Lipid Chemistry

Lipid Chemistry
Lipids are hydrophobic organic compounds which are insoluble in water but
soluble in fat solvents (non-polar solvents) e.g. benzene, chloroform, and acetone.

The main biological functions of lipids include:

1. Provide the body with energy (9.3 kcal/gm).

2. Acting as structural components of cell membranes (phospholipids and
cholesterol).
3. Serve as thermal insulators.
4. Serve as precursors for hormones (steroid hormones).
5. They dissolve the vitamins, which are fat-soluble and assist their digestion.

Classification:

Lipids are classified into:

1. Simple lipids.
2. Compound (conjugated) lipids.
3. Derived lipids.

1
 Lipid Chemistry

Fatty Acids
• Fatty acids are long-chain hydrocarbon molecules containing a carboxyl
group at one end.
• The numbering of carbons in fatty acids begins with the carbon of the
carboxylate group.

Classification of fatty acids:

I. FA are classified according to presence or absence of double bonds, into:
1. Saturated fatty acids:
- Fatty acids that contain no double bonds, e.g palmitic acid (16 C) and
stearic acid (18 C).
- Palmitic acid is the commonest fatty acid in human tissues.
- Sources:
• Animal sources: whole milk, whole milk dairy products (cream,
cheese, butter) and fatty meats.
• Plant sources: coconut oil and palm oil.
- Biomedical importance
Increased intake of saturated fatty acids may lead to an increase in plasma
cholesterol levels and incidence of coronary heart disease.
2. Unsaturated fatty acids (USFA )

They contain one or more double bonds and further classified according to:

a) The number of double bonds into:

- Monoenoic acids: contain only one double bond, e.g. oleic acid.

2
 Lipid Chemistry

- Polyenoic acids (polyunsaturated fatty acids) (PUFAs): contain more

than one double bond per molecule, e.g. α-Linolenic acid (ω3,18:3),
Linoleic acid (ω6, 18:2), and Arachidonic acid (ω6, 20:4).
b) The orientation of hydrogen atoms around the double bond into:
- Cis type:
• Both hydrogen atoms are on the same side.
• They are liquid at room temperature.
• Sources: Fatty acids with cis type are typical in natural foods. Nuts,
plant oils (olive, sunflower, cottonseed, corn, and flaxseed), and fish
oil are rich sources.
- Trans type:
• Both hydrogen atoms are on opposite sides.
• They are solid at room temperature.
• Sources: Most of trans fatty acids are formed during hydrogenation
of vegetable oils (during manufacture of margarine). They are
present in many commercial baked foods as cakes and cookies,
frozen pizza and most fried foods.

3
 Lipid Chemistry

Biomedical importance of unsaturated fatty acids:

- Intake of cis USFAs may reduce the incidence of atherosclerosis and

cardiovascular diseases as they:
• Lower blood pressure.
• Lower plasma cholesterol levels.
• Lower plasma triacylglycerol levels.
• Decrease tendency to intravascular thrombosis.
- Increase intake of Trans fatty acids may lead to hypercholesterolemia and
atherosclerosis.
II. Nutritional Classification of Fatty Acids:
a) Essential Fatty Acids:
- They are not synthesized in our body, so it is essential to take them in diet.
- They include α linolenic and linoleic acids.
- Arachidonic acid is synthesized in our bodies from linoleic but in its
absence, arachidonic acid might be considered as an essential fatty acid.
- Deficiency of essential fatty acids produces: Dermatitis in infants, fatty
liver, growth retardation as well as defective sperms, brain and retina.
a) Non-Essential Fatty Acids:
- They include all other fatty acids because they are formed in our body in
good amounts mainly from carbohydrates. It is not essential to take them in
diet.

4
 Lipid Chemistry

I-Simple lipids
These are esters of fatty acids with an alcohol. According to the type of alcohol,
they are classified into:
1. Neutral fats {triacylglycerols (TAG) or triglycerides (TG)}.
2. Waxes: They are esters of one fatty acid with long chain
monohydroxy alcohol higher than glycerol, e.g. bee wax

Triacylglycerols
Triacylglycerols are composed of a glycerol backbone to which 3 fatty acids are
esterified.

TAG may be present in the form of:

Fats: solid at room temperature due to their high content of saturated fatty acids.

Oils: Liquid at room temperature due to their high content of unsaturated fatty
acids.

5
 Lipid Chemistry

II-Compound Lipids
These are fatty acids with alcohol and an extra group.

According to this extra group, compound lipids are classified into:

1. Phospholipids (containing phosphate)
2. Glycolipids (containing carbohydrates)

1-Phospholipids
They are classified according to the alcohol present into two main sub-groups:
A- Glycerophospholipids: Containing glycerol.
B- Sphingomyelin: Containing sphingosine (sphingol).
Glycerophospholipids:
• The basic structure of glycerophospholipids is composed of glycerol
backbone, 2 fatty acids and phosphoric acid.

• They include:

1 -Phosphatidic acid

2 -Phosphatidyl serine (Cephalin)

3 -Phosphatidyl ethanolamine

4 -Phosphatidyl choline (Lecithin)

5- Phosphatidyl inositol

N.B: Snake venom contains lecithinase enzyme which converts lecithin to

lysolecithin. This leads to hemolysis (break of RBCs).

