LIPIDS

Nomenclature of fatty acids and acylglycerols

There are three naming systems used for fatty acids:
1. Delta nomenclature
2. Omega nomenclature
3. Common names
The omega nomenclature and common names are used more in the field of nutrition than the
delta nomenclature when describing specific fatty acids.
1. Delta Nomenclature
For delta nomenclature you need to know 3 things:
1. Number of carbons in the fatty acid
2. Number of double bonds

3. Number of carbons from the carboxylic acid (alpha) end to the first carbon in the double
bond(s)

Let’s consider the example in the figure below.

1. Number of carbons in the fatty acid = 18

2. Number of double bonds = 1
3. Number of carbons from the carboxylic acid end to the first carbon in the double bond = 9
This is then written as shown in Figure 2.331.
2. Omega Nomenclature
The omega nomenclature is almost exactly the same as the delta nomenclature, the only
differences being:
• Carbons are counted from the methyl (omega) end instead of the carboxylic acid end
• The omega symbol is used instead of the delta symbol
For omega nomenclature you need to know 3 things:
1. Number of carbons in the fatty acid
2. Number of double bonds
3. Number of carbons from the methyl end (aka Omega end) to the first carbon in the double
bond closest to the methyl end
We will again consider the same fatty acid.

Figure 2.332 Omega Nomenclature

1. Number of carbons in the fatty acid = 18

2. Number of double bonds = 1
3. Number of carbons from the methyl (aka omega) end to the first carbon in the double bond
closest to the methyl end = 9
If it is a saturated fatty acid, then the omega nomenclature is not added to the end of the name.
If it is an 18-carbon saturated fatty acid, then it would be named 18:0.
This is written as shown in figure 2.332. Instead of an omega prefix, the prefix n- (i.e. n-3) is
also commonly used.
3. Common Names
The common names of fatty acids are something that, for the most part, have to be
learned/memorized. The common name of the fatty acid we have been naming in this section
is oleic acid.

Figure 2.333 Oleic acid

However, it can also be called oleate. The only difference is that, instead of a carboxylic acid
on the end of the fatty acid, it has been ionized to form a salt (shown below). This is what the
-ate ending indicates and the two names are used interchangeably.

Figure 2.334 Oleate

The table below gives the common names and food sources of some common fatty acids.
Omega Name Common Name

4:0 Butyric Acid

12:0 Lauric Acid

14:0 Myristic Acid

16:0 Palmitic acid

18:0 Stearic Acid

20:0 Arachidic Acid

24:0 Lignoceric Acid

18:1 (n-9) Oleic Acid

18:2 (n-6) Linoleic Acid

18:3 (n-3) Alpha-linolenic Acid

20:4 (n-6) Arachidonic Acid

20:5 (n-3) Eicosapentanoic Acid

22:6 (n-3) Docosahexanoic Acid

Food Sources of Fatty Acids
After going through this wide array of fatty acids, you may be wondering where they are found
in nature. The figure below shows the fatty acid composition of certain oils and oil-based foods.
As you can see, most foods contain a mixture of fatty acids. Stick margarine is the only product
in the figure that contains an appreciable amount of trans fatty acids. Corn, walnut, and soybean
are rich sources of n-6 polyunsaturated fatty acids, while flax seed is fairly unique among plants
in that it is a good source of n-3 polyunsaturated fatty acids. Canola and olive oil are rich
sources of monounsaturated fatty acids. Lard, palm oil, butter and coconut oil all contain a
significant amount of saturated fatty acids.
Properties of Lipids
• Lipids may be either liquids or non-crystalline solids at room temperature.
• Pure fats and oils are colourless, odorless, and tasteless.
• They are energy rich organic molecules
• Insoluble in water
• Soluble in organic solvents like alcohol, chloroform, acetone, benzene etc.
• No ionic charges
• Solid triglycerols (Fats) have high proportions of saturated fatty acids.
• Liquid triglycerols (Oils) have high proportions of unsaturated fatty acids.

