Lipid chemistry-1

Simple lipids

Dr. Laila Mahdi Mohamed

Medical Biochemistry & Molecular Biology Department
Faculty of Medicine-Helwan University
 Learning objectives

• Describe general classification of lipids.

• Define the types, structure and functions of fatty acids.
• Define simple lipids & classify them into two main subgroups.
• Describe structure & properties of triacylglycerol.
 Outlines
Lipids
• Definition

• Biomedical importance

• Classification (simple- conjugated- derived)

Fatty acids
• Definition

• Numbering

• Classification
• Properties (Physical & Chemical)

Simple lipids (Triacylglycerol and Waxes)

 Triacylglycerol

• Structure {glycerol + 3 FAs}

• Properties of TAG (Physical & Chemical)

• Rancidity (Definition, Causes, Types, Hazards & Prevention)
 Waxes
Lipids- Definition and Biomedical importance

Definition:
Lipids are organic substances relatively insoluble in water but soluble in organic
solvents like chloroform, ether and benzene.
Lipids- Classification
Lipids- Classification

Classification of lipids (3 main groups);

• Simple lipids: Esters of fatty acids with various alcohols. According to the
type of alcohol, this group is subdivided into triacylglycerol & waxes.
• Compound (Conjugated or Complex) lipids: They are simple lipids (esters
of fatty acids with alcohol) associated with other groups. This group includes
phospholipids, glycolipids and lipoproteins.
• Derived lipids: They are produced by hydrolysis of the previous groups or
they are present in association with them in nature.
 Outlines
Lipids
• Definition

• Biomedical importance

• Classification (simple- conjugated- derived)

Fatty acids
• Definition

• Numbering

• Classification
• Properties (Physical & Chemical)

Simple lipids (Triacylglycerol and Waxes)

 Triacylglycerol

• Structure {glycerol + 3 FAs}

• Properties of TAG (Physical & Chemical)

• Rancidity (Definition, Causes, Types, Hazards & Prevention)
 Waxes
Fatty acids- Definition

• Fatty acids (FA) are carboxylic acids with hydrocarbon side chain (mostly
monocarboxylic with carboxyl & methyl ends).
• They occur mainly as esters in natural fats and oils, but as free fatty acids (FFA)
in plasma.
Fatty acids- Numbering
Fatty acids- Numbering
Fatty acids- Classification
Fatty acids- Classification according to total carbon atoms (even or odd)
Fatty acids-Classification according to presence of double bonds (Saturated & unsaturated)
Fatty acids- Classification according to presence of double bonds- Saturated fatty acids (SFA)
Saturated fatty acids (SFA)
• They have no double bonds in the hydrocarbon side chain (straight hydrocarbon tails without kinking).
• They have the general formula : CH3–(CH2)n–COOH. {n=total number of C – 2)
• They are further classified, according to the number of carbon atoms, into short chain, medium
chain, long chain & very long chain.
• Palmitic & Stearic acids are widely distributed in animal fats.
• Palmitic acid is the commonest FA in human tissues.
• Examples of food rich in SFA: Cream, cheese, butter, other whole milk dairy products and fatty
meats. Certain vegetable products as coconut oil & palm oil.
• Biomedical importance of SFA: high intake of SFA may lead to increase in plasma cholesterol
levels and incidence of coronary heart diseases.
Fatty acids- Classification according to presence of double bonds- Saturated fatty acids (SFA)

Chain length Name No. of Chemical formula

Carbon
atoms
Short chain • Acetic acid 2C CH3-COOH
(2C to 6C) • Butyric acid 4C CH3-(CH2)2-COOH

Medium chain • Capric acid 10 C CH3-(CH2)8-COOH

(8C to 10C)

Long chain • Palmitic acid 16 C CH3-(CH2)14-COOH

(12C to 22C) • Stearic acid 18 C CH3-(CH2)16-COOH
• Arachidic acid 20 C CH3-(CH2)18-COOH

