Module 2.

Biochemistry

Module Title: Lipids

Course Title: Biochemistry
Course Number: Chem 102

Course Description:

The course will give insights on the process occurs within the living organisms. It includes the
study in carbohydrates, lipids, proteins, metabolism, fats and oils and the like.

Course Facilitator: Dr. Nelinda V. Duero

Overview
Biochemistry is the study of the chemical substances and processes that occur in plants,
animals, and microorganisms and of the changes they undergo during development and life. It
deals with the chemistry of life, and as such it draws on the techniques of analytical, organic, and
physical chemistry, as well as those of physiologists concerned with the molecular basis of vital
processes.

Lesson Outcomes
 To become acquainted with the general properties of lipids and fatty acids.
 To understand the classification of lipids
 To distinguish between fats and oils
 To distinguish between soaps and detergents
 To understand the role of phospholipids in cell membrane
 To understand the role of the eicosanoids

Indicative Content
1. Lipids
2. Fatty Acids
3. Fats
4. Oils

Let’s Discuss
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Module 2. Biochemistry

LIPIDS

General Properties

A second group of organic compounds that serve as food for the body is the lipids.
Lipids are organic compounds of biologic origin and in general
1. Are insoluble in water
2. Are soluble in nonpolar organic solvents such as ether, acetone, and carbon tetrachloride
3. Contain carbon, hydrogen, and oxygen; sometimes contain nitrogen and phosphorus
4. In most cases yield fatty acids on hydrolysis or combine with fatty acids to form esters
5. Take part in plant and animal metabolism

Fatty Acids

Both simple and compound lipids yield fatty acids on hydrolysis. Fatty acids are straight-
chain organic acids. The fatty acids found in natural fats usually contain an even number of
carbon atoms. Fatty acids can be either saturated or unsaturated. Saturated fatty acids contain
only single bonds between carbon atoms. Unsaturated fatty acids contain a few double bonds
between carbon atoms. Polyunsaturated fatty acids contain many double bonds.
Table 21 -1 lists some common fatty acids and where they are found in nature. Note that
they all contain an even number of carbon atoms.
Unsaturated fatty acids have lower melting points than the corresponding saturated fatty
acids, and the greater the degree of unsaturation, the lower the melting point. The 18~carbon
saturated fatty acid, stearic acid, melts at 70° C. The 18-carbon fatty acid with one double bond,
oleic acid, melts at 13° C. The 18-carbon fatty acid with two double bonds, linoleic acid, melts at
—5° C; and the 18-carbon fatty acid with three double bonds, linolenic acid, melts at — 10° C.

Unsaturated fatty acids can be subdivided into the following categories.

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Module 2. Biochemistry

1. Monounsaturated, those that contain only one double bond

2. Polyunsaturated, those that contain many double bonds
3. Eicosanoids, which include the prostaglandins, leukotrienes, prostacyclins, and
thromboxanes

Linoleic acid is called the nutritionally essential fatty acid—it is essential for the
complete nutrition of the human body. It cannot be synthesized in the body and must be supplied
from food we eat. Arachidonic and linolenic acids, which were formerly also designated as
essential fatty acids, can be synthesized in the body from linoleic acid. Linoleic acid is found in
large concentrations in corn, cottonseed, peanut, and soybean oils but not in coconut or olive
oils. One of the functions of this essential fatty acid is in the synthesis of prostaglandins.
The absence of the essential fatty acid from the diet of an infant causes loss of weight and
also *eczema. These conditions can be cured by administering corn oil or linseed oil.
Commercial boiled linseed oil should never be used for this purpose because it can contain
litharge, a poisonous lead compound.
The percentages of fatty acids in corn oil, linseed oil, butter, and lard are listed in Table
21-2. The percentages are given as averages because the percent composition of a fat or oil can
vary considerably because of weather conditions or the type of food eaten by the animal or both.
Oleic acid (C17H33COOH) occurs in nature as the cis configuration, as do most naturally
occurring unsaturated fatty acids. The trans form is called elaidic acid.

The need to lower the amount of saturated fat in the diet has been well publicized, and
many individuals as well as commercial establishments have switched to vegetable oils for food

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Module 2. Biochemistry

preparation. Saturated fats are found in meat and dairy products and oils such as palm oil.
Dietary saturated fats increase the blood levels of low-density lipoproteins (LDL), which aid in
the deposition of cholesterol on artery walls.
Partially hydrogenated vegetable oils have been substituted for saturated fats as a way to
lower both cholesterol and LDL levels in the blood. However, partially hydrogenated oils such as
those found in solid vegetable shortening and margarines have an effect opposite to that which
was desired.
Natural vegetable oils contain primarily cis isomers, but partial hydrogenation produces a
mixture of cis and trans isomers. It is the trans isomers that cause many undesirable effects such
as lowering HDL (the good cholesterol) levels, raising LDL (the bad cholesterol) levels, and
raising total cholesterol levels.

