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Notes on Lipids

NOTES ON LIPIDS
Lipids are a class of organic compounds in plants and animals that share a common physical property
SOLUBILITY IN NONPOLAR SOLVENT such as diethyl ether, benzene, and carbon tetrachloride, and
INSOLUBILITY IN WATER.
Lipids are NOT a family of compounds in the same sense as previously discussed families, i.e., they do not
possess one characteristic functional group. A number of functional groups are found on lipids carboxylic acid
and ester, phosphate ester, amide, alcohol, ether, ketone. Many lipids contain more than one kind of functional
group. Some lipids contain none of these functional groups.

SOLUBILITY EXPERIMENT FOR LIPIDS


Undecomposed plant or animal matter is crushed into small particles or powder using a blender or other
mechanical device and then a nonpolar solvent is added. Lipids dissolve in the nonpolar solvent while other
compounds (proteins, carbohydrates, nucleic acids, and inorganics) do not. The solution is filtered from the
insoluble matter and then the solvent evaporated to yield the LIPIDS.
Even lipids with polar functional groups such as ester and amide have the same solubility behavior as other
lipids. These molecules contain large portions that are nonpolar with a very small portion comprising the polar
groups, too small to impart a significant polarity to the molecule as a whole.

CLASSIFICATION OF LIPIDS
Lipids are categorized into SAPONIFIABLE and NONSAPONIFIABLE LIPIDS. Saponifiable lipids
contain at least one ester group, which undergoes hydrolysis in the presence of an acid, a base, or an enzyme.
Hydrolysis by a base is referred to as SAPONIFICATION. Hydrolysis cleaves a saponifiable lipid into two or
more smaller molecules. Nonsaponifiable lipids do not undergo hydrolytic cleavage into smaller molecules. Figure
1 gives an overview of the different types of lipids.

Saponifiable lipids

Triacylglycerols

Fats

Oils

Waxes

Phosphoglycerides

Phospholipids

Plasmalogens

Spingolipids

Sphingomyelins

Glycolipids

Nonsaponifiable lipids

Steroids

Phostaglandins
Leukotrienes

Terpenes

Figure 1. Classification of Lipids

Lipids perform a variety of biological roles. TRIACYGLYCEROLS are used for energy storage and
metabolic fuel. PHOSPHOLIPIDS, SPHINGOLIPIDS, and CHOLESTEROL (a steroid) are structural components
of cell membranes. Nonsaponifiable lipids perform a variety of regulatory functions (hormones, vitamins).

FATTY ACIDS

Fatty acids are the carboxylic acids used as building blocks for saponifiable lipids. Only very small amounts
of fatty acids are found in uncombined form in nature. Several different fatty acids have been isolated from various

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Notes on Lipids

plant and animal lipids. Table 1 lists the most important fatty acids, all of which have long hydrocarbon chain
attached to the carboxyl (COOH) group.
Table 1. Common Saturated and Unsaturated Fatty Acids
No. of
C=C
SATURATED FATTY ACIDS
Butyric
0
Caproic
0
Caprylic
0
Capric
0
Lauric
0
Myristic
0
Palmitic
0
Stearic
0
Arachidic
0
Behenic
0
Lignoceric
0
Cerotic
0
Name of Acid

No. of
C
4
6
8
10
12
14
16
18
20
22
24
26

M.P.
C

Structure

CH3(CH2)2COOH
CH3(CH2)4COOH
CH3(CH2)6COOH
CH3(CH2)8COOH
CH3(CH2)10COOH
CH3(CH2)12COOH
CH3(CH2)14COOH
CH3(CH2)16COOH
CH3(CH2)18COOH
CH3(CH2)20COOH
CH3(CH2)22COOH
CH3(CH2)24COOH

-8
-3
17
32
44
54
63
70
75
80
85
88

UNSATURATED FATTY ACIDS


Palmitoleic
1
16
CH3(CH2)5CH=CH(CH2)7COOH
32
Oleic
1
18
CH3(CH2)7CH=CH(CH2)7COOH
1
Linoleic
2
18
CH3(CH2)4 (CH=CHCH2)2 (CH2)6COOH
-5
Linolenic
3
18
CH3CH2(CH=CHCH2)3(CH2)6COOH
-11
Arachidonic
4
20
CH3(CH2)4 (CH=CHCH2)5 (CH2)2COOH
-50
* Butyric acid is included among long-chain fatty acids because of its occurrence in butter and its
importance in fatty acid metabolism.