1. Hydrolysis of triglycerols
Triglycerols like any other esters react with water to form their carboxylic acid and alcohol– a
process known as hydrolysis.
2. Saponification:
Triacylglycerols may be hydrolysed by several procedures, the most common of which utilizes
alkali or enzymes called lipases. Alkaline hydrolysis is termed saponification because one of
the products of the hydrolysis is a soap, generally sodium or potassium salts of fatty acids.
3. Hydrogenation
The carbon-carbon double bonds in unsaturated fatty acids can be hydrogenated by reacting
with hydrogen to produce saturated fatty acids.
4. Halogenation
Unsaturated fatty acids, whether they are free or combined as esters in fats and oils, react with
halogens by addition at the double bond(s). The reaction results in the decolorization of the
halogen solution
5. Rancidity:
The term rancid is applied to any fat or oil that develops a disagreeable odour. Hydrolysis and
oxidation reactions are responsible for causing rancidity. Oxidative rancidity occurs in
triacylglycerols containing unsaturated fatty acids.

Lipid Structure
• Lipids are made of the elements Carbon, Hydrogen and Oxygen, but have a much lower
proportion of water than other molecules such as carbohydrates. Unlike polysaccharides
and proteins, lipids are not polymers—they lack a repeating monomeric unit.
• They are made from two molecules: Glycerol and Fatty Acids.
• A glycerol molecule is made up from three carbon atoms with a hydroxyl group attached
to it and hydrogen atoms occupying the remaining positions.
• Fatty acids consist of an acid group at one end of the molecule and a hydrocarbon chain,
which is usually denoted by the letter ‘R’.
• They may be saturated or unsaturated.
• A fatty acid is saturated if every possible bond is made with a Hydrogen atom, such that
there exist no C=C bonds.
• Saturated fatty acids on the other hand do contain C=C bonds. Monounsaturated fatty acids
have one C=C bond, and polyunsaturated have more than one C=C bond.

Structure of Triglycerides
• Triglycerides are lipids consisting of one glycerol molecule bonded with three fatty acid
molecules.
• The bonds between the molecules are covalent and are called Ester bonds.
• They are formed during a condensation reaction.
• The charges are evenly distributed around the molecule so hydrogen bonds to not form with
water molecules making them insoluble in water.
Classification of Lipids
Lipids can be classified according to their hydrolysis products and according to similarities in
their molecular structures. Three major subclasses are recognized:
1. Simple lipids
(a) Fats and oils which yield fatty acids and glycerol upon hydrolysis.
(b) Waxes, which yield fatty acids and long-chain alcohols upon hydrolysis.

Fats and Oils

Both types of compounds are called triacylglycerols because they are esters composed of three
fatty acids joined to glycerol, a trihydroxy alcohol. The difference is on the basis of their
physical states at room temperature. It is customary to call a lipid a fat if it is solid at 25°C, and
an oil if it is a liquid at the same temperature. These differences in melting points reflect
differences in the degree of unsaturation of the constituent fatty acids.
Waxes
A wax is an ester of a long-chain alcohol (usually mono-hydroxy) and a fatty acid.
The acids and alcohols normally found in waxes have chains of the order of 12-34 carbon atoms
in length.

2. Compound lipids
(a) Phospholipids, which yield fatty acids, glycerol, amino alcohol sphingosine, phosphoric
acid and a nitrogen-containing alcohol upon hydrolysis. They may be glycerophospholipids
or sphingophospholipid depending upon the alcohol group present (glycerol or sphingosine).
(b) Glycolipids, which yield fatty acids, sphingosine or glycerol, and a carbo hydrate upon
hydrolysis. They may also be glyceroglycolipids or sphingoglycolipid depending upon the
alcohol group present (glycerol or sphingosine).
3. Derived lipids:
Hydrolysis product of simple and compound lipids is called derived lipids. They include fatty
acid, glycerol, sphingosine and steroid derivatives. Steroid derivatives are phenanthrene
structure that are quite different from lipids made up of fatty acids.