Very long • Lignoceric acid 24 C CH3-(CH2)22-COOH

chain
(24C or more)
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)
Unsaturated fatty acids (USFA)
• Most of the double bonds present in USFA are of the cis type and they are liquid in room
temperature (USFA containing trans-double bonds are solid in room temperature).
• They have one or more double bonds (monounsaturated or monoenoic) or (polyunsaturated
or polyenoic).
• In case of polyunsaturated fatty acids (PUFA), each two double bonds are separated by a
methylene group (CH2) as follows: -CH=CH-CH2-CH=CH-CH2-
• Biomedical importance of unsaturated fatty acids:
 Intake of USFA (cis type) has beneficial effects as decreased plasma cholesterol levels and
reducing the incidence of coronary heart diseases.
 Increased USFA content in cell membrane increases the membrane fluidity because the
kinks of the cis-double bonds prevent the packing of phospholipids closely together,
keeping them away from each other and allow greater mobility (straight hydrocarbon tails
of SFA interact strongly with each other decreasing membrane fluidity).
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)

Monounsaturated or monoenoic fatty acids

• They are present in all animal & vegetable oils (Olive oil is a particular rich source).
• The most important examples are:
Palmitoleic acid (C16:1, ∆9 -7)
It has 16 carbons and one double bond located between C9 and carbon C10 from
the carboxyl end and between C7 and C8 from the methyl end.
CH3-(CH2)5-CH=CH-(CH2)7-COOH
Oleic acid (C18:1, ∆9 -9)
It has 18 carbons and one double bond located between C9 and carbon C10 from
the carboxyl end and between C9 and C10 from the methyl end.
CH3-(CH2)7 -CH=CH-(CH2)7-COOH
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)

Polyunsaturated fatty acids (PUFA)

They include two important families which are 3 and 6 PUFA:
Omega three (3) PUFA,
• They are present in fish oil and plant oils (flaxseed & canola).
• Linolenic acid (C18:3, 3) is the precursor of 3 PUFA.
(It has 18 carbons and three double bonds, the first double bond located between C3 and C4 from the
methyl end).
Omega six (6) PUFA,
• They are present in nuts, olives, various oils as sunflower oil, corn oil & cottonseed oil.
• Linoleic acid (C18:2, 6) is the precursor of 6 PUFA.
• Arachidonic acid (C20:4, 6) is an important example of 6 PUFA.

Note: Eicosanoids are physiologically active compounds formed from PUFA with C20 mainly
arachidonic acid. They are hormone like molecules functioning in diverse physiological & pathological
processes such as: inflammation, allergy, fever and other immune responses. They are classified into two
main groups, including most prominently the prostaglandins.
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)
Unsaturated fatty acids (USFA)
Trans fatty acids
 They are formed mainly during the hydrogenation of liquid vegetable oils (during the manufacture of
margarine & partially hydrogenated oils).
 Examples of food rich in trans fatty acids: many commercial baked foods & most fried foods.
Partially hydrogenated oils are used to improve the texture, shelf-life and flavor of foods and because
these oils can be used many times in commercial friers.
 Biomedical importance of trans fatty acids: Similar to high intake of SFA, increased intake of trans
fatty acids may lead to increase in plasma cholesterol levels and incidence of coronary heart diseases.
Fatty acids- Classification according to presence of double bonds- Unsaturated fatty acids (USFA)
Fatty acids- Classification according to the nutritional value (essential & non-essential)

Essential fatty acids

• They are the polyunsaturated fatty acids (PUFA).
• They must be taken in diet because the body cannot synthesize them, as the
enzymes that are needed for their synthesis are absent in humans.
• They include Linolenic acid (C18:3, 3) and Linoleic acid (C18:2, 6)
• Note: Arachidonic acids (C20:4, 6) is synthesized in our body from Linoleic
acid but in absence of Linoleic acid, Arachidonic acid is considered as an
essential fatty acid.

Non-essential fatty acids

They include all other fatty acids. The body can synthesize them in good amounts.
Fatty acids- Classification according to the nutritional value (essential & non-essential)

Functions of essential fatty acids

1. They are essential for growth.
2. They are essential for phospholipids formation.
3. Arachidonic acid is important for biosynthesis of prostaglandins.
4. They form cholesterol esters (less liable to be deposited in blood vessels), so they
protect against atheroscelerosis.
5. They enter in the structure of all cellular and subcellular membranes.
6. They are essential for skin integrity and reproduction and important in preventing and
treating fatty liver.
7. Important in health of the retina and vision.
8. They can be oxidized for energy production
Deficiency of essential fatty acids leads to:
• Impaired growth and dermatitis
• Fatty liver and sterility in adults
Fatty acids- properties

Physical properties of fatty acids:

• Solubility in water: The short chain fatty acids (up to 6 carbons) are soluble in water.
• Melting point:
 The melting point of saturated fatty acids increases with the chain length.
 The lower members of saturated fatty acids are liquid & volatile at room
temperature.
 The higher members of saturated fatty acids (more than 10 carbons) are solid.
 Thus acetic acid is liquid while palmitic and stearic acids are solids.
 Unsaturated fatty acids are liquid due to presence of cis-double bonds (USFA

containing trans-double bonds are solid in room temperature).

