LIPID CHEMISTRY

FATTY ACIDS

Dr Naim
 FATTY ACIDS
• Fatty acids are water-soluble, long-chain
hydrocarbons with one carboxyl group at the end of
the chain and a methyl group at the other end (the ω-
carbon).
CH3-(CH2)-CH2-CH2-CH2-COOH
• At physiologic pH, the terminal carboxyl group
(COOH) ionizes and becomes -C00-.
• The -COO- group has an affinity for water and the
rest of the region is hydrophobic. This results in the
formation of an amphipathic molecule.
Amphipathic Lipids

• These are lipids having a hydrophilic polar head’

region and a hydrophobic non-polar tail’ region.

• Amphipathic lipids stabilize emulsions and form the

lipid bilayer of membranes.

• Ionized fatty acids, phospholipids, sphingomyelins.

glycosphingolipids and bile acids are examples.
Fatty acids are carboxylic acids with
hydrocarbon side chain

R COOH
 Occurrence

• Esterified with variouslipids

Esterified
• Common

• FFA
Free
• Blood
D/U Total no D/U Length of D/U Nature of
of carbon hydrocarbon hydrocarbon
atoms chain chain
Short chain FA Saturated FA
Even chain FA
Medium chain FA Unsaturated FA

Long chain FA Branched chain FA

Odd chain FA
Very long chain FA Hydroxy FA
Fatty Acids

• The fats and oils used almost universally as stored

forms of energy in living organisms are derivatives
of fatty acids

• Fatty acids are aliphatic carboxylic acids with

hydrocarbon chains

• Fatty acids occur in the body mainly as esters in

natural fats and oils,
• but are found in the unesterified form as free fatty
acids, a transport form in the plasma
• Fatty acids that occur in natural fats usually contain
an even number of carbon atoms ranging from 4 to
36 carbons (C4 to C36)

• Fatty acids are named after the corresponding

hydrocarbons

• A fatty acid consists of a hydrophobic hydrocarbon

chain with a terminal carboxyl group that has a
pKa of about 4.8
• At physiologic pH, the terminal carboxyl group (-
COOH) ionizes, becoming –COO-

• This anionic group has an affinity for water, giving

the fatty acid its amphipathic nature (having both a
hydrophilic and a hydrophobic region)

• However, for long-chain fatty acids (LCFA), the

hydrophobic portion is predominant
• These molecules are highly water-insoluble, and
must be transported in the circulation in association
with protein

• More than ninety percent of the fatty acids found

in plasma are in the form of fatty acid esters
(primarily triacylglycerol, cholesteryl esters, and
phospholipids) contained in circulating lipoprotein
particles

• Unesterified fatty acids are transported in the

circulation in association with albumin
 Fatty acids have important roles:

• They act as energy stores and fuel molecules.

• They are components of membrane.
• They modify proteins covalently.
• Fatty acid derivatives serve as hormones and
intracellular secondary messengers.
 Biomedical Importance
• Fatty acids exist free in the body (unesterified) and
also are found as fatty acyl esters in more complex
molecules, such as triacylglycerols

• Low levels of free fatty acids occur in all tissues,

but substantial amounts sometimes can be found
in the plasma, particularly during fasting

• Plasma free fatty acids FFA (transported by serum

albumin) are in route from their point of origin
(triacylglycerol of adipose tissue or circulating
lipoproteins) to their site of consumption (most
tissues)
• Free fatty acids can be oxidized by many tissues-
particularly liver and muscle-to provide energy

• Fatty acids are also structural components of

membrane lipids, such as phospholipids and
glycolipids
• Fatty acids are attached to certain intracellular
proteins to enhance the ability of those proteins to
associate with membranes

• Fatty acids are also precursors of the hormone-like

prostaglandins

• Esterified fatty acids, in the form of triacylglycerols

stored in adipose cells, serve as the major energy
reserve of the body
 Saturation of fatty acids

• Fatty acid chains may contain no double bonds, that

is be saturated, or contain one or more double
bonds that is, be mono- or polyunsaturated

• When double bonds are present, they are nearly

always in the cis rather than in the trans
configuration
• The introduction of a cis double bond causes the
fatty acid to bend or "kink" at that position
• If the fatty acid has two or more double bonds they
are always spaced at three carbon intervals
 Physical and Physiologic Properties of Fatty Acids
Reflect Chain Length and Degree of Unsaturation

• The melting points Tm of even-numbered carbon

fatty acids increase with increasing chain length and
decrease with increasing unsaturation