Classification of Lipids

Lipids are divided into three main categories: simple, complex, and precursor and derived.

Simple Lipids
Simple lipids are esters of fatty acids. The hydrolysis of a simple lipid may be expressed as

If the hydrolysis of a simple lipid yields three fatty acids and glycerol, the simple lipid is called a
fat or an oil. If the hydrolysis of a simple lipid yields a fatty acid and a high molecular mass
monohydric alcohol, the simple lipid is called a wax.

Complex Lipids

Complex lipids on hydrolysis yield one or more fatty acids, an alcohol, and some other
type of compound. In this category are phospholipids and glycolipids (also called cerebrosides
because they are found in the cerebrum of the brain). Phospholipids undergo hydrolysis as
follows:

Phospholipids are further subdivided into (1) phosphogyljcerides, in which the alcohol is
glycerol, and (2) phosphosphingosides, in which the alcohol is sphingosine.
Glycoljpids (glycosphingolipids) undergo hydrolysis as follows.

Other complex lipids include the sulfolipids and aminolipids as, well as the lipoproteins. ,
Precursor and Derived Lipids

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Module 2. Biochemistry

Precursor lipids are compounds produced when simple and complex lipids undergo
hydrolysis. They include such substances as fatty acids, glycerol, sphingosine, and other
alcohols. Derived lipids are formed by metabolic transformation of fatty acids. They include
ketone bodies, steroids, fatty aldehydes, prostaglandins, and lipid-soluble vitamins.

Fats and Oils

Fats are esters formed by the combination of a fatty acid with one particular alcohol,
glycerol. If one molecule of glycerol reacts with one molecule of stearic acid (a fatty acid),
glyceryl monostearate is formed.

The product of this reaction can react with a second molecule and then with a third molecule of
stearic acid.
Glyceryl tristearate (also called tristearin) is formed by the reaction of one molecule of
glycerol with three molecules of stearic acid. Since stearic acid is a saturated fatty acid, the
product is a fat. As the degree of unsaturation of the fatty acid increases, the melting point
decreases. Fats with a melting point below room temperature are called oils.

The glycerol molecule contains three—OH groups and so combines with three fatty acid
molecules. However, these fatty acids molecules do not have to be the same. Fats and oils can

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Module 2. Biochemistry

contain three different fatty acid molecules, which can be saturated, unsaturated, or some
combination of these.

Exercise -1

Write out the structure for a tryglyceride formed by glycerol and three palmitic acids.

Solution

The formula for palmitic acid is C15H31COOH. Attaching three palmitic acids to glycerol will
produce the following:

Self—test

Write out the structural formula for the triglyceride containing a stearic acid, a myristic acid, and
a capric acid.

Answer:

An example of a mixed trigylcerideⴕ formed from the reaction of glycerol with three
different fatty acid molecules follows. The fatty acids are oleic, stearic, and linoleic.

Oleic acid has a cis configuration around its double bond; linoieic acid has a cis-cis
configuration.

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Module 2. Biochemistry

The preceding formula for a mixed triglyceride can be written in condensed form as
shown in structure (21-1).

or simple as

(21-2)

A more correct representation of the triglyceride structure (21-2) is

indicating the L configuration of most naturally occurring triglycerides, but for simplicity we will
use structure (21-2).

Iodine Number

Unsaturated fats and oils will readily combine with iodine, whereas saturated fats and oils
will not do so readily The more unsaturated the fat or oil, the more iodine it will react with.
The iodine number of a fat or oil is the number of grams of iodine that will react with the
double bonds present in 100g of that fat or oil. The higher the iodine number, the greater the

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Module 2. Biochemistry

degree of unsaturation of the fat or oil. The iodine number of some fats and oils are listed in
Table 21-2.

In general, animal fats have a lower iodine number than vegetable oils. This indicates that
vegetable oils are more unsaturated. This increasing unsaturation is also accompanied by a
change of state: animal fats are solid, and vegetable oils are liquid. Fats have iodine numbers
below 70, oils above 70.
Animal and vegetable oils should not be confused with mineral oil, which is a mixture of
saturated hydrocarbons, or with essential oils, which are volatile aromatic liquids used as flavors
and perfumes.

Exercise -2

Using Table 21-1, decide which fat or oil is the most unsaturated and the least unsaturated.