Functions of lipids
• Energy storage, mobilization, and utilization
• Prostaglandin, cytokine synthesis
• Cell differentiation and growth
• Cell membrane structure, myelination
• Signal transmission
• Hormone synthesis
• Bile acid synthesis
Phospholipids
• These are made up of fatty acid, glycerol or other alcohol, phosphoric acid and
nitrogenous base.
• Phospholipids are the major lipid constituents of cell membranes.
• Like fatty acids, phospholipids are amphipathic in nature, i.e. each has a hydrophilic
or polar head (phosphate group) and a long hydrophobic tail (containing two fatty acid
chains)
Diagrammatic representation of amphipathic phospholipid
Classification of Phospholipids
There are two classes of phospholipids
1. Glycerophospholipids or phosphoglycerides, that contain glycerol as the alcohol.
2. Sphingophospholipids that contain sphingosine as the alcohol.
Glycolipids (Glycosphingolipids)
• Glycolipids as their name implies, are sugar containing lipids. Glycolipids consist of
alcohol sphingosine.
• The amino group of sphingosine is esterified by a fatty acid and one or more sugar units
are attached to the hydroxyl group of sphingosine.
• Glycolipids are widely distributed in every tissue of the body, particularly in nervous tissue
such as brain.
Classification of Glycolipids
Four classes of glycolipids have been distinguished:
1. Cerebrosides
2. Sulfatides
3. Globosides
4. Gangliosides.

Eicosanoids
• Prostaglandins and the related compounds thromboxanes and leukotriens, are
collectively known as eicosanoids.
• Eicosanoids are synthesized from arachidonic acid, A polyunsaturated fatty acid
containing 20-carbon atoms from which they take their general name (Greek: eikosi means
twenty).
Prostaglandins
• Prostaglandins are a group of 20-carbon compounds derived from arachidonic acid. They
derive their name from the tissue in which they were first recognized (the prostate gland)
but they are now known to be present in almost all tissues.
• Chemically, the prostaglandins are derivatives of the hypothetical parent compound
prostanoic acid, having cyclopentane (5 carbon) ring and two aliphatic side chains R1 and
R2.
• Prostanoic acid does not occur naturally but is regarded as the parent compound of the
prostaglandins and thromboxanes for the purpose of classification and carbon numbering.

Lipoproteins
• Lipoproteins are large water-soluble complexes formed by a combination of lipid and
protein that transport insoluble lipids through the blood between different organs and
tissues.
• Lipoproteins consist of a lipid core containing nonpolar triacylglycerol and cholesterol
ester surrounded by a single layer of amphipathic phospholipids and free cholesterol
molecules with some proteins, (apoprotein)
• The protein components are referred to as an apoprotein or apolipoprotein. There are four
major types of apolipoproteins designated by letters A, B, C and E with subgroups given in
Roman numerals I, II, III, etc.

Structure of lipoprotein where, TG: triacylglycerol, CE: cholesterol ester

Classes of Lipoproteins
Lipoproteins have been categorized into four major classes according to their physical and
chemical properties. These are :
1. Chylomicrons
2. Very low density lipoproteins (VLDL)
3. Low density lipoprotein (LDL)
4. High density lipoprotein (HDL).
• These lipoprotein complexes contain different proportions of lipids and proteins. The
density of these lipoproteins is inversely proportional to triacylglycerol content. As the
density increases, the diameter of the particle decreases as shown in
 • Chylomicrons containing about 1 percent protein and 99 percent triacylglycerol have the
lowest density.
• While HDL containing 50 percent of protein and 50 percent of lipid have the highest
density.
• Triacylglycerol is the predominant lipid in chylomicrons and VLDL. Cholesterol is the
predominant lipid in LDL, whereas phospholipid is the predominant lipid in HDL.