6
 Lipid Chemistry

Phospholipids are amphipathic molecules that contain nonpolar groups of fatty

acid side chains and polar groups of glycerol, phosphate, ….

Importance of phospholipids:
I. Due to the amphipathic nature of phospholipids:
1) They are good emulsifying factors, important for digestion and absorption
of dietary fats.
2) They are good hydrotropic substances; they prevent deposition of
cholesterol as cholesterol stones.
3) They are important constituents of lipid bilayer in cell membranes.
4) They are important constituents of plasma lipoproteins.
II. Dipalmitoyl-lecithin is a major component of lung surfactant which is
needed to prevent lung collapse. Deficiency of lung surfactant leads to
neonatal respiratory distress syndrome.
III. They provide arachidonic acid for synthesis of eicosanoids.
IV. They are essential for blood clotting, as they provide the platelet
activating factor.
V. Intracellular signal transduction through phosphatidylinositol 4,5-
bisphosphate (PIP2).

2-Glycolipids
These are compound lipids containing sphingosine alcohol + FA +
carbohydrate. According to the type of carbohydrates, they are classified into:

1-Cerebrosides. 2-Sulfatides 3-Gangliosides

Importance of glycolipids:
They are found in brain tissues, myelin sheath & cell membranes of RBCs .
They act as:
1- Cell membrane receptors for hormones.
2- Provide cell recognition properties.

7
 Lipid Chemistry

III-Derived lipids
They are produced by the hydrolysis of simple or conjugated or they are
associated with lipids in nature. They include the following:
• Fatty acids.
• Alcohols: The most important are:
Glycerol in TAG
Sphingosine in sphingolipids
• Steroids.

STEROIDS

Sex Hormones
(male sex hormone &
female sex hormones)
Steroid
hormones
Corticoids
Sterols (Mineralocorticoids &
Steroids Glucocorticoids
(cholesterol)

Bile Acids

8
 Lipid Chemistry

STEROLS
CHOLESTEROL:

Sources:
- Exogenous (Dietary): The richest sources are eggyolk, red meat, liver,
kidney, butter, and brain. It is the most important animal sterol .
- Endogenous: Every cell can synthesize its own cholesterol (from acetyl Co
A). Plasma cholesterol is synthesized by the liver and intestine.
Forms: It is present either free (non-esterified) or esterified with fatty acid to
form cholesteryl-ester. Free cholesterol contains 27 carbon atoms .
Distribution of cholesterol: It is widely distributed in all tissues, but higher
concentrations are present in the nervous tissue, liver, adrenals, gonads, skin and
adipose tissue.
Plasma level of cholesterol:
- Normally it ranges from 120 to 200 mg/dL (30% as free cholesterol and
70% as cholesteryl-esters) . The recommended level is < 200 mg/dL.
- Increase plasma level of cholesterol is called Hypercholesterolemia which
predisposes to atherosclerosis and hypertension.
Importance and derivatives of cholesterol:
1. It is converted into bile acids and bile salts in the liver.
2. It is the precursor of all steroid hormones.
3. It can be oxidized in the liver into 7-dehydrocholesterol which can be
converted into vitamin D3 under the skin by ultraviolet rays.
4. It is an important constituent of cell membranes.
9
 Lipid Chemistry

BILE ACIDS
Types of Bile acids Synthesis Examples
Primary bile acids In liver from cholesterol Cholic acid
Chenodeoxycholic acid
Secondary Bile Acids By the action of bacteria Deoxycholic acid
in large intestine on Lithocholic acid
primary bile acids

Bile salts: They are formed by conjugation of bile acid with glycine (80%) or
taurine (20%) then they are excreted by liver in bile as sodium glycocholate or
sodium taurocholate.
Importance of bile salts:
1- Conversion of cholesterol to bile salt is an important mechanism for removal
of excess cholesterol from blood.
2- They are good emulsifying factors important for digestion and absorption of
fats.
3- They prevent precipitation of cholesterol in the bile as cholesterol stones.

STEROID HORMONES

Sex Hormones
I. Male sex hormones (androgens) (19 C):
• The main hormone secreted by the testes is Testosterone.
• Dihydrotestosterone (DHT) is the active form.

II. Female sex hormones:

I. Estrogens (18 C)
• The most potent is estradiol, which is the main hormone, secreted by
the ovaries. It is also formed by the placenta during pregnancy.

10
 Lipid Chemistry

II. Progesterone (21 C)

• It is secreted in females mainly by the ovaries and by placenta during
pregnancy.

Corticoids
Corticoids are mainly formed and secreted by the adrenal (suprarenal) cortex.
They are classified according to their action into two types (Glucocorticoids and
mineralocorticoids).

I. Glucocorticoids (21 C):

• They are termed glucocorticoids because they increase blood
glucose level.
• Examples: Corticosterone, Cortisol and Cortisone.
• Cortisol is the most potent glucocorticoid.

II. Mineralocorticoids (21 C):

Aldosterone:
• It is the main mineralocorticoid secreted by the adrenal cortex.
+
• It acts mainly on the kidneys where it promotes secretion of K and
+ +
H and reabsorption of Na (termed mineralocorticoids due to their
effect on minerals).

11