Solution

Using the iodide number in the table, we find that corn oil is the most unsaturated, with a number
of 116; butter has an iodine number of 26, making it the least unsaturated. .

Self-test

Which fat or oil in Table 21-1 has the most linoleic acid? the most myristic acid?

Answer: Cottonseed or corn oil; butter

Use of Fats in the Body

Fats serve as a fuel in the body, producing more energy per gram than either carbohydrate
or protein. Metabolism of fat produces 9 kcal / g, whereas the metabolism of either carbohydrate
or protein produces 4 kcal/ g.
Fats also serve as a reserve supply of food and energy for the body. If a 70 kg person
stored energy in the form of carbohydrate rather than fat, that person would weigh an additional
55 kg. Fat is stored in the adipose tissue and serves as a protector for the vital organs; that is, fats
surround the vital organs to keep them in place and also act as shock absorbers. Fats in the outer
layers of the body act as heat insulators, helping to keep the body warm in cold weather. Fats act
as electrical insulators and allow rapid propagation of nerve impulses. The fat content of nerve
tissue is particularly high. Fats are a constituent of lipoproteins, which are found in cell
membranes and in the mitochondria and also serve as a means of transporting lipids in the
bloodstream.

Physical Properties

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Module 2. Biochemistry

Pure fats and oils are generally white or yellow solids and liquids, respectively. Pure fats
and oils are also odorless and tasteless. However, over a period of time fats become rancid; they
develop an unpleasant odor and taste.
Fats and oils are insoluble in water but are soluble in such organic liquids as benzene,
acetone, and ether. Fats do not diffuse through a membrane. Fats are lighter than water and have
a greasy feeling. Fats and oils form a temporary emulsion when shaken with water. The emulsion
can be made permanent by the addition of an emulsifying agent such as soap. Fats and oils must
be emulsified by bile in the body before they can be digested.

Chemical Reactions

Hydrolysis

When fats are treated with enzymes, acids, or bases, they hydrolyze to form fatty acids
and glycerol. When tripalmitin (glyceryl tripalmitate) is hydrolyzed, it forms palmitic acid and
glycerol and requires three molecules of water. Recall that in the formation of a fat, water is a
product.
When fats are hydrolyzed to fatty acids and glycerol, the glycerol separates from the fatty
acids and can be drawn off and purified. Glycerol is used both medicinally and industrially.

Saponification

Saponification is the heating of a fat with a strong base such as sodium hydroxide to
produce glycerol and the salt of a fatty acid.

The sodium (or potassium) salt of a fatty acid is called a soap. Reactions and properties of soaps
are discussed later in this chapter.
Hydrogenation

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Module 2. Biochemistry

Fats and oils are similar compounds except that oils are more unsaturated; that is, oils
contain many double bonds. These double bonds can change to single bonds upon the addition of
hydrogen. Vegetable oils can be converted to fats by the addition of hydrogen in the presence of
a catalyst. This process is called hydrogenation. Hydrogenation is used to produce the so-called
vegetable shortenings used in the home. Oleomargarine is prepared by hydrogenating certain fats
and oils, then adding flavoring and coloring agents, plus vitamins A and D. Compounds that give
butter its characteristic flavor are sometimes added.

In actual practice, vegetable oils are not completely hydrogenated. Enough hydrogen is
added to produce a solid at room temperature. If the oil were completely hydrogenated, the solid
fat would be hard and brittle and unsuitable for cooking purposes.
As should be expected, hydrogenation lowers the iodine number to a value within the
range of fats.

Acrolein Test

The acrolein test, which is a test for the presence of glycerol, is sometimes used as a test
for fats and oils, since all fats and oils contain glycerol.
When glycerol is heated to a high temperature, especially in the presence of a
dehydrating agent such as potassium bisulfate (KHSO4), a product called acrolein results.

This substance is easily recognized by its strong, pungent odor. When fats or oils are
heated to a high temperature or are bumed, the disagreeable odor is that of acrolein.

