CHAPTER FOUR

LIPIDS

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Lipids
Lipids are substances that are soluble in organic solvents such as
chloroform and methanol but insoluble in water.

 Unlike nucleic acids, proteins, and polysaccharides, lipids are not

polymeric.

 Lipids include fats, cholesterol, fatty acids, lipid-soluble

vitamins, waxes, glycerophospholipids, sphingolipids,
and others.
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The lipids of physiological importance for humans have four
major functions:
1. They serve as structural components of biological
membranes. e.g phospholipids
2. They provide energy reserves, predominantly in
the form of triacylglycerols.
3. Both lipids and lipid derivatives serve as vitamins
and hormones.
4. Lipophilic bile acids aid in lipid solubilization.
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Other lipids, which are present in smaller amounts act as
enzyme cofactors,
electron carriers,
light absorbing pigments,
hydrophobic anchors for proteins,
emulsifying agents,
 Fat under skin serve as thermal insulator against low temperatures.

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Fatty Acids
Are long-chain hydrocarbon molecules containing a carboxylic acid moiety at one end.

They are carboxylic acids with an even number of carbon atoms, usually between 4 up to and
36.

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rarely occur in free form and are usually found in esterified form as the
major components of various lipids.

The most commonly occurring fatty acids have even numbers of carbon atoms in an
unbranched chain of 12 to 24 carbons.

Fatty acids with less than 12 and more than 24 carbon atoms are uncommon.

The most abundant species are those with 16 and 18 carbon atoms. 6
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Classification of fatty acids
Based on composition lipids are classified as simple, complex and
derived lipids.

1. Simple lipids: Esters of fatty acids with various alcohols.

a. Fats and oils – esters of fatty acids with glycerol.
Oils are fats in liquid state.
b. Waxes – esters of fatty acids with high molecular weight
(14 carbon atoms to 36 carbon atoms) monohydric alcohols.
c. Sterol esters such as cholesterol ester

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2. Complex lipids: Esters of fatty acids containing groups in addition to
an alcohol and a fatty acid.
a. Phospholipids–contains fatty acids, alcohol (glycerol or
sphingosine), phosphate and head group alcohol

(usually contain nitrogen). Based on backbone

alcohol phospholipids can be grouped as:
i/ Glycerophospholipids – the backbone alcohol is glycerol
ii/ Sphingophospholipids – the backbone alcohol is sphingosine

b. Glycolipids (or glycosphingolipids) – lipids containing a fatty

acid, sphingosine and carbohydrate.
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3. Derived lipids: These include hydrolytic products of simple and

complex lipids.
Classification of fatty acids

 Saturated fatty acids do not contain (-C=C-) , cannot undergo further

hydrogenation.

 unsaturated fatty acids contain double bonds (-C=C-)→→

hydrogenated.

 If a fatty acid contains more than one carbon-carbon double bond, it is

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called polyunsaturated fatty acid.
 The physical properties of fatty acids, and of the lipids that contain them, are largely
determined by the length and degree of unsaturation of the hydrocarbon chains.

 Their poor solubility in water is because of the presence of non-polar hydrocarbon

chain.

 The numeric designations used for fatty acids come from the number
of carbon atoms, followed by the number of sites of unsaturation
(example, palmitic acid is a 16-carbon fatty acid with no unsaturation
and is designated by 16:0).
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 The site of unsaturation in a fatty acid is indicated by the symbol ∆
and the number of the first carbon of the double bond

(example, palmitoleic acid is a 16-carbon fatty acid with one site of

unsaturation between carbons 9 and 10, and is designated by 16:1∆9).

 Saturated fatty acids of less than eight carbon atoms are liquid at
physiological temp, whereas those containing more than ten are solid.

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Saturated fatty acids

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Saturated fatty acids

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Some unsaturated fatty acids

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Some unsaturated fatty acids

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Nomenclature of fatty acids
 Fatty acids can be named in at least three ways –
common name,
systematic name and
simplified (or shorthand) notation.