Percentage of three major lipid classes, i.e. triacylglycerol, cholesterol and phospholipids
present in lipoproteins

Steroid Derivatives
Sterols functions
-While cholesterol (CHO) is the major sterol of vertebrates, ergosterol (ERG) plays a key role
in fungi.
-Plants usually possess more complex sterol compositions. Stigmasterol (STI) and sitosterol
(SIT), two 24-ethyl sterols, are major constituents of the sterol profiles of plant species. They
are involved in the embryonic growth of plants.
-Hopanoids such as bacteriohopanetetrol (BHT) are sterol surrogates of primitive bacteria
(archebacteria, cyanobacteria, etc.) that develop in very extreme conditions such as hot springs,
very high deep-sea pressure, highly saline water, and ice-covered lakes. They are considered
as good markers of geological samples containing organic matter.
Sterols are critical for the formation of liquid-ordered membrane states (lipid “rafts”) that are
supposed to play an important role in fundamental biological processes such as signal
transduction, cellular sorting, cytoskeleton reorganization, asymmetric growth, and infectious
diseases. They maintain membranes in a state of fluidity adequate for function. For instance,
phytosterols have been recently shown to increase membrane cohesion in order to maintain
plant membranes in a state of dynamics less sensitive to temperature shocks.
Cholesterol
• It is a major structural constituent of the cell membranes and plasma lipoproteins.
• Cholesterol serves as the precursor for a variety of biologically important products,
including:
1. Steroid hormones: Cholesterol is the precursor of the five steroid hormones, e.g.
i. Progesterones
ii. Glucocorticoids
iii. Mineralocorticoids
iv. Androgens (male sex hormones)
vi. Estrogen (female sex hormones).

2. Bile acids: Bile acids, derived from cholesterol, act as a detergent in the intestine,
emulsifying dietary fats to make them readily accessible to enzyme lipase.
3. Vitamin D: It is derived from cholesterol and is essential in calcium and phosphate
metabolism. Sterols, the third lipid class, also regulate biological processes and sustain the
domain structure of cell membranes where they are considered as membrane reinforcers

The structure of cholesterol

• Cholesterol is the major sterol in animal tissues. Sterols are a class of steroids containing
hydroxyl group.
• It consists of steroid nucleus namely phenanthrene containing 19-carbon atoms
• It consists of methyl side chains at position C10 and C13 which are shown as single bonds.
• Cholesterol, a 27-carbon compound, has an 8-carbon side chain attached to the D ring at
C17 and a hydroxyl group attached to C3 of the A ring, with one double bond between
carbon atoms 5 and 6.
 The steroid nucleus, phenanthrene (ring A, B and C), to which cyclopentane D ring is
attached

• Cholesterol is amphipathic, with a polar head the hydroxyl group at C3 and a nonpolar, the
steroid nucleus and hydrocarbon side chain at C17.
• Most of the cholesterol in the body exists as a cholesterol ester, with a fatty acid attached to
the hydroxyl group at C3.
• Cholesterol is widely distributed in all the cells of the body but particularly in nervous tissue.

Cholesterol is a waxy substance. It’s not inherently “bad.” In fact, your body needs it to build
cells. But too much cholesterol can pose a problem.
Cholesterol comes from two sources. Your liver makes all the cholesterol you need. The
remainder of the cholesterol in your body comes from foods derived from animals. For
example, meat, poultry and full-fat dairy products all contain cholesterol, called dietary
cholesterol.
Those same foods are high in saturated and trans fats. Those fats cause your liver to make more
cholesterol than it otherwise would. For some people, this added production means they go
from a normal cholesterol level to one that’s unhealthy.
Some tropical oils – such as palm oil, palm kernel oil and coconut oil – can also trigger your
liver to make more cholesterol. These oils are often found in baked goods.
Cholesterol circulates in the blood. As the amount of cholesterol in your blood increases, so
does the risk to your health. That’s why it’s important to have your cholesterol tested, so you
can know your levels.
There are two types of cholesterol: LDL cholesterol, which is bad, and HDL, which is good.
Too much of the bad kind, or not enough of the good kind, increases the risk that cholesterol
will slowly build up in the inner walls of the arteries that feed the heart and brain.
Cholesterol is essential for making the cell membrane and cell structures and is vital for
synthesis of hormones, vitamin D and other substances. Cell membrane synthesis – Cholesterol
helps to regulate membrane fluidity over the range of physiological temperatures

Disorders associated with cholesterol

Two cholesterol disorders are hyperlipidemia, and hypolipidemia.
Hyperlipidemia means you have an unusually high level of fat (lipids) in your blood. This
puts you at risk for many health problems, including heart attack and stroke. It is sometimes
called high blood cholesterol.
Hypolipidemia means you have an unusually low level of fat in your blood. It is sometimes
called low blood cholesterol.