Fatty acids without double bonds are referred to as SATURATED FATTY ACIDS. Fatty acids with double
bonds are referred to as UNSATURATED FATTY ACIDS. MONOUNSATRATED FATTY ACIDS are those
with only one double bond while POLYUNSATURATED FATTY ACIDS are those with two or more double
bonds. The double bonds in fatty acids are exclusively CIS double bonds, not TRANS double bonds.
The most abundant saturated fatty acids are palmitic and stearic acids and the most abundant unsaturated
fatty acids are oleic and linoleic. Linoleic and linolenic acids are ESSENTIAL FATTY ACIDS, i.e., they cannot be
synthesized in the human body. All other fatty acids are NONESSENTIAL FATTY ACIDS since they can be
synthesized either from other fatty acids or from carbohydrates and proteins.
COMMON STRUCTURAL FEATURES OF FATTY ACIDS used to synthesize SAPONIFIABLE LIPIDS in
PLANTS AND ANIMALS
They ALL are mono-carboxylic acids. (R-COOH)
Their R groups are unbranched chains of carbons.
The total number of carbons is an even number (except bacterial lipids).

Problem 1: Which of the following carboxylic acids are incorporated into animal and plant lipids?
CH3
CH3CH2CH(CH2)10COOH
A

CH3(CH2)17COOH
B

CH3(CH2)4(CH=CHCH2)2(CH2)4COOH
C

UNSATURATED FATTY ACIDS are often referred to by an omega (, ) number to indicate the location
of the double bond nearest to the methyl end of the carbon chain.

Example: Palmitoleic acid is omega-7 (-7).


CH3(CH2)5CH=CH(CH2)7COOH
Methyl end

A number is placed after the omega sign to indicate the number of the first carbon of the double bond,
counting from the methyl carbon.

Problem 2: Give the omega designation for the fatty acids LINOLEIC, LINOLENIC, and OLEIC CIDS.

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Notes on Lipids

Figure 2. Chemical structure of alpha-linolenic acid (ALA), an essential omega-3 fatty acid

DIFFERENCES IN MELTING POINTS BETWEEN SATURATED AND UNSATURATED FATTY ACIDS


The melting points of unsaturated fatty acids are lower than those of saturated fatty acids with the same
number of carbons. The more double bonds present, the lower the melting point of the fatty acid. The effect of
double bond in lowering the melting point is a consequence of its existence in the CIS geometry instead of TRANS.
Unsaturated fatty acids are liquids at temperatures where saturated fatty acids are solids.
The intramolecular forces of attraction of saturated fatty acids are relatively high since their elongated
molecules can pack together tightly in an orderly fashion. Higher temperatures are needed during melting to
overcome the higher intramolecular forces.
CIS double bonds introduce rigid kinks or bends into the carbon chain. Packing of molecules in the solid
state is looser and less orderly, intramolecular attractive forces are lower, and high temperatures are not needed to
separate molecules during melting. The more double bonds there are the more kinks in the chain, the less orderly
the solid state packing, and the lower the melting temperatures. TRANS double bonds do not affect the melting
point in the same manner as CIS double bonds. TRANS double bonds, although rigid, do not introduce significant
bends into the chain. The melting point of the TRANS isomer of oleic acid is much higher than that of the CIS
isomer. The molecular shapes of stearic, oleic, and linoleic acids are shown in Figure 2.

Figure 3. Molecular shapes of saturated and unsaturated fatty acids

TRIACYGLYCEROLS (Triglycerides)

Triacyglycerols are triesters of GLYCEROL (1,2,3- propanetriol) where each of the three OH groups
forms an ester group by reacting with COOH group of a fatty acid. Animal fats such as butter, beef, pork, and
poultry fats and vegetable oils such as corn, peanut, and olive oils are triacyglycerols.

A variety of triacylglycerols are possible. SIMPLE TRIACYGLYCEROLS are those in which the three Rs
are the same, i.e. three molecules of the same fatty acids react with glycerol. COMPLEX TRIACYLGLYCEROLS
are those in which the Rs are different. Naturally occurring triacyglycerols are complex triacyglycerols.

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Notes on Lipids

Problem 3: Write the equation showing triacylglycerol formation from one mol of glycerol and 1 mol
of each of palmitic, stearic, and oleic acids.

The answer to problem 3 will result to three structural isomers. The reaction that involves 1 mol each of
palmitic, oleic and stearic acids will give a mixture of these three structural isomers.