1. Common (trivial) name

Most fatty acids are known by their common (or trivial) names.
Some of the trivial names are based on the source from which the fatty
acid was first extracted.
e.g butyric acid, palmitic acid, stearic acid, oleic acid, linoleic
acid, linolenic acid, or arachidonic acid.
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2. Systematic (scientific) names
 The scientific nomenclature system names fatty acid after
the hydrocarbon with the same number and arrangement of
carbon atoms, with –oic being substituted for the final –e.

Thus, saturated acids end in –anoic, and

unsaturated fatty acids with double bonds end in –enoic.

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For e.g
a fatty acid containing 18 carbon atoms with no double bond
has a systematic name of octadecanoic acid and

a systematic name for unsaturated fatty acid containing 16

carbon atoms and one double bond is cis-9-hexadecenoic acid.

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Rules of scientific names
1. The number of carbon atoms are identified by Greek
number (buta, penta, hexa,…)
2. Carbon atoms are numbered beginning with the carboxyl
carbon as carbon 1
3. The carbon atoms, C-2, C-3, and C-4 are known as the α, β,
and γ carbons, respectively, and the terminal methyl carbon
is known as the ω-carbon regardless of chain length.
4. Position of double bond is referred to by the 1 st carbon
atom of the double bond
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The simplified (or shorthand) notation
 are represented by abbreviation that specifies the chain
length, number of double bonds, and the positions of
double bonds if available.
 The notation take a form n:y Δ p,q,r, …, where n= number
of carbon atoms, y = number of double bonds, Δ = means
double bond, p, q, r = the first carbon of each double bond.
 For example, the 16-carbon saturated palmitic acid is
abbreviated as 16:0, and the 18-carbon oleic acid, with one
double bond, is designated as 18:1Δ9. 21
 Name and occurrence of saturated fatty acids
Common name Scientific name Abbreviation Occurrence

Acetic acid Vinegar

Propionic acid Catabolic product of odd carbon fatty acids

Butyric acid Butanoic acid 4:0 Butter

Valeric acid Pentanoic acid 5:0 Catabolic intermediate of odd C fatty acids

Caproic acid Hexanoic acid 6:0 Butter

Caprylic acid Octanoic acid 8:0 Butter

Capric acid Decanoic acid 10:0 Butter and coconut oil

Lauric acid Dodecanoic acid 12:0 Coconut oil

Myristic acid Tetradecanoic acid 14:0 Coconut oil

Palmitic acid Hexadecanoic acid 16:0 Major storage lipid in adipose tissue

Stearic acid Octadecanoic acid 18:0 Body fat / adipose

Arachidic acid Eicosadecanoic acid 20:0 Peanut oil

Behanic acid Docosanoic aid 22:0

Lignoceric acid Tetracosanoic acid 24:0 Peanut oil, cerebrosides

Cerotic acid Hexacosanoic acid 26:0 22

 Name and Occurrence of unsaturated fatty acids
Common name Scientific name Abbreviation Occurrence

Palmitoleic acid cis-9-Hexadecenoic acid 16: 1 9 Body fat

Oleic acid cis-9-Octadecenoic acid 18: 1 9 Body fat

Linoleic acid cis-cis-9,12-Octadecadienoic acid 18: 2 9,12 Vegetable oils

Linolenc acid All cis-9,12,15-Octadecatrienoic acid 18: 39,12,15 Vegetable oils

Ricinoleic acid 2-Hydroxy-cis-9-octadecenoic acid 18: 19 (2-OH) Brain lipid

Arachidonic acid All cis-5,8,11,14-Eicosatetraenoic acid 20: 4 5,8,11,14 Vegetable oils

Timnodonic acid All cis-5,8,11,14,17 –Eicosapentaenoic acid 20: 5 5,8,11,14,17 Fish oil, brain