Rancidity

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Module 2. Biochemistry

Fats develop an unpleasant odor and taste when allowed to stand at room temperature for
a short period of time. That is, they become rancid. Rancidity is due to two types of reactions—
hydro1ysis and oxidation.
Oxygen present in the air can oxidize some unsaturated parts of fats and oils. If this
oxidation reaction produces short-chain acids or aldehydes, the fat turns rancid, as evidenced by
a disagreeable odor and taste. Since oxidation, as well as hydrolysis, takes place more rapidly at
higher temperatures, fats and foods containing a high percentage of fats should be stored in a
cool place. Oxidation of fats, especially in hydrogenated vegetable compounds, can be inhibited
by the addition of antioxidants, substances that prevent oxidation. Two naturally occurring
antioxidants are vitamin C and vitamin E.
When butter is allowed to stand at room temperature, hydrolysis takes place between the
fats and the water present in the butter. The products of this hydrolysis are fatty acids and
glycerol. One of the fatty acids produced, butyric acid, has the disagreeable odor that causes one
to say that the butter is rancid. The catalysts necessary for the hydrolysis reaction are produced
by the action of microorganisms present in the air acting on the butter. At room temperature this
reaction proceeds rapidly so that the butter soon turns rancid. This effect can be overcome by
keeping the butter refrigerated and covered.

Soaps

Soaps are produced by the saponification of fats. Soaps are salts of fatty acids. When the
saponifying agent used is sodium hydroxide, a sodium soap is produced. Sodium soaps are bar
soaps. When the saponifying agent used is potassium hydroxide, a potassium soap is produced.
Potassium soaps are soft or liquid soaps.
Soaps can also be produced by the reaction of a fatty acid with an inorganic base,
although this method is much too expensive to be of commercial value.

Various substances can be added to soaps to give them a pleasant color and odor.
Floating soaps contain air bubbles. Germiciclal soaps contain a germicide. Scouring soaps
contain some abrasive. Tincture of green soap is a solution of a potassium soap in alcohol. .
Calcium and magnesium ions present in hard water react with soap to form insoluble calcium
and magnesium soaps.

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The soap “precipitate” is mostly organic and floats to the top rather than sinking to the
bottom as most precipitates do. This precipitated soap is seen as ” the ring around the bathtub.”
More soap is required to produce a_ lather in hard water than in soft water.
Zinc stearate is an insoluble soap used as a dusting powder for infants. It has antiseptic
properties but is irritating to mucous membranes. Zinc undecylenate is used in the treatment of
athlete's foot.
Children who suffer from celiac disease cannot absorb fatty acids from the small
intestine. The unabsorbed fatty acids combine with calcium ions to form insoluble calcium
compounds, or soaps. These calcium compounds are eliminated from the body, and the body will
become deficient in calcium unless additional amounts of this necessary element are given to the
child.

Cleansing Action

Soaps are cleansing agents. Consider a soap molecule such as sodium stearate.

The long-chain aliphatic part is nonpolar, whereas the carboxylate part is polar. A simplified
representation of soap molecule is ------- O, the line representing the nonpolar partand the circle
the polar part.
In general, nonpolar compounds dissolve in nonpolar liquids, and polar compounds
dissolve in polar liquids. If soap is added to a mixture of water and oil and then shaken rapidly,
the nonpolar end of the soap molecule will dissolve in the oil, a nonpolar liquid. At the same
time, the polar end of the soap molecule will dissolve in the water, a ‘polar liquid. The nonpolar
end of the soap molecule is said to be ‘hydrophobic (water-repelling). The polar end is
hydrophilic (water-loving). The carboxylate end of the soap molecule, which is in the water,
yields sodium ions, which are free to move about. Structures such as this are called micelles.
Note that the oil drop has a negative charge because of the negative ends of the soap
molecules sticking out into the water. This negatively charged oil drop will repel all other oil
drops, which will have acquired a like charge. That is, the oil will have become emulsified, with
the soap acting as the emulsifying agent.
This is the manner in which soap cleanses, since most dirt is held on skin and clothing by
a thin layer of grease or oil. Mechanical washing causes the oil or grease to break up into small
drops. the soap then emulsifies that oil or grease, which can then be easily washed away. Soap
also acts as a surfactant; it lowers the surface tension of the water, making emulsification easier.
Soap has little effect as an antibacterial agent. Nurses and surgeons in the operating room
scrub for at least l0 minutes to remove most of the debris, such as keratin and natural fats, from
the skin. A germicidal soap, one that contains a germ—killing compound, usually is used.

Detergents

Detergents (syndets) are synthetic compounds used as cleansing agents. They work like
soaps but are free of several of the disadvantages that soaps have.

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Module 2. Biochemistry

Detergents work as well in hard water as they do in soft water. That is, calcium and
magnesium salts of detergents are soluble and do not precipitate out of solution (as do calcium
and magnesium soaps). Recall that soaps do not work as well in hard water because insoluble
calcium and magnesium salts precipitate out of solution. Detergents are generally neutral
compounds compared with soaps, which are usually alkaline or basic substances. Therefore,
detergents can be used on silks and woolens but soaps cannot. Detergents are used for washing
clothes and also as cleansing agents in toothpastes and toothpowders.
Detergents are sodium salts of long-chain alcohol sulfates. For example, sodium lauryl
sulfate can be prepared by treating lauryl alcohol, a 12—carbon alcohol, with sulfuric acid and
then neutralizing with sodium hydroxide. The reactions are

Note that the detergent, like a soap, has a nonpolar part and a polar part.
Detergents containing straight chains are biodegradable and do not cause water pollution,
whereas those containing branched chains are nonbiodegradable and cause pollution.

