require omega-3 linolenic acid (ALA) in the diet because

it is used to synthesize two other omega-3, which are important in
cellular
function:
eicosapentaenoic
acid
(EPA)
and
docosahexaenoic acid (DHA)

-6 and -3 fatty acids

Cholesterol forms plaques adhering to the walls of the blood
vessels in atherosclerosis and heart disease
Consequently, blood pressure rises because it has to squeeze
through a smaller opening in the blood vessel
As more plaque forms, there is also a possibility of blood clots
blocking the blood vessels and causing a heart attack. Omega-3 fatty
acids lower the tendency of blood platelets to stick together and
thus reduces the possibility of blood clots

Naturally occurring unsaturated fatty acids have

mostly cis- configuration

The physical properties of fatty acids are dependent on

chain length and degree of unsaturation
The long hydrocarbon chain decreases the solubility of fatty acids
in water. The slight aqueous solubility exhibited by short chain fatty
acids is due to the presence of polar carboxylic group
Melting points are influenced by the length and degree of
unsaturation present in fatty acids. Saturated fatty acids are wax and
unsaturated fatty acids are oils at room temperature
The difference in melting points is due to the different degree of
packing of fatty acid molecules

The unsaturated fatty acids have lower melting point than saturated
fatty acids of same chain length

Triglycerols
The simplest lipids constructed from
fatty
acids
are
triglycerols/triglycerides
Contain three fatty acids in ester
linkage. Called simple or mixed.
Naturally occurring triglycerols are
mixed
Since the polar hydroxyl group (-OH)
are bound in ester linkage, triglycerols
are polar hydrophobic molecules,
essentially insoluble in water

Triglycerols
In most eukaryotes, triacylglycerols
form a oily droplets in the aqueous
cytosol
In vertebrates, specialized cells
called adipocytes, or fat cells, store
large amounts of triacylglycerols as fat
droplets that nearly fill the cell
Triglycerols are also stored as oils in
the seeds of many types of plants,
providing energy and biosynthetic
precursors during seed germination
Moderately obese people with 15 to
20 kg of triacylglycerols deposited in
their adipocytes could meet their
energy needs for months by drawing
on their fat stores

Triglycerols

Seals, walruses, penguins, and other warm-blooded polar

animals are amply padded with triacylglycerols. In hibernating
animals (bears, for example), the huge fat reserves accumulated
before hibernation serve the dual purposes of insulation and energy
storage

Triglycerols
About 90% of the weight of the head is made up of the spermaceti
organ, a blubbery mass that contains up to 3,600 kg (about 4 tons) of
spermaceti oil, a mixture of triacylglycerols and waxes containing an
abundance of unsaturated fatty acids

This mixture is liquid at the normal resting body temperature of the

whale, about 37 oC, but it begins to crystallize at about 31 oC and
becomes solid when the temperature drops several more degrees

Hydrolysis

Triacylglyercol
hydrolysis requires an
acid or a base. Under
acidic conditions, the
hydrolysis
products
are glycerol and fatty
acids

Base hydrolysis

Base hydrolysis is known as saponification and used to produce

soap and detergents

Oxidation

The carboncarbon double bonds present in the fatty acid residues

of a triacylglycerol are oxidized in presence of molecular oxygen,
which breaks the carboncarbon double bonds and produces aldehyde
and carboxylic acid
The short-chain aldehydes and carboxylic acids so produced have
unpleasant odor. Fats and oils containing them are said to have
become rancid

Hydrogenation

Addition of hydrogen to multiple across carboncarbon double

bonds, which increases the degree of saturation and leads to a
corresponding increase in the melting point of the substance
Many food products are usually partially hydrogenated. In this
process some, but not all, double bonds present are converted to
single bonds. Liquids (usually plant oils) are thus converted to semisolid materials

Trans fats
Commercial vegetable oils
are partially hydrogenated
to improve the shelf life of
vegetable oils and stability at
the high temperatures

It converts many of the cis double bonds to single bonds

As double bonds are broken and reconstituted, some cis double
bonds convert to trans. Dietary intake of trans fatty acids leads to a
higher incidence of cardiovascular disease