What causes cholesterol disorders?

High blood cholesterol
When you eat meat, eggs, and dairy products – any food that comes from an animal – you are
adding cholesterol to your blood. A diet high in saturated fat and cholesterol is just one thing
that may cause high blood cholesterol. Other factors include:
• Being overweight
• Not exercising regularly
• Overuse of alcohol
• Family history. High blood cholesterol can be an inherited condition.
• Age and sex. As you age, your LDL ("bad cholesterol") level rises. After age 55, women
have higher LDL levels than men.
• Diseases like diabetes, hypothyroidism, Cushing's syndrome, and kidney failure
• Medications like birth control pills, beta-blockers, estrogen, corticosteroids, and certain
diuretics
Low blood cholesterol
Hypolipidemia can be caused by several things:
• Hypothyroidism
• Anemia (a low amount of red blood cells)
• Malnutrition, or a lack of food
• Liver disease
• The body being unable to absorb food (malabsorption)
• Rare genetic conditions, such as hypobetalipoproteinemia and abetalipoproteinemia
• Tangier disease
How does my doctor tell if I have a cholesterol disorder?
Blood cholesterol tests tell how much fat is in your blood. A total cholesterol level test
measures both your LDL (low-density lipoprotein, or "bad cholesterol,") and HDL (high-
density lipoprotein, or "good cholesterol") levels in milligrams per deciliter (mg/dL).
Normal total cholesterol levels are below 200 mg/dL. HDL levels should be above 40 mg/dL.
Triglyceride levels also should be below 200 mg/dL.
How are cholesterol disorders treated?
1. High blood cholesterol
-Lifestyle
-To reduce cholesterol in your blood:
• Follow a healthful diet, eating foods low in total fat and saturated fat
• Maintain a healthful weight
• Exercise at least three times a week, for 30 minutes at a stretch
• Have your total cholesterol rechecked in one to two years if:
o Your cholesterol reading was above 240 mg/dL
o You have other risk factors for heart disease, such as high blood pressure,
diabetes, or being overweight
Medications
• Statins lower LDL ("bad cholesterol") levels
• Bile Acid Sequestrants (seh-KWES-trants) are sometimes prescribed with statins, and
help lower LDL cholesterol levels
• Nicotinic (Nick-o-tin-ick) Acid lowers LDL cholesterol and triglycerides, and raises
HDL ("good" cholesterol) levels
• Fibrates lower triglyceride levels, and may increase HDL levels
• Ezetimibe blocks cholesterol absorption, and lowers LDL cholesterol
2. Low blood cholesterol
Treatment focuses on the root causes of hypolipidemia

Pharmaceutical significance of lipids

One of the most important functions of lipids is the role they play in cell membrane structure
and metabolic processes, especially as cell membrane transport agents and precursors of
signaling eicosanoids. Several lipids, when highly purified and refined to meet pharmaceutical
specifications, are used to act as fillers, binders, lubricants, solubilizers, emulsifiers, and
emollients in a variety of delivery forms including tablets, capsules, suppositories, emulsions
(enteral/parenteral), ointments, creams, and lotions. Several lipids and lipid soluble ingredients,
including triglycerides, modified fats, phospholipids, oil soluble micronutrients, and waxes are
widely used in many cosmetic applications. Typical applications of lipids in cosmetics include
emollients, skin care and treatment, hair care, make-up, and decorative products. Basically the
quality of oils and fats and other lipids used in both the cosmetics and pharmaceutical industries
has to be equal or superior to that of edible products.