• Odor & Taste: The short chain fatty acids have an irritating odor and a sour taste,
while the long chain ones are odorless and tasteless.
Fatty acids- properties
Chemical properties of fatty acids:
• Properties due to presence of carboxylic group
 Ester formation (TAG formation)
 Salt formation (Saponification)
 Reduction (giving the corresponding fatty aldehyde (R-CHO) which is further reduced to the corresponding fatty
alcohol (R-CH2OH))

• Properties due to presence of double bond

 Addition of hydrogen (giving the corresponding SFA)

 Addition of oxygen (giving the corresponding peroxide which is further oxidized producing splitting of the
fatty acid chain with formation of lower chain fatty aldehyde and lower chain fatty acid)
 Outlines
Lipids
• Definition

• Biomedical importance

• Classification (simple- conjugated- derived)

Fatty acids
• Definition

• Numbering

• Classification
• Properties (Physical & Chemical)

Simple lipids (Triacylglycerol and Waxes)

 Triacylglycerol

• Structure {glycerol + 3 FAs}

• Properties of TAG (Physical & Chemical)

• Rancidity (Definition, Causes, Types, Hazards & Prevention)
 Waxes
Lipids- Classification, Simple lipids (Triacylglycerol and Waxes)
Lipids- Classification, Simple lipids (Triacylglycerol and Waxes)
Lipids- Classification, Simple lipids (Triacylglycerol), structure of TAG
Triacylglycerol (TAG) / Triglycerides (TG) / Neutral fats or oils
• They are the most abundant lipids in nature.
• They are the storage form of lipids in the body.
• They are esters of 3 fatty acids (FA) with glycerol (trihydric alcohol with three hydroxyl
groups).

• They are similar chemically, but they differ in physical properties, as oils are
liquid while fats are solid at room temperature.
• They are called neutral due to absence of ionizable groups in it.
• They are called triacylglycerol or triglycerides because they are tri-esters formed
of glycerol and 3 fatty acids.
• They may be :
a- Simple TAG: The 3 fatty acids are the same e.g. palmitic or stearic acids
forming>>>> tripalmitate or tristearate respectively.
b- Mixed TAG: TAG with 3 different fatty acids. TAG are usually of mixed type.
Lipids- Classification, Simple lipids (Triacylglycerol), structure of TAG
Lipids- Classification, Simple lipids (Triacylglycerol), structure of TAG
Lipids- Classification, Simple lipids (Triacylglycerol), structure of TAG
Lipids- Classification, Simple lipids (Triacylglycerol), structure of TAG ˃˃˃˃ glycerol

Glycerol:
 It is a trihydric alcohol (an alcohol containing three hydroxyl groups) which
can be esterified with one, two or three fatty acids giving mono-, di-, or
triglycerides respectively.
 Mono and diacylglycerols are of particular significance in the synthesis and
hydrolysis of triacylglycerols.
 It is colorless, odorless and has a sweet taste.
 It is liquid & soluble in water.
 Biomedical importance of glycerol:
• Formation of TAG, the storage form of lipids in body.
• It is used in pharmaceutical and cosmetic preparations (glycerine).
• It is used as a vasodilator agent in coronary heart diseases (nitroglycerine).
• It is used as a laxative.
• It can cause rapid, temporary decrease in the internal pressure of the eye. This
can be useful for the initial emergency treatment of severely elevated eye
pressure (treatment of glucoma).
• It is used as explosive in the form of trinitroglycerine.
Lipids- Classification, Simple lipids (Triacylglycerol), Properties of TAG

Physical properties of triacylglycerol (TAG):

• Pure, freshly prepared (non-rancid) TAG are colorless, odorless and tasteless
(the yellow color of fats and oils is due to the presence of fat soluble pigments
called carotenoids).
• They are insoluble in water & soluble in fat solvents.
• Physical state at room temperature;
 Solid triacylglycerols are called fats e.g. ghee (butter fat) and margarine (artificial
butter). Their solid state is due to their high content of the SFA (higher members).
 Liquid triacylglycerols are called oils e.g. olive, cotton seed, linseed and maize oils.
Their liquid state is due to their high content of the USFA.
Chemical properties of triacylglycerol (TAG):
• Addition of hydrogen (Hardening)
• Hydrolysis of TAG (Acidic- enzymatic- alkaline)
Lipids- Classification, Simple lipids (Triacylglycerol), Properties of TAG

