LIPID CHEMISTRY

What are Lipids?

Lipids are bio-molecules that are:

• Hydrophobic in nature because of the high amount of Hydrocarbons in their

structure

• Relatively insoluble in water but readily soluble in nonpolar solvents such as

Chloroform, Benzene and Ether,

• Easily separated from other biological materials by extraction into organic

solvents because of their hydrophobic properties,

• Examples of lipids: Fats, Oils, Steroids, Waxes, Fat-soluble Vitamins

What are fatty acids?

• Aliphatic Carboxylic Acids containing Long Hydrocarbon chains that may be

Saturated or Unsaturated,

• Fatty acid has both Hydrophobic and Hydrophilic properties, thus are Amphipathic
in nature, Fatty acid can be separated into two distinct parts: Non-polar
Hydrophobic Hydrocarbon Chain (Tail) ,Polar (-COOH) group (Hydrophilic Head) .

• Most naturally occurring fatty acids, obtained from hydrolysis of natural fats and
oils contain Even number of carbon atoms because they are synthesized from Two-
carbon units, • Examples of fatty acids: Palmitic Acid, Oleic Acid, Arachidonic
Acid, Linoleic Acid, Linolenic Acid, et

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Simple diagram to illustrate the structure of Fat

NOMENCLATURE OF SATURATED FATTY ACIDS

Systematic nomenclature of saturated fatty acids

1. IUPAC system (Systematic name or Genevan system)

• IUPAC or Systematic name of a fatty acid is formed by replacing the ending -e

with suffix -oic acid in the name of the Alkane with the same number of carbon
atoms,

• Carboxyl Carbon is Carbon number one,

• Examples: 16C fatty acid is: Hexadecanoic acid (from Hexadecane) 18C fatty
acid is: Octadecanoic acid (from Octadecane).

2. Common names

Common names of fatty acids are generally derived from either the Latin or Greek
name of their source of origin,

•Greek letters or symbols (, , , , , etc.) can be used to number Carbon atoms in
fatty acid molecules,

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• Examples of Common names: • Palmitic acid from Latin - Palma (palm tree); •
Arachidic acid from Greek - Arachne (spider), etc

IMPORTANT TO NOTE

Nomenclature of fatty acids should not mix Greek letters or symbols with
Systematic names of fatty acids, nor should numerals be mixed with Common
names of fatty acids;

• Carboxyl Carbon in a fatty acid molecule is always considered as the First Carbon
(C-1) in Systematic name, it has no corresponding Greek letter or symbol in
Common name,

• In Systematic name: Second Carbon atom (C-2) in Fatty Acid molecule

corresponds to the -Carbon in Common name, Third Carbon atom (C-3) in Fatty
Acid molecule corresponds to -Carbon atom in Common name and so on,

Last or Terminal Carbon atom in a fatty acid molecule is considered as the -

Carbon or the n-carbon atom,

Common names, Systematic names and Short Hand Formula of some Saturated
Fatty Acids

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SYSTEMATIC NOMENCLATURE OF UNSATURATED FATTY ACIDS

Carboxyl Carbon is the First Carbon Atom (C-1)

• Systematic Nomenclature indicates:

Number of Carbon atoms in the Fatty acid,

• Number of Double bonds (unless it has only one double bond),

• Position of the Double bonds,

• Contain the suffix enoic,

• The delta () numbering system is used to indicate the position of the double bond
in fatty acids.

Schematic diagrams of Saturated and Unsaturated Fatty Acids

What are the groups of polyunsaturated fatty acids?

• Polyunsaturated fatty acids are grouped into Three series or families based on the
Omega nomenclature.

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The groups are:  9 or n-9 series: • Fatty acids in which the first double bond is
between C9 and C10 counting from the -carbon; • Examples: Oleic acid and
Gondoic acid

 6 or n-6 series: • Fatty acids in which the first double bond is between C6 and C7
counting from the -carbon; • Examples: Linoleic acid and Arachidonic acid

 3 or n-3 series: • Fatty acids in which the first double bond is between C3 and C4
counting from the -carbon; • Examples: -Linolenic acid and Timnodonic acid

What are the essential fatty acids?

• ESSENTIAL FATTY ACIDS are Unsaturated fatty acids that cannot be

biosynthesized in tissues of some animals including humans, thus they must be
obtained in the diet.