The most abundant fatty acid units, both saturated and unsaturated, in fats and oils are the C16 and C18
acids. Vegetable oils differ from animal fats in the relative amount of saturated and unsaturated fatty acid units.
Animal fats generally contain less than 50% to 60% unsaturated fatty acid units. Vegetable oils generally contain
more than 80% unsaturated fatty acid units.
The term FAT and OIL convey the physical state of triacyglycerols at ambient temperatures. Animal
triacyglycerols are solids while vegetable triacyglycerols are liquids since the melting points of animal fats are
higher than the melting points of vegetable oils.

Problem 4: Triacyglycerols A contains 48% oleic acid, 36% linoleic acid, 10% palmitic acid, 3%
stearic acid, 1% linolenic acid and lesser amounts of other fatty acids. Triacyglycerol B
contains 50% oleic acid, 26% palmitic acid, 15% stearic acid, 6% linoleic acid, and
lesser amounts of other fatty acids. One of the samples is corn oil and the other is pork
fat (lard). Which is which?

Notable exceptions to the generalization that vegetable triacyglycerols are liquids while animal
triacyglycerols are solid are coconut, palm and fish oils. Coconut and palm oils contain smaller amounts of
unsaturated fatty acids than other vegetable oils and are solids. Fish oils contain larger amounts of unsaturated fatty
acid units than other animal fats and are liquids.

CHEMICAL REACTIONS
The chemical reactions of triacyglycerols are those expected of molecules containing ester and C=C
functional groups. The ester group undergoes hydrolysis while the C=C undergoes addition reactions. Hydrolysis
of a triacylglycerol yields a glycerol and fatty acids. The reaction requires an acid or base in the laboratory.
Biological hydrolysis of a triacylglycerol occurs during digestion and requires the appropriate enzymes, referred to
as LIPASES.
A.

LABORATORY HYDROLYSIS
1. Acid-catalyzed hydrolysis yields equimolar amounts of the fatty acids and glycerol present.

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Notes on Lipids

2. Saponification by NaOH yields glycerol and sodium salts of the fatty acids involved.

Hydrolysis by base is referred to as SAPONIFICATION because this is the reaction for manufacturing soaps.
The mixture of the sodium (or potassium) salts of fatty acids is a soap.
The C=C double bonds present in triacyglycerols undergo addition reaction with H2 and halogen (Cl2, Br2,
I2). Hydrogen addition referred to as HYDROGENATION, requires the presence of a metallic catalyst such as
palladium or platinum. Hydrogenation of vegetable oils such as corn oil is used to produce margarine.
3. Addition Reactions
3.1 Hydrogenation (H2)

3.2

Halogenation (Cl2, Br2, I2)

Problem 5: Write the equations for a) acid-catalyzed hydrolysis,


b) saponification by NaOH,
c) hydrogenation, and
d) halogenations by I2
of the triacylglycerol containing equimolar amounts of Myristic, Linolenic, and Stearic
acids.

Fats and oils become RANCID on standing, i.e., they develop disagreeable odors and tastes. Two reactions
are involved in this process HYDROLYSIS and OXIDATION.
Under moist air conditions the triacylglycerol in butter can hydrolyze to form BUTYRIC and CAPROIC
acids, responsible for the rancid odors. This can be prevented by storing butter in a closed container to minimize
the contact with microorganisms in air and by refrigeration, which slows the rate of all reactions.
Polyunsaturated oils are also susceptible to rancidity through oxidation reactions. Oxygen in air reacts with
the double bonds and cleaves long chains into shorter-chain fatty acids with rancid odors.
(o)
CH3(CH2)5CH=CH(CH2)7COOH

CH3(CH2)5COOH + HOOC(CH2)COOH
Figure 4. Oxidation of Palmitoleic Acid

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Notes on Lipids

To avoid unwanted oxidation, the food industry adds


antioxidants such as BHA and BHT to food products.
BHT
Butylated hydroxytoluene

BHA and BHT preferentially react with oxygen and


prevent the reaction of oxygen with the double bonds in
polyunsaturated oil. Potato chips are so treated.
BHA and BHT are phenols that are easily oxidized.

