Week 6

Lipids
Structure, Classification, & Reactions

Dr. Kay Oduse

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Learning Objectives

Recognize the structures of common fatty acids and classify them as

Recognize saturated, monounsaturated, or polyunsaturated.

Explain Explain why fats and oils are referred to as triglycerides.

Explain how the fatty acid composition of the triglycerides

Explain determines whether a substance is a fat or oil.

Describe the importance of key reactions of triglycerides, such

Describe as hydrolysis, hydrogenation, and oxidation.

Identify and Identify and describe the functions derived lipids such as steroids,
describe membrane lipids, waxes.
Introduction
• Fats and oils, found in many of the foods we eat, belong to a class of biomolecules known as lipids.
• Gram for gram, they pack more than twice the caloric content of carbohydrates: the oxidation of fats and oils supplies about 9 kcal of energy for
every gram oxidized, whereas the oxidation of carbohydrates supplies only 4 kcal/g.
• Although the high caloric content of fats may be bad news for the dieter, it says something about the efficiency of nature’s designs.
• We store our reserve energy in lipid form, which requires far less space than the same amount of energy stored in carbohydrate form.
• Lipids have other biological functions besides energy storage. They are a major component of the membranes of the 10 trillion cells in our
bodies.
• They serve as protective padding and insulation for vital organs.
• Furthermore, without lipids in our diets, we would be deficient in the fat-soluble vitamins A, D, E, and K.
• Lipids are mainly hydrocarbons molecules of C-H bonds and are insoluble in polar solvent such as water.
• Includes waxes, phospholipids, steroids etc.

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Introduction

Lipid Organization based on structural relationships

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Lipids - Structure of Lipids

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Fatty Acids
• Fatty acids are carboxylic acids that are structural components of fats,
oils, and all other categories of lipids, except steroids.
• More than 70 have been identified in nature.
• They usually contain an even number of carbon atoms (typically 12–20),
are generally unbranched, and can be classified by the presence and
number of carbon-to-carbon (C=C) double bonds.
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Types of Fatty Acids
• Saturated fatty acids contain no carbon-to-carbon double bonds (C-C).

• Monounsaturated fatty acids contain one carbon-to-carbon double bond

(C=C), and

• Polyunsaturated fatty acids contain two or more carbon-to-carbon

double bonds (C=C) (C=C) (C=C) …
8 Unsaturated FAs
Cis and Trans Configuration
• A cis configuration means that the two hydrogen atoms
adjacent to the double bond stick out on the same side of the
chain.
• When a chain has many cis bonds, it becomes quite curved in
its most accessible conformations. For example, oleic acid,
with one double bond, has a "kink" in it, whereas linoleic
acid, with two double bonds, has a more pronounced
bend. α-Linolenic acid, with three double bonds, favors a
hooked shape.
• A trans configuration, by contrast, means that the adjacent
two hydrogen atoms lie on opposite sides of the chain. As a
result, they do not cause the chain to bend much, and their
shape is similar to straight saturated fatty acids.
• Most fatty acids in the trans configuration (trans fats) are not
found in nature and are the result of human processing
(e.g., hydrogenation).
Configuration of Saturated FAs & Unsaturated FAs

Three-dimensional representations of several fatty

acids. Saturated fatty acids have perfectly straight chain
structure. Unsaturated ones are typically bent, unless they have
a trans configuration.

Shea butter

Stearic acid (Fat) commonly found in cocoa butter

and the African Shea butter
Oleic acid in olive oil
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Common Saturated and Unsaturated Fatty Acids in Natural Fats

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Essential and Non-Essential Fatty Acids
• Essential fatty acids must be obtained from food while Non-Essential fatty acids can be synthesized by
the body (e.g., stearic acid, palmitic acid).
Essential Fatty Acids
• They fall into two categories—omega-3 and omega-6.
• The 3 and 6 refer to the position of the first carbon double bond and the omega refers to the methyl
end of the chain.
• Omega-3 and omega-6 fatty acids are precursors to important compounds called eicosanoids.
• Linoleic and α-linolenic acids are examples of essential fatty acids.
• Both substances are required for normal growth and development, but the human body does not
synthesize them.
Linoleic and α-linolenic acids are examples of essential fatty acids. How?
Using the table below