Waxes

A wax is a compound produced by the reaction of a fatty acid with a high molecular mass
monohydric alcohol such a myricyl alcohol (C30H61OH) or ceryl alcohol (C26H53OH). Carnauba
wax is largely C25H31COOC30H61, an ester of myricyl alcohol. Beeswax is largely
C15H31COOC30H61, also an ester of myricyl alcohol.
Note that waxes are primarily esters of long-chain fatty acids with an even number of
carbon atoms and long-chain alcohols, also with an even number of carbon atoms. The number
of carbon atoms is usually 26 to 34. The alcohol may also be a steroid such as lanosterol. The
wax thus produced, lanolin, is widely used in cosmetics and ointments.
Waxes are insoluble in water, nonreactive, and flexible; hence, waxes make excellent
protective coatings. Excessive loss of water through the feathers of birds, through the fur of
animals, and through the leaves of plants is prevented by the presence of waxes.
Some of the common waxes are listed in Table 21-3.
Paraffin wax is different from these waxes because it is merely a mixture of hydrocarbons
and is not an ester.

Complex Lipids

Phospholipids

Phospholipids are phosphate esters and can be divided into two categories—
phosphoglycerides and phosphosphingosides—depending on whether the alcohol is glycerol or

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sphingosine. As indicated in Section 21-3, phospholipids also contain a nitrogen compound.

Phospholipids are found in all tissues in the human body, particularly in brain, liver, spinal
tissue, and cell membranes.
Phospholipids also occur in the membranes of all cells. Their peculiar properties are
responsible for passage of various substances into and out of the cells.

Consider a phosphoglyceride whose structure can be represented as

At carbons 1 and 2 of the glycerol there are esters of fatty acids. At carbon 3 there is a phosphate
group, which in turn is bonded to a nitrogen compound. There are many different
phosphoglycerides, depending on the types of fatty acids bonded to the glycerol and also on the
identity of the nitrogen compound bonded to the phosphate group. Most phosphoglycerides have
a saturated fatty acid connected at carbon 1 and an unsaturated fatty acid at carbon 2.
The phosphate group and the nitrogen compound are polar substances, whereas the fatty
acid molecules are nonpolar.
The fatty acid chains, are *hydr0ph0bic—they point away from water. The other end of
the molecule, the one containing the nitrogen compound and phosphoric, acid is *hydrophilic
and dissolves in water. Molecules of this type, with a hydrophobic (nonpolar) and a hydrophilic
(polar) end, are said to be ‘amphipathic. Soaps are amphipathic, as are phospholipids.

Cell Membranes

Cell membranes serve two important functions. (1) They act as a mechanical support to
separate the contents of a cell from its external environment, and (2) a structural support for
certain proteins that serve to transport ions and polar molecules across the membrane. Some of

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Module 2. Biochemistry

these proteins act as ”gates” and "pumps" to move certain materials through the membrane but
exclude others. Other membrane proteins act as "receptor sites” by which molecules outside the
cell can send messages inside the cell. An example of such a protein is the hormone insulin,
which regulates the metabolism of glucose in certain cells but does not cross membranes itself.
Instead, the insulin reacts with the specific receptor protein on the outer surface of the
membrane, and that receptor protein in turn communicates the specific message to the inside of
the cell.
Cell membranes are composed, on the average, of 40 to 50 percent lipids and 50 to 60
percent protein. However, these percentages vary considerably even among the cells of the same
individual, as shown in Table 21-4. In addition, membranes also contain cholesterol and a small
amount of carbohydrate. The cell membrane is relatively fluid, as it must be to account for the
flexibility of the cell and its deformation without disruption of structure.
How do lipids form a membrane, and where do the proteins fit into that membrane?
Recall that phospholipids have a polar end and a nonpolar end. In the marginal diagram, the long
lines represent the nonpolar (hydrophobic) end, the fatty acid chains, whereas the circles
represent the polar (hydrophilic) end, the end that dissolves in water. Such amphipathic
molecules can form a bilayer, as shown at the left.
Such a simple model is not satisfactory for cell membranes because this type of bilayer
would be highly impermeable to ions and most polar molecules, which cannot pass through the
center of such a system. The current theory of cell membranes involves a phospholipid bilayer in
which are embedded proteins, as shown in Figure 21-2.
In this type of membrane, called the fluid mosaic model, some proteins are embedded in
the surface of the membrane, others are embedded in the center, and still others provide channels
all the way through to transport polar molecules and ions through the membrane. The proteins
are believed to be mobile and to move through the bilayer, as well as across its surface.