BHA
Butylated hydroxyanisole

WAXES

Waxes form natural coatings in fruits, leaves, furs, feathers and skin. These coatings have protective
functions against physical damage such as water-repellency functions (waterproofing of birds, control of water loss
by transpiration in plants).
Waxes derived from natural sources are used commercially in polishes, cosmetics, and ointments. Most
waxes are mixtures of esters although some are hydrocarbon, alcohols, or ketones.
The ester waxes are esters of a monohydric alcohol (an alcohol containing one OH) and a fatty acid. The
alcohols and fatty acids are those of 16 to 36 carbons with unbranched structure and an even number of carbons.

Problem 6: Which of the following are found in waxes?


CH3(CH2)27COO(CH2)21CH3
A

CH3(CH2)26COO(CH2)22CH3
B

CH3(CH2)26COO(CH2)21CH3
C

Table 2. Some Common Waxes


Structure

Name

Sources/Uses

CH3(CH2)14CO-(CH2)29CH3

BEESWAX
(merisyl palmitate)

Found in bees
Used in candles, cosmetics,
confections, medicinal and art
preservations
From heads of sperm whales
Used in the manufacture of cosmetics,
soaps, candles
from Brazilian palm trees
used as coatings for perishable
products, for polishing candies and
pills, as auto and floor.

CH3(CH2)14CO-(CH2)15CH3
O

(HO)aCH2(CH2)bCO-(CH2)cCH3
a =0 to 1
b =17-29
c =31 or 33
O

CH3(CH2)mCO-(CH2)nCH3
m =20 or 22
n = 21-35
O

CH3(CH2)xCO-(CH2)yCH3
X = 12-16

SPERMACETI
(cetyl palmitate)
CARNAUBA WAX

RICE BRANWAX

from rice bran


as lipstick base, plastic processing aid.

BAYBERRY WAX

from berries of myrtle shrubs


used as candle wax

PHOSPHOLIPIDS

Phospholipids are saponifiable lipids that contain phosphate ester functional group and ionic charges.
A. PHOSPHOGLYCERIDES are phospholipids based on glycerol. Two of the three OH groups of glycerol
are esterified as in the triacylglycerols but the third OH is a phosphate diester.
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Notes on Lipids

General Representation of Phospoglycerides


G
L
Y
C
E
R
O
L

fatty acyl group

fatty acyl group

phosphate

amino
alcohol

A phosphoglyceride is formed by the reaction of glycerol with two fatty acids and one phosphoric acid to
produce PHOSPHATIDIC ACID. The latter is then further esterified with a small amino alcohol such as
ethanolamine, HOCH2CH2NH2. The reactions are dehydrations; between glycerol -OH and fatty acid -OH, glycerol
-OH and phosphoric acid -OH, phosphoric acid OH and amino acid OH.

Figure 5. Formation of phosphoglyceride

Amine alcohol:

CHOLINE (lecithin)
HO-CH2CH2N+(CH3)3

H2C

fatty acid

HC

fatty acid

H2C

phosphate + choline

hydrophobic

hydrophilic

ETHANOLAMINE (cephalin)
+

HO-CH2CH2NH3

H2C

fatty acid

HC

fatty acid

H2C

phosphate + ethanolamine

hydrophobic

hydrophilic
Hein, M. et al (2005) INTRODUCTION TO GENERAL, ORGANIC AND BIOCHEMISTRY, 8 th Ed.

Phosphoglycerides are named by placing PHOSPHATIDYL- before the name of the amino alcohol.
PHOSPHATIDYLETHANOLAMINE cephalin
PHOSPHATIDYLCHOLINE
lecithin

At physiological pH (7), phosphoric acid groups are usually ionized, thus nearby amine nitrogen would be
protonated. Phophoglycerides actually exist as having negative and positive charges. This ionic nature of the
phosphate and amino portion of the molecule is essential to the structure of the lipid bilayer of cell membranes.
Problem 7: Write the structure of the phosphoglyceride formed from one mol each of glycerol,
palmitic and stearic acids, phosphoric acid and choline.

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Notes on Lipids

A typical phosphoglyceride showing the hydrophilic and hydrophobic portions

The hydrophobic and hydrophilic portions repel each


other and are directed away from each other.

hydrophilic
hydrophobic

B.

PLASMALOGENS are phospholipids similar to phosphoglycerides except that the fatty ester unit at
C-1 is replaced by a fatty vinyl ether unit.
General Representation of Plasmalogens

-O-CH=CH-R
A fatty vinyl ether unit

The structure on the right


shows a plasmalogen that
contains a stearic acid unit,
choline, and C18 vinyl unit.

C18 vinyl ether


unit
Stearic acid
Choline

SPHINGOLIPIDS

Sphingolipids are saponifiable lipids characterized by the presence of sphingosine as their backbone rather
than glycerol.