Erucic acid Cis-13-Docosaenoic acid 22: 1 13 Mustard and Rape seed oil

Clupandonic acid All cis-7,10,13,16,19-Docosapentaenoic acid 22: 5 7,10,13,16,19 Fish oil, brain

Cervonic acid All cis-5,8,11,14,17,19-Docosapentaenoic acid 22: 65,8,11,14,17,19 Fish oil, brain

Nervonic acid Cis-15-Tetracoasaenoic acid 24: 115 Brain lipids

Cerebronic acid 2-Hydroxy tetracosanoic acid 24: 2-OH Brain lipids 23

Triacylglycerides

 The fats and oils that occur in plant and animal consist
largely of mixtures of triacylglycerols (also referred to as
triglycerides or neutral fats).

 Non-polar, water-insoluble substances are fatty acid

triesters of glycerol
 All three acyl groups in a triacylglycerol may be the same,
all three may be different, or one may be different from the
other two. 24
 Triacylglycerols function as energy reservoirs in animals
they are not components of biological membranes.
 Triacylglycerols differ according to the identity and
placement of their three fatty acid residues.
 Triglycerides (triacylglycerols or TAG’s) are triesters of
glycerol and fatty acids.

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Depend on whether it contains the same type of fatty acids or
not we can classify them as

1. simple triacylglycerols (same

kind of fatty acid in all three
positions )
are named after the fatty acid they
contain.
Simple triacylglycerols of 16:0,
18:0, and 18:1, for example, are
tristearin, tripalmitin, and triolein,
respectively. 26
2. Mixed triacylglycerols
They contain two or more different fatty acids
Most naturally occurring triacylglycerols are mixed

Q3. Why triacylglycerols are insoluble

in water?
Because the polar hydroxyls of glycerol and
the polar carboxylates of the fatty acids are
bound in ester linkages, triacylglycerols are
nonpolar, hydrophobic molecules, essentially
insoluble in water.
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Steroids and other lipids
containing the steroid nucleus

 consists of three cyclohexane rings and one cyclopentane ring fused

together

 Cholesterol is one of the most important and abundant steroids in the

body. the precursor of all other steroids.
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 Cholesterol is biosynthesized from squalene, a triterpene.
 Cholesterol is an important component of cell membranes.
 Its ring structure makes it more rigid than other membrane
lipids.

Because cholesterol has eight

asymmetric carbons, 256
stereoisomers are possible, but
only one exists in nature.
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 Cholesterol contains this tetracyclic skeleton modified to include an
alcohol function at C-3, a double bond at C-5, methyl groups at C-10
and C-13, and a C8H17 side chain at C-17.

 Animals accumulate cholesterol from their diet, but are also able to
biosynthesize it from acetate.

 The male sex hormones, known as androgens, are secreted by the

testes.
 They are responsible for the development of male secondary sex
characteristics during puberty.
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 They also promote muscle growth.
 Testosterone and 5α- dihydrotestosterone are androgens

Estradiol and estrone are female sex hormones known as

estrogens.
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Waxes
 Waxes are esters of long chain (14 to 36 carbon) saturated and unsaturated fatty acids with
long chain (16 to 30 carbon) alcohols.

 They have higher melting point than triglycerides and have water-repellent properties.

 They are widely used in pharmaceutical, cosmetic and other industries for the manufacture
of ointments and polish

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Fats and Oils

 Triglycerides (triacylglycerols or TAG’s) are triesters of glycerol and fatty acids.

They are the major form of energy storage in animals.

R, R’, and R’’ can either be identical (simple TAG) or non-identical (mixed
TAG)
 Fats are solids at room temp → come from animal
sources. 33
Glycerophospholipids (or phospholipids)

 Similar to TAG’s except that one hydroxyl group of glycerol is replaced by the ester
of phosphoric acid and an amino alcohol, bonded through a phosphodiester
bond.

 are triesters of glycerol that contain charged phosphate diester groups and are
abundant in cell membranes.