Phosphoglycerides

One category of phospholipid is the phosphoglycerides, whose general structure is shown

below. Phosphoglycerides can in turn be subdivided into several types, depending on the
nitrogen compbund present. Among these are the lecithins and the cephalins.

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Module 2. Biochemistry

Lecithins

Lecithins, now called phosphatidylcholines, are compounds that are particularly

important in the metabolism of fats by the liver. In lecithins, the nitrogen compound is choline,
an alcohol. Choline is an example of a quaternary ammonium compound.

A typical formula for a lecithin (phosphatidylcholine) is shown as structure (21-3). In

most lecithins, the fatty acid at carbon 1 of the glycerol is saturated, whereas the fatty acid at
carbon 2 is unsaturated. The carbon marked with an asterisk is chiral, indicating optical activity.
Naturally occurring lecithins have the L form.

Lecithins are insoluble in water but are good emulsifying agents. They are also good
sources of phosphoric acid, which is needed for the synthesis of new tissue. Lecithin is abundant
in egg yolk and soybeans. It is used commercially as an emulsifying agent in dairy products and
in the manufacture of mayonnaise.
Fats are partly converted to lecithins in the body and are transported as lecithins from one
part of the body to another. Lecithins are widely distributed in all cells and have both metabolic
and structural functions in membranes.
Dipalmitoyl lecithin (lecithin in which the two fatty acids are palrnitic acid) is a very
good surface active agent (see page 169). It prevents adherence on the inner surfaces of the
lungs. The absence of dipalmitoyl lecithin from the lungs of premature infants causes respiratory
distress syndrome.
Removal of one molecule of fatty acid from lecithin produces lysolecithin.The removal
of this molecule of fatty. acid is catalyzed by the enzyme lecithinase A, which is found in the
venom of poisonous snakes. The venom is poisonous because it produces lysolecithin, which in
turn causes hemolysis——the destruction of the red blood cells.

Cephalins

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Module 2. Biochemistry

Cephalins (21-4) are similar to lecithins except that another nitrogen compound,
ethanolamine, is present instead of choline. The newer name for this compound is
phosphatidylethanolamine.

Cephalins are important in the clotting of the blood and also are sources of phosphoric
acid for the formation of new tissue.
Similar compounds, phosphatidylserine and phosphatidylinositol, are abun- dant in brain
tissue. In these compounds, serine and inositol, respectively, occur in place of the choline or
ethanolamine of (21-3) and (21-4).

Plasmalogens

Plasmalogens structurally resemble lecithin and cephalin but have an unsaturated ether at
carbon 1 instead of an ester. The fatty acid at carbon 2 of the glycerol is usually unsaturated.
Plasmalogens constitute up to 10 percent of the phospholipids found in membranes of brain and
muscle cells. The structure of a plasmalogen is

Phosphosphingosides

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Module 2. Biochemistry

Phosphosphingosides, also called sphingolipids, differ from phosphoglycerides in that

they contain the alcohol sphingosine in place of glycerol. One particular type of sphingolipid,
called sphingomyelin, is present in large amounts in brain and nerve tissue. The general formula
for a sphingolipid, is given below and the structural formula for sphingomyelin is structure (21-
5).
In Niemann-Pick disease, a disease of infancy or early Childhood, sphingomyelins
accumulate in the brain, liver, and spleen. Accumulation of the sphingomyelins results in mental
retardation and early death. It is caused by the lack ofa specific enzyme, sphingomyelinase.

Note that the fatty acid in sphingomyelin is bonded to an —NH2 group rather than to an -
OH group as in phosphoglycerides.
In multiple sclerosis, a demyelinating process, there is a loss of phospholipids and
sphingolipids. An increased phosphate level occurs in the cerebrospinal fluid.
GIycolipids

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Glycolipids are similar to sphingomyelins except that they contain a carbohydrate, often
galactose, in place of the choline and phosphoric acid. The general structure for a glycolipid is