HO CH CH = CH (CH2)12CH3
CH NH2
CH2 OH

Reaction
Sites

A. SPHINGOMYELINS may be categorized as both sphingolipid and phospholipid since they contain the
phosphate diester group and amino alcohol present in other phospholipids but their backbone is
sphingosine instead of glycerol.
General representation of Sphigomyelins

Other structural units are


incorporated into sphingosine
through reactions at the -NH2 and
-OH
groups
to
form
sphingomyelins.

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Notes on Lipids

Problem 8: Show the formation of the sphingomyelins containing a carbohydrate component in


place of the phosphate fragment of sphingomyelins.

B. GLYCOPLIPIDS are a group of sphingolipids containing carbohydrate component in place of the


phosphate fragment of sphingomyelins.
General representation of Glycolipids

OH

HC

CH=CH(CH2)12CH3

HC

H
N

Carbohydrate unit

H2C

O-D-glucose or D-galactose

CEREBROSIDES are the simplest glycolipids where the carbohydrate component is a glucose ring or
galactose ring. They occur in the cell membranes of the brain.
GANGLIOSIDES are complex lipids. The carbohydrate components are oligosaccharide chains of up to seven
units. They are found in the cell surfaces in neural tissue and are often parts of the receptor sites for
neurotransmitters.
All sphingolipids in cell membranes are in a dynamic state, as are many biological structures. They are
constantly broken down and replaced by new molecules. Some genetic diseases involve the inability of individuals
to breakdown sphingolipids and results to the accumulation in tissues, especially brain tissues. This may lead to
swelling of tissues and cause disastrous physiological effects.
Examples:
Tay-Sachs Disease lacks enzymes to degrade Gangliosides
Nhemann Pick Disease lacks enzymes to breakdown Sphingomyelins.
*Both may result to mental retardation and eventually death

Hein, M. et al (2005) INTRODUCTION TO GENERAL, ORGANIC AND BIOCHEMISTRY, 8 th Ed.

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Notes on Lipids

Figure 6. The structure of a cerebroside containing oleic and -D-Glucose

THE NONSAPONIAFIABLE LIPIDS


Nonsaponifiable lipids are not cleaved into smaller molecules by hydrolysis (including saponification and
digestion) because of the absence of ester groups.

STEROIDS
Steroids are a group of nonsaponifiable lipids that contain a four ring system of three 6-membered rings and
one 5-membered ring. This structure affects the properties of cell membranes.

CHOLESTEROL is the most abundant steroid.


An important constituent of the cell membrane
Acts as a raw material for the synthesis of other
steroids
Important constituent of the cell membrane
Found dissolved in dietary fats and oils and
synthesized in the liver from acetyl coenzyme A
Excessive amount of cholesterol due to faulty metabolism and inefficient transport may result to
GALLSTONE, hard chunks of precipitated cholesterol in the gall bladder or bile ducts; or
ARTHEROSCLEROSIS, a degenerative disease in which lipid deposits build up on the inner walls of arteries and
present obstruction.
Table 3. PHYSIOLOGICALLY ACTIVE STEROIDS (Natural and Synthetic)

Name

Structure

Function

Bile Salts

Emulsify fat and oil digestion

Vitamin D3

Needed for healthy bones and teeth

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Notes on Lipids

Cortisone

Regulate use of glucose


Reduces symptoms of arthritis and
allergies

Aldosterone

Regulates sodium chloride and


water retention

Prednisone

Used clinically as substitute to


cortisone (the slight structural
variation reduces the side effects of
cortisone)

Testosterone

Regulates the development of male


reproductive organs and masculine
characteristics
An androgen

Estradiol

One of the estrogens which


regulates female characteristics

Ethisterone

The first oral contraceptive

Norethindrone

A
synthetic
hormone
that
suppresses the release of ova and
thus prevent pregnancy

Progesterone

Prepares the uterus wall to accept a


fertilized egg and maintain
pregnancy

Mestranol

A synthetic estrogen combines


with the actual contraceptive
component in birth control pills in
order to reduce side effects
Regulates the menstrual cycle

EICOSANOIDS
A key metabolic unsaturated fatty acid is arachidonic acid. It is an important precursor to four members of
the eicosanoid family of compounds. These eicosanoids act as hormonelike substances involved in intercellular
signaling processes. The biochemicals derived from the fatty acid arachidonic acid are collectively termed
eicosanoids.
The four classes of eicosanoids are prostaglandins, prostacyclins (associated with swelling and
inflammation),
leukotrienes (associated with allergic reactions and asthma attacks), and thromboxanes
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Notes on Lipids

(associated with blood clotting).