Chemical properties of triacylglycerol (TAG)

Addition of hydrogen (Hardening):
• Addition of hydrogen to the double bonds to convert USFA to SFA. So the liquid oils will be
converted to the corresponding solid fats or margarine & hence the name (Hardening).
• These are now widely used as a substitute to natural fats .
Lipids- Classification, Simple lipids (Triacylglycerol), Properties of TAG

Chemical properties of triacylglycerol (TAG)

Hydrolysis of TAG (Acidic- enzymatic- alkaline)

• Acidic hydrolysis: TAG dil. HCL/ 3 H2O Glycerol + 3 FFA

• Enzymatic hydrolysis: TAG Lipase enzyme/ 3 H2O Glycerol + 3 FFA

• Alkaline hydrolysis (Saponification): TAG 3 KOH Glycerol + 3 RCOOK (K soap)

Alkaline hydrolysis produces glycerol and salts of fatty acids (soaps). Soaps cause
emulsification of oily material this help easy washing of the fatty materials.
Lipids- Classification, Simple lipids (Triacylglycerol), Rancidity
Rancidity
 Definition of rancidity:
•It is a change in the natural properties of fats & oils leading to the development of bad odor and taste
(bad flavor) after exposure to Moisture, atmospheric Oxygen, High temperature, Metals, light, and
bacterial contamination.
• Saturated fats resist rancidity more than unsaturated fats that have double bonds.
 Types of rancidity (hydrolytic & oxidative):
1-Hydrolytic rancidity
It results from hydrolysis of TAG by lipase present in bacteria specially at high temperature and
moisture leading to the liberation of short chain fatty acids which are volatile and have bad odor.
Lipids- Classification, Simple lipids (Triacylglycerol), Rancidity

 Types of rancidity (hydrolytic & oxidative):

2-Oxidative Rancidity:
• This occurs due to addition of oxygen at the double bond of the unsaturated fatty acids of oils
producing peroxides, fatty aldehydes, and dicarboxylic acids that are toxic and have bad odor.
• Peroxidation of lipids is responsible for the deterioration of food, damage of cellular &
mitochondrial membranes, and destruction of fat soluble vitamins (particularly vitamin A) causing
cancer, inflammatory disease, atherosclerosis and aging.
 Hazards of rancidity:
• The products of rancidity are toxic, i.e., causes food poisoning and cancer.
• Rancidity destroys the fat-soluble vitamins (vitamins A, D, K and E).
• Rancidity destroys the polyunsaturated fatty acids (the essential fatty acids).
• Rancidity causes economical loss because rancid fat is inedible.
 Prevention of rancidity:
• Avoidance of the causes by keeping fats or oils in well-closed containers in cold, dark and dry place
(i.e., good storage conditions).
• Addition of anti-oxidants to prevent peroxidation of fat as vitamin E, phenols & quinones. The most
common natural antioxidant is vitamin E (tocopherol).
 Outlines
Lipids
• Definition

• Biomedical importance

• Classification (simple- conjugated- derived)

Fatty acids
• Definition

• Numbering

• Classification
• Properties (Physical & Chemical)

Simple lipids (Triacylglycerol and Waxes)

 Triacylglycerol

• Structure {glycerol + 3 FAs}

• Properties of TAG (Physical & Chemical)

• Rancidity (Definition, Causes, Types, Hazards & Prevention)

 Waxes
Lipids- Classification, Simple lipids (Waxes)
Waxes
• Esters of fatty acids with long chain monohydric alcohol higher than glycerol.
• They are solid at room temperature.
• The most important waxes in human body are cholesterol esters, which are present in
blood and other tissues.
• Examples of waxes:
True wax (bee’s wax) which is the ester of 30 C alcohol with palmitic acid.
Cholesterol esters
These are esters of cholesterol with palmitic, stearic or oleic acids e.g. lanoline.
Vitamin A (retinol) & vitamin D (calciferol) esters
These are esters of vitamins A and D with palmitic or stearic acids.
Summary
Summary
Summary
Summary
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