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Why Essential Fatty Acids are important
• The body uses linoleic acid to synthesize many of the other unsaturated fatty acids, such as arachidonic acid, a
precursor for the synthesis of prostaglandins.
• Eicosanoids are powerful hormones that control many other hormones and important body functions, such as
the central nervous system and the immune system.
• Eicosanoids derived from omega-6 fatty acids are known to increase blood pressure, immune response, and
inflammation.
• In contrast, eicosanoids derived from omega-3 fatty acids are known to have heart-healthy effects.
• Given the contrasting effects of the omega-3 and omega-6 fatty acids, a proper dietary balance between the two
must be achieved to ensure optimal health benefits.
• In addition, the essential fatty acids are necessary for the efficient transport and metabolism of cholesterol.
• The average daily diet should contain about 4–6 g of the essential fatty acids.
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Sources of Essential Fatty Acids
• Dietary sources of the omega 6 fatty acids include some leafy vegetables, seeds
nuts, grains, vegetable oils and meats.
• Dietary sources of the omega 3 fatty acids include some vegetable oils, nuts and
seeds, shellfish and fish.
• Some dietary supplement sources of essential fatty acids and nonessential fatty
acids include
• Evening Primrose oil,
• Borage oil,
• Flax seed oil and
• Fish oils (marine lipid concentrate)
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Omega-9 fatty acids
• Unlike omega-3 fatty acids and omega-6 fatty acid, omega−9 fatty
acids are not classed as essential fatty acids (EFA).
• Omega-9 fatty acids are from a family of unsaturated fats that are
commonly found in vegetable and animal fats.
• This monounsaturated fat is described as omega-9 because the double
bond is in the ninth position from the omega end.
1.

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3.

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Four Groups of Lipids
Fats &
oils

Waxes Lipids Phospholipids

Steroids
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Fats & Oils
• Fats and oils are the most abundant lipids in nature.
• They provide energy for living organisms.
• Storage tissues can have up to 15-20% lipid.
• insulate body organs
• transport fat-soluble vitamins through the blood.
• Can be refined and used as edible oil and fat
• Source of essential fatty acids and vitamins (fish liver oil, beef liver,
cheese)
23 Natural Sources of Fats and Oils

• Animal fat – Lard, suet; Cattle, sheep, pigs

• Plant source: Vegetable oil – sunflower oil,
coconut oil, Soybean, cotton seed,
sunflower seed, safflower seed, corn germ,
peanut, olive, rice, rape seed, canola,
coconut, palm fruit etc.
• Marine oil – cod liver oil, whale oil, tallow,
and fish oil.
Plant sources for industrial Applications

• Castor- lubricant Tung- wood coating Jojoba - medicinal

• Flax seed –paints and coating

Cooking – Food Industry (Next class)
 Structure of Fats and Oils
• Fats and oils are called triglycerides because they are esters composed of three fatty acid units joined
to glycerol, a trihydroxy alcohol.

Glycerol
• commonly called glycerin or glycerine
• Glycerol is classified by the FDA among the sugar alcohols as a caloric macronutrient.
• Glycerol has three hydrophilic hydroxyl groups that are responsible for its solubility in water and its
hygroscopic.
• Glycerol is sweet-tasting and of low toxicity.
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Structure of Fats and Oils
• If all three OH groups on the
glycerol molecule are esterified with the
same fatty acid, the resulting ester is called
a simple triglyceride (they rarely occur in
nature though – usually synthesized).
• Typical triglyceride (naturally occurring fats
and oils) contains two or three different
fatty acid components and is thus termed
a mixed triglyceride.
Fats and Oils
• Fats and oils are ESTERS of glycerol and long chain carboxylic fatty acids.