Cell membranes release arachidonic acid in response to a variety of
circumstances, including infection and allergic reactions.

Hein, M. et al (2005) INTRODUCTION TO GENERAL, ORGANIC AND BIOCHEMISTRY, 8 th Ed.

Figure 7. Structures of Some Eicosanoids

LEUKOTRIENES

Leukotrienes contain 20 carbons in a continuous chain with a COOH group at one end.
compounds that trigger responses to inflammation, allergy and asthma.

These are

PROSTAGLANDINS

Prostaglandins are the best known of the eicosanoid class. Prostaglandins are similar to leukotrienes except
that there is a 5-membered ring as part of the 20 carbon chain. Prostaglandins can cause smooth muscle contraction
or relaxation, vasodilation, stimulation of blood clotting, and a variety of other effects.
Though produced by the body in minute amounts, they are associated with an amazing number of
physiological actions. A great deal of interest is currently focused on the involvement of prostaglandins in tissue
inflammation and associated pain as well as their role in increasing body temperature (fever). A current theory is
that aspirin (acetylsalicylic acid), the most widely used fever-reducing and anti-inflammatory drug, may inhibit
prostaglandin formation.
Knowledge of the functions of prostaglandins has led to effective treatment for many medical conditions.
Prostaglandins cause uterine contractions and thus are used to induce labor. Drugs that block prostaglandin
formation are now prescribed to treat several menstrual cramps. Prostaglandins are used to inhibit the secretion of
stomach acid in people suffering from peptic ulcers and to treat ulcers on the hands and feet of people suffering
from Reynauds disease, diabetes, or other atherosclerosis. Other prostaglandins relax the smooth muscles and are
used to relieve asthma and to treat high blood pressure. Blue babies are treated with prostaglandins to keep fetal
duct open, thereby increasing the oxygen content of their blood until they are strong enough to undergo corrective
surgery.

TERPENES

Terpenes contain multiples of five carbons since they are synthesized by linking together ISOPRENE
UNITS. The isoprene unit is a branched C5 unit.
Isoprene unit

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Notes on Lipids

Vitamins A, D, and E are terpenes.


Vitamin A

Table 4. Biological Functions of Nonsaponifiable Lipids


Compound
Steroids
Cholesterol
Androgens*
Synthetic Androgens
Progesteones, Estrogens
Synthetic estrogens
Aldosterone
Cortisone
Bile Salts
Vitamin D
Prostaglandins
Leukotrienes
Terpenes
Vitamin A
Vitamin E
Vitamin K
* Androsterone, testosterone

Referred to as anabolic steroids

Estrone, estradiol

Function
Component of cell membranes
Development of male reproductive organs; maintenance of secondary
sex characteristics
Muscle development for athletes
Development of female reproductive organs; maintenance of
secondary sex characteristics; control of menstrual cycle
Oral contraceptives
Controls water and electrolyte balances
Controls metabolism of proteins, carbohydrates, lipids; controls
water and electrolyte balances; controls inflammation
Facilitate digestion of saponifiable lipids; facilitate absorption of fat
soluble vitamins (A,D,E,K) in intestinal tract
Controls calcium absorption in intestinal tract and deposition in bone
Lower or raise blood pressure; involved in blood clotting; control
gastric secretions; cause inflammation; induce labor
Trigger responses to inflammation, allergy, asthma
Facilitates vision in dim light (night vision)
Antioxidant; maintains cell membrane integrity by preventing
oxidation of unsaturated fatty acid units
Essential for blood clotting

CELL MEMBRANES
Cell membranes provide the mechanical barrier that separates cells from their environment. Their ability to
control the entry of various materials into cells and the exit of other material from the cells are critical to the
functioning of the cells.
Metabolic fuels to generate energy and building blocks for synthesizing proteins, nucleic acids, and other
compounds are extracted from the environment and concentrated in the cells. Waste materials from cell activities
are expelled into the environment.
Enzymes, which are structural components of membranes, maintain the intracellular pH and ionic
composition within narrow limits to regulate intracellular enzyme activity. They also generate appropriate ionic
concentration gradients across cell membranes, essential for nerve and muscle action. Similar membranes separate
intracellular organelles such as the nucleus and mitochondria from the cytoplasm.
Cell membranes are constructed principally from phospholipids but glycolipids and cholesterol are
involved. The common feature of the membrane lipids is their similarity to soap and detergent molecules the
presence of both HYDROPHILIC and HYDROPHOBIC portions in the same molecule. Such molecules are
referred to as AMPHIPATHIC MOLECULES.