Trans fats

Cholesterol, bile salts, and steroid hormones are

steroidal lipids

Steroids refers to compounds that contain steroid nucleus- three

cyclohexane and one cyclopentane ring fused together
These rings are designated as A, B, C, and D

Cholesterol

Cholesterol is among the most important and abundant steroid in

the body
Categorized as sterol because of the presence of OH group on C-3
in A ring
A component of cell membranes, myelin sheath, brain, and
nerve tissue. Found in liver, bile salt, and skin (produces vitamin D).
Present in adrenal glands and produces steroid hormones
Present in animal sources (milk, egg, and meat; synthesized by the
liver) but not in vegetable and plant products

Cholesterol in food

Recommended consumption is not more than 300 mg cholesterol

per day
Clinically cholesterol levels are considered elevated if the plasma
cholesterol level exceeds 200 mg/dl

Cholesterol increases the risk of cardiovascular disease

High level of cholesterol leads to the
accumulation of lipid deposits (plaque) in
blood that lines and narrows the blood
artery thereby increasing the risk of
cardiovascular disease

Saturated fat in diet may stimulate the

production of cholesterol by liver. There
are other risk factors too- family history,
smoking, lack of exercise, obesity,
diabetes, gender, and age

Lipoproteins transport lipids

Lipoproteins transport lipids

In the body, lipids have to transported through the blood stream
(aqueous) to tissues but lipids are insoluble in the aqueous
environment of blood. Therefore, lipids are made water soluble by
combining with glycerophospholipids and proteins to form water
soluble complex called lipoproteins

Lipoproteins are spherical particles with an outer surface of polar

proteins and glycerophopsholipids that surrounds hundreds of nonpolar lipid molecules
Based on density, these are categorized into three groups: very low
density lipoprotein (VLDL), low density lipoprotein (LDL), and
high density lipoprtien (HDL). The density increases with increase
in protein content of lipoprotein

Lipoproteins transport lipids

Very low density lipoprotein (VLDL) transports triglycerols,

cholesterol, etc. to tissues for storage and muscle for energy

Lipoproteins transport lipids

Low density lipoproteins (LDL) carries cholesterol to tissues for
the synthesis of cell membranes, steroid hormones, and bile salts. If
the level of cholesterol is more than the amount needed by the
tissues, it is deposited in the arteries. This restricts the blood flow and
increases the risk of heart disease and/or myocardial infarctions
(heart attack). LDL are referred to as bad cholesterol
High density lipoprotein (HDL) carries excess cholesterol to liver
for conversion to bile salt and excretion. When the HDL levels are
high, excess cholesterol is removed from the arteries. HDL are
referred to as good cholesterol

Lipoproteins transport lipids

Bile acids are emulsifier

An emulsifier is the
substance
that
disperse and stabilize
water
insoluble
substances as colloidal
particles in aqueous
solution

A bile acid is a cholesterol derivative that functions as a lipid

emulsifying agent in the aqueous environment of the digestive tract.
One-third of daily cholesterol produced in liver is converted to bile
acids. They are obtained by the oxidation of cholesterol

Bile acids are emulsifier

The medium through
which bile acids are
supplied to intestine is
called bile

Bile is a fluid that contains emulsifying agent secreted by the liver

and stored in gall bladder. It is released into the small intestine during
digestion. Bile also contains bile pigment, cholesterol, and
bicarbonate ion as an electrolyte
The mechanism of action is very similar to cleansing action of soap

High cholesterol levels in gall bladder results into the

formation of gallstone

If large amounts of cholesterol is present in gallbladder, it may

precipitate out and form gallstone (80% of gallstones are pure
cholesterol). The gallstone gives severe pain while passing through
the bile duct
The gallstone obstruct the bile duct and bile is not excreted. As a
result, the bile pigment (bilirubin) is released into the blood, resulting
into jaundice. Bilirubin gives yellow color to the skin, eyes and urine