• Removal of water in the condensation reaction gives

28 Fats and Oils
• A triglyceride is called a fat if it is a solid at 25°C.
• it is called an oil if it is a liquid at that temperature.
• These differences in melting points reflect differences in the degree of unsaturation and number
of carbon atoms in the constituent fatty acids.
• Triglycerides obtained from animal sources are usually solids, while those of plant origin are
generally oils.
• Therefore, we commonly speak of animal fats and vegetable oils.
• Fats and oils are not part of the composition of fruits, and many vegetables.
• The composition of any given fat or oil can vary depending on the plant or animal species it
comes from.
• Palmitic acid is the most abundant of the saturated fatty acids, while oleic acid is the most
abundant unsaturated fatty acid.
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 Physical Properties of Fats and Oils
• Pure fats and oils are colorless, odorless, and tasteless.
• The characteristic colors, odors, and flavors are imparted by foreign substances that are lipid soluble
and have been absorbed by these lipids.
• For example, the yellow color of butter is due to the presence of the pigment carotene;
• the taste of butter comes from two compounds—diacetyl and 3-hydroxy-2-butanone-produced by
bacteria in the ripening cream from which the butter is made.

• Fats and oils are lighter than water, having densities of about 0.8 g/cm3.
• They are poor conductors of heat and electricity and therefore serve as excellent insulators for the
body, slowing the loss of heat through the skin.

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31 Chemical Reactions of Fats and Oils

• Hydrolysis: They can be hydrolyzed in the

presence of an acid, a base, or specific
enzymes known as lipases.
• The hydrolysis of fats and oils in the
presence of a base is used to make soap.
 Chemical Reactions of Fats and Oils
• Hydrogenation: The double bonds in fats and oils can undergo hydrogenation.
• The hydrogenation of vegetable oils produce semisolid fats.

• Double bonds that are hydrogenated to produce fats with the desired consistency (soft and pliable).
• Inexpensive and abundant vegetable oils (canola, corn, soybean) are transformed into margarine and
cooking fats.

In the preparation of margarine, for example, partially hydrogenated oils are mixed with water, salt, and nonfat
dry milk, along with flavoring agents, coloring agents, and vitamins A and D, which are added to approximate
the look, taste, and nutrition of butter. (Preservatives and antioxidants are also added.)

• In most commercial peanut butter, the peanut oil has been partially hydrogenated to prevent it from
separating out.
• Consumers could decrease the amount of saturated fat in their diet by using the original unprocessed oils
on their foods, but most people would rather spread margarine on their toast than pour oil on it.
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33 Chemical Reactions of Fats and Oils
• Oxidation and rancidity: Fats and oils that are in contact with moist air at room
temperature eventually undergo oxidation and hydrolysis reactions that cause them to
turn rancid, acquiring a characteristic foul odor.
• Butter, for example, releases foul-smelling (from hydrolysis of triglycerides) butyric,
caprylic, and capric acids.

To prevent rancidity or oxidation reaction; add Antioxidants.

• Examples are Vitamin E, BHT, BHA added in very small amounts (0.001%–0.01%).
• Antioxidants have strong affinity for oxygen and are able to cut off supply of oxygen
absorbed into the product.
• Also, in the case of butter or fat, cover and keep refrigerated.
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 • Hydrolysis of triglycerides may be carried out in either an acidic or a basic solution, or by
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.
This hydrolysis reaction also provides a useful analytical method for the determination of a
constant, called the saponification number, which is characteristic of the simple lipids.
• Saponification number of a lipid is an arbitrary unit, defined as the number of milligrams of
potassium hydroxide required to saponify 1.000 g of a fat or oil.
• A lipid, which contains long-chain fatty acids, will have a lower number of these acids per
Saponification unit weight than one containing the short-chain fatty acids.
• Therefore, a lipid with lots of long-chain fatty acids will have a low saponification number
Number in comparison to a lipid containing short-chain fatty acids.
• In other words, a small saponification number for a fat or oil indicates a high molecular
weight.