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 Together with other lipids, control the flow of molecules into and out of cells.
Sphingolipids (an amino alcohol)

 Esters of an 18 carbon alcohol called sphingosine (instead of glycerol)

 We find them in the biological membranes of the brain and nerve tissues.

 contain a carbohydrate such as galactose or glucose → Glycosphingolipids

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Vitamins
 Some vitamins (A, D2, E and K1) are fat soluble, therefore, considered lipids.
 have important roles in
vision,
bone growth, and
blood clotting.

Terpenes
 Natural products or secondary metabolites are often derived from
primary metabolites.
 These groups include terpenes, steroids, alkaloids (contain basic N
function such as cocaine and nicotine), phenolic compounds
(flavonoids) and pigments.
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 defined as materials with molecular structures containing carbon back
bones made up of isoprene (2-methylbuta-1, 3-diene) units.

 Isoprene contains five carbons atoms and therefore, the number of

carbon atoms in any terpenoid is a multiple of five.

 Degradation products of terpenoids in which carbon atoms have been

lost through chemical and biochemical processes may contain
different number of carbon atoms, but their overall structure will
indicate their terpenoid origin and they will still be considered as
terpenoids.
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The Phospholipid Bilayer

 All Biological Membranes are made of the same basic

structure.
 This is composed of molecules called Phospholipids, which
form a Phospholipid Bilayer.
 Phospholipids are fats.
 They are composed of two Fatty Acid 'tails' and a Phosphate
'head'.

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 The Phosphate 'heads' are Hydrophilic whereas the Fatty Acid 'tails'
are Hydrophobic, meaning that Phospholipids are Amphipathic.

 When placed in water, the 'heads' orientate themselves towards water

molecules and the 'tails‘ away, meaning that phospholipids will form a
layer above water leaflets.

 If Phospholipid Molecules are completely surrounded by water, they

may form a Bilayer.
 A Phospholipid Bilayer consists of two layers of Phospholipids where
the 'tails' point inwards and the 'heads‘ point outwards, towards water.

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 One layer is like a mirror image of the other
Components of Biological Membranes
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Lipids Functions
 Storage of energy Water repellant
Prevents loss of water via evaporation
 Insulation from environment
Membrane structure
•Low thermal conductivity
Main structure of cell membranes
•High heat capacity (can “absorb” heat)
•Mechanical protection (can absorb shocks) Cofactors for enzymes
Vitamin K: blood clot formation
Pigments
Coenzyme Q: ATP synthesis in
Color of tomatoes, carrots, pumpkins, mitochondria
some birds Antioxidants
 Signaling molecules Vitamin E
• Steroid hormones (act body-wide)
• Growth factors
• Vitamins A and D (hormone precursors)
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Triacyl glycerols

 are carboxylic acid triesters of glycerol (a three-carbon trialcohol).

 make up the fats stored in our bodies and most dietary fats and oils.

 are a major source of biochemical energy.

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Condensation of glycerol with three fatty acids produces a molecule of fat or oil
Some key points about structure and properties of triacylglycerols

 TAG that are solid at room temp are classified as fats (animal-based).

 TAG that are liquid at room temp are classified as oils (vegetable-

based)

 the more unsaturated the fatty acids in a TAG, the less solid it is

 Most liquid TAG come from plant sources (olives, corn, safflower)

 Most solid or primarily saturated fats come from animal sources

Oil contains high proportions of unsaturated fatty acids → liquid

Fats contains high proportions of saturated fatty acids → solid 44

Its chemical property

Hydrolysis of triglycerols: esters react with water to form their carboxylic

acid and alcohol a process known as hydrolysis.
In body, it is catalyzed by the enzyme hydrolase.
 In the laboratory and commercial production of soap, hydrolysis of fats and oils is
usually carried out by strong aqueous bases such as NaOH and KOH and is called
saponification.
 Hydrogenation of triglycerols
 Rxn with H2/Pt converts unsaturated carbons to saturated. (oil → fat).or liquid-solid

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Thank you !!
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