Protecting coating lipid: biological waxes

Biological waxes are lipids, which are monoester of a long-chain

fatty acid and a long-chain alcohol. Waxes are monoesters
The fatty acids in biological waxes are saturated and contain
from 14-36 carbon atoms. The alcohols found in waxes may be
saturated or unsaturated and may contain from 16-30 carbon atoms

Steroid hormones
A hormone is a biochemical
substance, produced by a gland,
and has a messenger function
Some hormones, though not all,
are lipids
A steroid hormone is a
cholesterol derivative and depends
on cholesterol for its synthesis

Androgens

The term androgens is used to collectively male sex hormones

Examples include testosterone and androsterone

Produced in testes and adrenal cortex and promote the
development of secondary male characteristics (growth of muscle
and facial hair and the maturation of the male sex organs and of
sperm).
They also promote muscle growth

Estrogens

Estrogens refers to group of female hormones, synthesized in the

ovaries and adrenal cortex
Responsible for the development of female secondary sex
characteristics at the onset of puberty (uterus increases in size, fat is
deposited in the breasts, and the pelvis broadens) and for the
regulation of the menstrual cycle

Progesterone

Progesterone prepares the uterus for the implantation of a fertilized

egg
If an egg is not fertilized, the levels of progesterone and estrogen
drop sharply, and menstruation follows
They also suppress ovulation

Oral contraceptives

Female sex hormones or their synthetic analogues (shown

above) are used as oral contraceptives to prevent pregnancy
A mixture of a synthetic estrogen and a synthetic progesterone
is used (combined oral contraceptive pill or the pill) or progesterone
alone (mini pill) is used
Come in a pack of 21, 28, 91 tablets and is taken by mouth once
every days

Oral contraceptives
Combinations of estrogen and progestin work by preventing
ovulation (the release of eggs from the ovaries). They also change
the lining of the uterus (womb) to prevent pregnancy from
developing and change the mucus at the cervix (opening of the
uterus) to prevent sperm (male reproductive cells) from entering

Side effects include weight gain and greater risk of forming blood
clots

Anabolic steroids

Testosterone increases the muscle mass and decreases body fat.

Derivatives of testosterone, called anabolic steroids, that enhance
these effects have been developed

Anabolic steroids

Anabolic steroids have been used by athletes to increase muscle

mass and physical strength. Such a use is not permitted by most
national and international sport organizations
Steroid abuse is associated with a wide range of adverse side
effects. Acne and breast development in men, heart attacks, and liver
problems. The male reproductive system is altered, causing testicular
shrinkage and decreased sperm production. In females, steroid abuse
causes masculinization. Breast size and body fat decrease, the skin
becomes coarse, and the voice deepens. Some may experience
excessive growth of body hair

Prostaglandins

A prostaglandin is a messenger lipid containing C20-fatty-acid

derivative that contains a cyclopentane ring and oxygen-containing
functional groups. Twenty carbon fatty acids are converted into a
prostaglandin structure when the eighth and twelfth carbon atoms of
the fatty acid become connected to form a five membered ring

Prostaglandins are named after the prostate gland, which was first
thought to be their only source. Today, more than 20 prostaglandins
have been discovered in a variety of tissues in both males and
females

Prostaglandins

Prostaglandins

The treatment of pain, fever, and inflammation is achieved by

inhibiting the
prostaglandins

enzymes

that

convert

arachidonic

acid

to

Prostaglandins

Several nonsteroidal anti-inflammatory drugs (NSAIDs), such as

aspirin, block the production of prostaglandins and in doing so
decrease pain and inflammation and reduce fever (antipyretics).
Ibuprofen has similar anti-inflammatory and analgesic effects
Long-term use leads to liver, kidney, and gastrointestinal damage

Biodiesel

Biodiesel is a nonpetroleum fuel (biofuel) that can be used in place

of diesel
Produced from vegetable oils (primarily soybean), waste vegetable
oils, and some animal fats

Biodiesel

Biodiesel is nontoxic and biodegradable, it burns in an engine to

produce much lower levels of carbon dioxide emissions, particulates,
unburned hydrocarbons, and aromatic hydrocarbons
Because biodiesel has extremely low sulfur content, it does not
contribute to the formation of the sulfur oxides that produce acid rain