As in sphingomyelins, the fatty acid is bonded to an —NH2 group on the sphingosine

molecule.
Glycolipids produce no phosphoric acid on hydrolysis because they do not contain this
compound. Glycolipids are also called cerebrosides because they are found in large amounts in
the brain tissue.
Among the glycolipids are kerasin, cerebron, nervon, oxynervon, and the gangliosides.
These compounds differ primarily in the identity of the fatty acid attached to the sphingosine.
In Gaucher's disease glycolipids accumulate in the brain and cause severe mental
retardation and death by age 3. Juvenile and adult forms of this disease are characterized by
enlarged spleen and kidneys, hemorrhaging, mild anemia, and fragile bones. This disease is
caused by the lack of a specific enzyme, ẞ-glucosidase.
In the absence of a particular enzyme, hexosaminidase A, glycolipids accumulate in the
tissues of the brain and eyes. This effect, called Tay-Sachs disease, is usually fatal to infants
before they reach age 2.

Derived Lipids

Eicosanoids

The eicosanoids are a biologically active group of compounds derived from arachidonic
acid. They are extremely potent compounds with a variety of actions, as will be discussed in the
following paragraphs. Among the eicosanoids are the prostaglandins, the thromboxanes,
prostacyclin, and the leukotrienes.

The Prostaglandins

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Module 2. Biochemistry

The prostaglandins consist of 20-carbon unsaturated fatty acids containing a five

membered ring and two side chains. One side chain has seven carbon atoms and ends with an
acid group (COOH). The other chain contains eight carbon atoms with an —OH group on the
third carbon from the ring (see structure given). The E series of prostaglandins has, in addition to
four chiral carbon atoms, a trans-configuration.
Prostaglandins are derived from arachidonic acid, which is formed from the nutritionally
essential fatty acid linoleic acid. The structures of arachidonic acid and prostaglandin E 1 (PGE1)
are

The abbreviation PGE1 refers to prostaglandin E with one double bond. Likewise, PGE2
refers to prostaglandin E with two double bonds.
Prostaglandins have been isolated from most mammalian tissues, including the male and
female reproductive systems, liver, kidneys, pancreas, heart, lungs, brain, and intestines. The
richest source of prostaglandins is human seminal fluid.
Prostaglandins have a wide range of physiologic effects. They seem to be involved in the
body's natural defenses against all forms of change including those induced by chemical,
mechanical, physiologic, and pathologic stimuli. Aspirin and other anti-inflammatory drugs
appear to partially operate by inhibiting prostaglandin synthesis. Prostaglandins are involved at
the cellular level in regulating many body functions, including gastric acid secretion, contraction
and relaxation of smooth muscles, inflammation and vascular permeability, body temperature,
and blood platelet aggregation. Prostaglandins stimulate steroid production by the adrenal glands
and also stimulate the release of insulin from the pancreas.
Prostaglandins markedly stimulate the movement of calcium ions from bone. Excessive
production of prostaglandins by malignant tissue may provide a partial answer for the
*hypercalcemia and *osteolysis observed in patients afflicted with such a condition.
Prostaglandins have also been used clinically to induce abortion or to induce labor in a
term prognancy, to treat hypertension, to relieve bronchial asthma, and to heal peptic ulcers.
Prostaglandins increase cyclic adenosine monophosphate (cAMP) (see page 576) in
blood platelets, thyroid, corpus luteum, adenohypophysis, and lungs but decrease CAMP in
adipose tissue.
Prostaglandin E1 (PGE1) is now used to strengthen babies born with cyanotic congenital
heart disease (”blue babies") to prepare them for corrective surgery.

Prostacyclin and Thromboxanes

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Module 2. Biochemistry

Prostacyclin is so called because it contains a second five»membered ring in addition to the ring
found in prostaglandins. Thromboxanes have a cyclopentane ring interrupted by an oxygen atom.
The structures of prostacyclin and thromboxane B2 (TXB2) are shown below.

Prostacyclin is a potent inhibitor of platelet aggregation and is a powerful vasodilator.

Thromboxanes have an effect opposite to that of prostacyclin. They are potent
aggregators of blood platelets and haveta profound contractive effect on a variety of smooth
muscles.
Thromboxanes function in conjunction with prostacyclin in maintaining a healthy
vascular system. Both substances exert their influence by regulating the production of cAMP,
with the thromboxanes acting as inhibitors and prostacyclin as a stimulator of cAMP production.
Leukotrienes Leukotrienes are another group of eicosanoids derived from arachidonic acid. The
tri refers to three alternate setgof double bonds in the molecule. One of this group, leukotriene C,
is involved in the ‘body's allergic responses. It constricts air passages to the bronchi during an
asthma attack. The structure of leukotriene C is

Steroids

Steroids are high molecular mass tetracyolic (four-ring) compounds. Those containing
one or more —OH groups and no C=O groups are called sterols. The most common sterol is
cholesterol, which is found in animal fats but not in plant fats. Cholesterol is found in all animal
tissues, particularly in brain and nervous tissue, in the bloodstream, and as gallstones.
Cholesterol aids in the absorption of fatty acids from the small intestine.