Hydrophilic head (polar)

Hydrophobic tail (nonpolar)

http://www.sleepingdogstudios.com/Network/Biology/Bio_3.2B_files/frame.htm#slide0027.htm

The hydrophilic head of glycolipids are the saccharide units because of the presence of several OH groups; while
cholesterol has a hydrophilic portion in its OH group. Phospholipids and sphingomyelins possess the ionic head

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Notes on Lipids

brought by the presence of the phosphate and nitrogen centers in the amino alcohol. All membrane lipids share this
common feature, the hydrophilic head and hydrophobic tail.
LIPID BILAYER
Cell membranes result from the association of membrane lipid molecules to form lipid bilayer. There are
two layers of lipid molecules. Each layer consists of lipid molecules associated with each other such that the
hydrophobic tails of one molecule are adjacent to the hydrophobic tails of other molecules. Simultaneously, the
hydrophilic heads of different lipid molecules are aligned next to each other.
Each layer is two sided; it has hydrophilic (ionic/polar) side and a hydrophobic (nonpolar) side. Two layers
form the lipid bilayer by association of their hydrophobic sides. Both sides of the lipid bilayer are hydrophilic and
in contact with aqueous solutions. The lipid bilayer is the cell membrane, surrounding the aqueous cell contents
and isolating them from the aqueous environment outside the cell.

Hein, M. et al (2005) INTRODUCTION TO GENERAL, ORGANIC AND BIOCHEMISTRY, 8 th Ed.

Figure 8: The fluid-mosaic model of a cell membrane

FLUID MOSAIC MODEL OF CELL MEMBRANES


Cell membranes have a FLUID MOSAIC STRUCTURE. The term FLUID conveys the fluid (flexible) or
liquid-like nature of the cell membrane. The term MOSAIC conveys the complex nature of cell membrane in terms
of their structure and composition. Not only does the lipid bilayer contain different lipids (phosphoglycerides,
plasmalogens, sphingomyelins, glycolipids, cholesterol), it also contains a variety of protein essential to cell
function.
Cholesterol is a regulator of membrane fluidity. It keeps the membrane from being too fluid. This is due to
the hydrophobic portion of cholesterol (steroid ring system) which is more rigid than that of other membrane lipids.
Cell membranes contain anywhere from 20 to 75 percent protein depending on the type of the cell. Proteins
are either integral proteins or peripheral proteins depending on whether or not they are imbedded in the lipid
bilayer. Integral proteins are imbedded in the lipid bilayer. Some integral proteins span the full lipid bilayer, going
from the intracellular side to the extracellular side. Others do not span the full lipid bilayer, being imbedded either
on the intracellular or extracellular side. Peripheral proteins are located on the membrane surface, either the
intracellular or extracellular surface.

http://thebasisoflife.wikispaces.com/Membrane+Structure+and+Function

Figure 9. Membrane Lipids


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Notes on Lipids

THREE PROCESSES FOR TRANSPORT OF MOLECULES AND IONS ACROSS CELL MEMBRANES
1.

Simple (Passive) Diffusion


Occurs in the direction of a concentration gradient, i.e, Movement from High Concentration
Region to a Low Concentration Region. Simple diffusion involves diffusion through the
hydrophobic regions of the lipid bilayer.
For small molecules and ions such as water, urea, ethanol, CO2, O2, NH3, Cl-

2.

Facilitated Diffusion
Occurs in the direction from high to low concentration. It involves the integral proteins acting as
channels or gates through which the diffusion occurs. There are integral proteins in the membrane
specific for each molecule or ion or group of similar molecules or ions to be transported.
For large polar uncharged molecules such as glucose and all ions

3.

Active Transport
Requires transport against the normal concentration gradient. It occurs through integral proteins
but requires the expenditure of energy (typically ATP). Active transport systems are often referred
to as PUMPS.
For red blood cells, the extracellular concentration of Na+ (sodium ion) is about 140 millimolar
(mM) while the intracellular concentration is about 10 mM. Active transport of the ion occurs
from inside of the red blood cells to outside (plasma).