• A triacylglycerol containing three saturated fatty

acids of 12 carbons or more is solid at body
temperature,
• whereas if the fatty acid residues are 18:2, it is
liquid to below 0°C
• At room temperature (250C), the saturated fatty
acids from 12:0 to 24:0 have a waxy consistency,
• whereas unsaturated fatty acids of these lengths
are oily liquids

• This difference in melting points is due to different

degrees of packing of the fatty acid molecules

• In the fully saturated compounds, the most stable

conformation is the fully extended form,
• in which the steric hindrance of neighboring atoms
is minimized
• These molecules can pack together tightly in nearly
crystalline arrays, with atoms all along their lengths
in contact with the atoms of neighboring molecules

• In unsaturated fatty acids, a cis double bond forces

a kink in the hydrocarbon chain

• Fatty acids with one or several such kinks cannot

pack together as tightly as fully saturated fatty
acids, and their interaction with each other are
therefore weaker
• In practice, natural acylglycerols contain a mixture
of fatty acids tailored to suit their functional roles

• The membrane lipids, which must be fluid at all

environmental temperatures, are more unsaturated
than storage lipids

• Because membrane lipids typically contain LCFA,

the presence of double bonds in some fatty acids
helps maintain the fluid nature of those lipids
Most of the fatty acids that occur in natural lipids are
even carbons.
 Seen in milk and microbial cell walls

Propionic acid Valeric acid

• 3 Carbon • 5 Carbon
 Nomenclature
• The most frequently used systematic nomenclature
names the 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, e.g. octanoic acid,

• and unsaturated acids with double bonds end in -
enoic, e.g. octadecenoic acid (oleic acid)

• The most commonly used system for designating

carbon atoms and the position of double bonds in an
unsaturated fatty acid is the delta (∆) numbering
system
• A simplified nomenclature for unbranched fatty
acids specifies the chain length and number of
double bonds, separated by a colon

• The carbon atoms are numbered, beginning with

the carboxyl carbon as carbon 1
CH3-(CH2)-CH2-CH2-CH2-COO-
omega gamma beta alpha
• The number before the colon indicates the number
of carbons in the chain, and those after the colon
indicate the numbers and positions of double
bonds. Eg 16:0
• The 16-carbon saturated palmitic acid is
abbreviated as
16:0,
• The 18-carbon oleic acid, with one double bond, is
18:1
• The carbon to which the carboxyl group is attached,
carbon 2 is also called the α-carbon, carbon 3 is the
β-carbon, and carbon 4 is the γ-carbon

• The positions of any double bonds are specified

relative to the carboxyl carbon, numbered l, by
superscript numbers following Δ (delta)
• A 20-carbon fatty acid with one double bond
between C-9 and C-10 (C-1 being the carboxyl
carbon) and another between C-12 and C-13 is
designated 20:2 Δ9,12

• The family of polyunsaturated fatty acids (PUFAs)

with a double bond between the third and fourth
carbon from the methyl end of the chain are of
special importance in human nutrition

CH3-(CH2)-CH2-CH2-CH2-COO-
omega beta alpha
• Because the physiological role of PUFAs is related
more to the position of the first double bond near
the methyl end of the chain than to the carboxyl
end, an alternative nomenclature is sometimes
used for these fatty acids

CH3-(CH2)-CH2-CH2-CH2-COO-
omega beta alpha

• In another numbering system known as ‘n’ or ω

numbering system, the carbon atoms are
numbered from methyl group end
• The carbon of the terminal methyl group is called
the -ω regardless of the chain length
CH3-(CH2)-CH2-CH2-CH2-COO-
omega beta alpha

• Arachidonic acid 20:4Δ5,8,11,14 is referred to as an ω-

6 fatty acid because the closest double bond to the
ω end begins six carbons from that end

• Another ω-6 fatty acid is the essential linoliec acid,

18:2 Δ9, 12

• In contrast, linolenic acid, 18:3Δ9, 12, 15 is an ω-3

fatty acid
 Numbering of carbon atoms inFA

Palmitic acid

Methyl end Carboxyl end

 Nomenclature of FattyAcids

Saturated FAhave both trivial names and systematicnames.

 Nomenclature of FattyAcids

They have trivial names, systematic names, ω-end

names and shorthand forms.
 Nomenclature of FattyAcids

Representation of double bonds of FA 2 systems

1. C- 2. ω-or n-
System System
 1. C-System

2. ω-or n-System
..
In which hydrocarbon side chain is saturated (no
doublebonds).
 Subclassified according to number of doublebonds

Monounsaturated
Polyunsaturated FA
FA
• One double bond • 2 or more double
bonds