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 • Unsaturated fatty acids, whether they are free or combined as esters in fat and
oil, react with halogens by addition at the double bond(s).
• This is called halogenation, and it results in the decolorization of the halogen
solution, such as iodine or bromine.
• Because the degree of absorption of halogens by a fat or oil is proportional to the
number of double bonds in its fatty-acid moieties, the amount of halogen absorbed
by a fat can be used to determine the degree of unsaturation.
• This chemical constant is called the iodine number, and it is defined as the
number of grams of iodine (or iodine equivalent) absorbed by 100 g of fat or oil.
Iodine • This value is influenced by a few factors, i.e., percentage of unsaturated fatty
acid in the triglyceride molecule, the degree of unsaturation of each fatty acid, and
Number the mean molecular weight of the fat or oil.
• The iodine number for saturated fatty acids is 0. As the degree of unsaturation
increases, the iodine number increases (e.g., oleic acid = 90, linoleic acid = 181,
and linolenic acid= 274).

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Four Groups of Lipids
Fats &
oils

Waxes Lipids Phospholipids

Steroids
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Steroids - Cholesterol
• The most important non-saponifiable lipids are the steroids.
• These compounds include the bile salts, cholesterol and related
compounds, and certain hormones (such as cortisone and the sex
hormones).
• Steroids occur in plants, animals, yeasts, and molds but not in
bacteria.
• They may exist in free form or combined with fatty acids
or carbohydrates
Steroids - Cholesterol
• Cholesterol does not occur in plants, but it is the most abundant steroid in the human body (240 g
is a typical amount).
• Excess Cholesterol is believed to be a primary factor in the development of atherosclerosis and
heart disease, which are major health problems.

Numerous small gallstones made up largely of cholesterol

• Excess cholesterol not metabolized by the body is released from the liver and transported by the
blood to the gallbladder.
• Sometimes, however, cholesterol in the gallbladder precipitates in the form of gallstones.
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Phospholipids

• Phospholipids (PL), also known as phosphatides, are a class of lipids whose molecule has
a hydrophilic "head" containing a phosphate group, and two hydrophobic "tails" derived
from fatty acids, joined by a glycerol molecule.
• Phospholipids can form lipid bilayers on cell membranes because of
their amphiphilic (hydrophilic + lipophilic head) characteristic.
• Common sources includes soya, rapeseed, sunflower, chicken eggs, bovine milk, fish eggs etc.
• Phospholipids can act as emulsifiers, enabling oils to form a colloid with water.
• Phospholipids are one of the components of lecithin (in egg yoke and soybeans).
41 Waxes
• Waxes are esters formed from long-chain fatty acids
and long-chain alcohols.
• Most natural waxes are mixtures of such esters.
• Plant waxes on the surfaces of leaves, stems, flowers,
and fruits protect the plant from dehydration and
invasion by harmful microorganisms.
• Animals also produce waxes that serve as protective
coatings, keeping the surfaces of feathers, ears (ear
wax) skin, and hair pliable and water repellent.
42 Summary
• Fatty acids are carboxylic acids that are the structural components of many lipids
• They may be saturated or unsaturated
• Most fatty acids are unbranched and contain an even number of carbon atoms.
• Unsaturated fatty acids have lower melting points than saturated fatty acids containing the same number of carbon atoms.
• Fats and oils are composed of molecules known as triglycerides which are esters composed of three fatty acid units linked
to glycerol.
• An increase in the percentage of shorter-chain fatty acids and/or unsaturated fatty acids lowers the melting point of a fat
or oil.
• The hydrolysis of fats and oils in the presence of a base makes soap and is known as saponification.
• Double bonds present in unsaturated triglycerides can be hydrogenated to convert oils (liquid) into margarine (solid).
• The oxidation of fatty acids can form compounds with disagreeable odors. This oxidation can be minimized by the addition
of antioxidants.
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 Reference
• Ball et al. (August 12, 2019). The Basics of GOB Chemistry- Lipids. Retrieved February 22
2021 from
https://chem.libretexts.org/Bookshelves/Introductory_Chemistry/Book%3A_The_Basics_o
f_GOB_Chemistry_(Ball_et_al.)/17%3A_Lipids

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 Lipids (Part II)

Next Class
Application in the Food Industry

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