Hein, M. et al (2005) INTRODUCTION TO GENERAL, ORGANIC AND BIOCHEMISTRY, 8 th Ed.

Figure 10. Transport of Molecules across Membrane

LIPIDS AND HEALTH


Cholesterol separates from the blood and deposits on the inner wall of arteries to form plaque. This narrows
the arteries that results in the heart working harder to pump blood. The blood pressure increases and the heart
enlarges in time. Plaque formation also converts the smooth inner walls of arteries to rough surfaces and this
promotes thrombosis, the formation of blood clots which block arteries. A heart attack involves the blockage of
arteries feeding the heart and results in the death of heart tissue. A stroke involves the blockage and usually also
the rupture of arteries in the brain and results in damage to brain tissue.
There are statistical links between our dietary lipids and cardiovascular disease. Medical practitioners
generally make the following dietary recommendations to decrease the incidence of cardiovascular disease.
1.
2.
3.

Eat less total meat, especially less red meat.


Eat more vegetables
Eat more fish

In terms of the chemical composition of our food intake, these recommendations mean:

1.
2.
3.

Decrease in the amount of lipid compared to protein and carbohydrate intake.


Decrease in the amount of lipids that contain saturated fatty acids and cholesterol.
Meat contains much more lipid and much greater saturated fatty acid content than vegetables.
Meat has high cholesterol content while vegetables contain no cholesterol.
Red meat tends to contain much more lipid than poultry (avoid the skin) or fish (avoid fatty fish). Fish
contains higher unsaturated fatty acid content than red meat or poultry.

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Notes on Lipids

HEALTH BENEFITS OF DECREASING THE AMOUNT OF CHOLESTEROL IN THE DIET


The major fraction of the cholesterol in the blood is synthesized in the liver. Decreasing dietary cholesterol
has some effect in decreasing the cholesterol level in the blood. The effect is measurable but not huge unless the
persons normal diet contains excessive animal fat. However dietary control is prudent for most people since any
decrease in blood cholesterol level decreases the tendency for plaque formation.
Cholesterol and Triacyglycerols are insoluble in the blood. They carried in the blood stream by complexation
with Phospholipids and Special Proteins The lipoproteins are classified according to the density.
Table 5. Blood Lipoproteins

VDL
Lipid, %
Protein, %
Density, g/mL

90
10
0.95 1.01

LDL
75
25
1.02 1.06

HDL
60
40
1.06 1.21

Chylomicrons
Transport exogenous (dietary) triacylglycerols and cholesterol from the intestine to other tissues.
Very low density lipoproteins (VLDL) and low density lipoproteins (LDL)
Transport endogenous (internally synthesized triacylglycerol and cholesterol from other tissues.
High density lipoproteins
Transports cholesterol back to the liver from other tissues.
In the liver, fats are processed for excretion. It provides a clean-up mechanism to dispose excess cholesterol.
Table 6. Average Blood level of HDL
mg/mL of plasma

Men

45

Women

55

Male runners

65

Female runners

75

*Women are less susceptible to heart attacks because of their higher HDL concentrations.
*Runners develop higher levels of HDL proportional to the extent to which they exercise.

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Berg, J.M. et al (2002) BIOCHEMISTRY. 5th Ed. W.H. Freeman and Co., New York.
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Denniston, K.J., et al. (2007) GENERAL, ORGANIC AND BIOCHEMISTRY, 5th Ed. McGraw-Hill, New York.
Garrett, R.H. and C.M. Grisham (2005) BIOCHEMISTRY. 3rd Ed.Thomson-Brooks/Cole, USA.
Hein, M. et al (2005) INTRODUCTION TO GENERAL, ORGANIC AND BIOCHEMISTRY, 8 th Ed. John Wiley and Sons, Inc., USA.
Hill, J.W. and D.K. Kolb (2004) CHEMISTRY FOR CHANGING TIMES, 10 th Ed. Pearson Education International. New Jersey,
USA.
Kroshwitz, J. and M. Winokur (l985) CHEMISTRY: GENERAL, ORGANIC, BIOLOGICAL. McGraw-Hill Book Co., USA.
Matthews, C.K. and K.E. Van Holde (1996) BIOCHEMISTRY. 2nd Ed. Benjamin Cummings Publishing Co., California.
Odian, G. and I. Blei (1994) THEORY AND PROBLEMS OF GENERAL, ORGANIC, AND BIOLOGICAL CHEMISTRY. McGrawHill, Inc. New York.
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