Most of the body's cholesterol is derived or synthesized from other substances such as
carbohydrates and proteins, as well as from fats. The rest comes from the diet (see Table 21-5).

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Module 2. Biochemistry

Atherosclerosis, a form of arteriosclerosis, results from the deposition of excess lipids,

primarily triglycerides and cholesterol, from the bloodstream (see Figure 21-3). Of these two,
cholesterol poses a greater threat to the well-being of a person, although excess triglycerides also
present a significant risk. One way of combating heart disease and atherosclerosis is to reduce the
concentration of lipids in the bloodstream—either by reducing lipid intake or by the use of
antihyperlipidemic drugs, those that tend to reduce blood lipid levels. It has been found that
certain unsaturated fish and vegetable oils, when substituted for saturated fats, lower the serum
cholesterol level.
Cholesterol levels in humans should be in the range of 200 to 220 mg/dL, with slightly
higher levels being normal for older individuals. Elevated cholesterol levels should be controlled,
usually by diet. In extreme cases, cholesterol-lowering drugs such as pravastatin or lovastatin
may be prescribed.
Cholesterol does not occur in plants.
Ergosterol is a sterol similar to cholesterol. When ergosterol is irradiated (exposed to
radiation) with ultraviolet light, one of the products formed is calciferol (vitamin D2). Other
steroids include bile salts, the sex hormones, and the hormones of the adrenal cortex. The
similarities of the structure of some of these steroids are indicated in the following structures:

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Module 2. Biochemistry

Anabolic Steroids

Anabolic steroids are hormones that control the synthesis of larger molecules from
smaller ones. Athletes have used these substances (even though they are illegal) to increase
muscle mass and, hence, body strength. An example of such an anabolic steroid is the male
hormone testosterone. While it does increase muscle mass, it has several undesirable side effects.
In men these side effects include testicular atrophy, impotence, hypercholesterolernia, breast
growth, and liver cancer. Women using anabolic steroids will develop larger muscles and greater
strength at the expense of increased masculinity, formation of a greater amount of body hair,
deepening of the voice, and menstrual irregularities. Another drawback of the use of such
anabolic steroids is that they cannot be taken orally; they must be injected. It is standard practice
today during athletic competitions to routinely test an athlete's urine for the presence of these
illegal substances.

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Module 2. Biochemistry

Name: _________________________________________________________
Course and Year _________________________________________________

Evaluation
Directions: Answer the following questions. Use another sheet if needed. Detach this
portion and attach your answer sheets here.

1. Compare the properties of lipids with those of carbohydrates.

2. What are simple lipids? complex lipids? precursor lipids? Give an example of each
3. What is a fatty acid? What is the difference between saturated and unsaturated fatty
acids?
4. What is the difference between a fat and an oil? Between a fat and a wax?
5. Do fatty acids in the body contain (usually) an even or an odd number of carbon atoms?
Why?
6. Which is the nutritionally essential fatty acid? Why is it important?
7. What determines the iodine number of a fat or oil? Which have higher iodine numbers,
fats or oils?
8. Draw the structure of the compound formed by the reaction of one molecule of glycerol
with three molecules of palmitic acid; one molecule each of stearic, palmitic, and oleic
acid.
9. What is the difference between an unsaturated fatty acid and a polyunsaturated one?
10. Compare soaps and detergents on the basis of structure; on their reactions with hard
water.
11. What causes rancidity in fat or oil? How can it be prevented?
12. Which types of soap are germicidal or have germicidal properties? Explain.
13. List the types of phospholipids and give an example of each.
14. What causes celiac disease?
15. List three phosphoglycerides and give a function of each.
16. What is meant by the term amphipathic?
17. What causes Gaucher’s disease? Neiman-Pick disease? respiratory distress syndrome?
Tay-Sachs disease?
18. What causes atherosclerosis and what might be done to prevent it?
19. Name several steroids in the body and indicate the function of each.
20. What purpose does cholesterol serve in the body? What can be done to reduce serum
cholesterol?
21. Compare the terms hydrophobic and hydrophilic.
22. Are Waxes important biologically? Why or why not?
23. How does the fluid mosaic model account for the movement of polar substances through
a membrane?
24. What is prostacyclin? PGE1? thromboxane? What function does each serve?
25. From what compound are the eicosanoids derived? List several eicosanoids.

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