Examples: • Linoleic acid (18:2;9,12) and • -Linolenic acid (18:3;9,12,15)

• Most of the essential fatty acids are members of the  6 and  3 series; • Some
animals including humans can biosynthesize Arachidonic acid from Linoleic acid
obtained in the diet;

What are the major classes of lipids?

Lipids can be separated into 3 major classes:

1. Simple lipids: Esters that fatty acids form with various alcohols;

• Simple lipids are made up of: • Fats, • Oils, • Waxes

• Fats and oils are esters of Fatty Acids and Glycerol;

• Waxes are esters of fatty acids and higher molecular weight monohydric alcohols

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Biological waxes are esters of long-chain (C14 to C36) saturated and unsaturated fatty

acids with long-chain (C16 to C30) alcohols. The structure of the wax,

triacontanoylpalmitate, which is the major component of the beeswax used in

honeycomb construction

• Complex lipids: Esters made up of Fatty Acids, Alcohol and other chemical
compounds, •Complex lipids are made up of: • Phospholipids, • Glycolipids, •
Glycosphingolipids

Simple Lipids:

Triacylglycerols (Triglycerides or Neutral Fats) are Triesters of Glycerol and 3 Fatty

acids,

• General structure of a Triacylglycerol contains 3 Fatty Acyl groups linked by ester

bonds to Glycerol (Propane1, 2, 3-triol), • If the fatty acyl groups that are esterified
to C-1 and C-3 of the glycerol molecule are different, then the C-2 of the Glycerol
molecule is asymmetric (Chiral center).

Why are Simple Triacylglycerols different from Mixed Triacylglycerols?

Triacylglycerol that contains identical fatty acyl groups that are esterified to the
three-ester positions of Glycerol is called a Simple Triacylglycerol;

• Eexample, Triolein (Tri-oleoyl-glycerol) contains three molecules of Oleic acid

residues esterified to a molecule of Glycerol, • Tri-stearin (Tri-stearoyl-glycerol)
contains three Stearic acid residues esterified to a molecule of glycerol.

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Diagrams of Simple Tri-acyl-glycerols

Mixed Triacylglycerols contain two or three different types of fatty acid residues
esterified to a molecule of Glycerol,

• Such compounds are named according to the placement of the fatty acid residues
on the glycerol molecule, • Examples: 1-palmitoleoyl-2-linoleoyl-3-stearoyl-
glycerol;

• Complex lipids: Esters made up of Fatty Acids, Alcohol and other chemical
compounds, •Complex lipids are made up of: • Phospholipids, • Glycolipids, •
sphingolipids

OVERVIEW OF PHOSPHOLIPIDS

Phospholipids are polar, ionic compounds composed of an alcohol that is attached

by a phosphodiester bridge to either diacylglycerol or sphing o sine. Like fatty acids,
phospholipids are amphipathic in nature, that is, each has a hydrophilic head (the
phosphate group plus whatever alcohol is attached to it, for example, serine,
ethanolamine, and choline), and a long, hydrophobic tail (containing fatty acids or
fatty acid–derived hydrocarbons, shown in orange in). Phospholipids are the

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predominant lipids of cell membranes. In membranes, the hydrophobic portion of a
phospholipid molecule is associated with the nonpolar portions of other membrane
constituents, such as glycolipids, proteins, and cholesterol.

The hydrophilic (polar) head of the phospholipid extends outward, interacting with
the intracellular or extracellular aqueous environment. Membrane phospholipids
also function as a reservoir for intracellular messengers, and, for some proteins,
phospholipids serve as anchors to cell membranes. Nonmembrane-bound
phospholipids serve additional functions in the body, for example, as components of
lung surfactant and essential components of bile, where their detergent properties
aid in the solubilization of cholesterol.

STRUCTURE OF PHOSPHOLIPIDS

There are two classes of phospholipids: those that have glycerol as a backbone and
those that contain sphingosine. Both classes are found as structural components of
membranes, and both play a role in the generation of lipid-signaling molecules.

Glycerophospholipids (I)

Glycerophospholipids, also called phosphoglycerides, are membrane lipids in which

two fatty acids are attached in ester linkage to the first and second carbons of
glycerol, and a highly polar or charged group is attached through a phosphodiester
linkage to the third carbon.

Glycerophospholipids are named as derivatives of the parent compound,

phosphatidic acid (Fig.) Phosphatidic acid is the simplest phosphoglyceride, and is

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the precursor of the other members of this group, according to the polar alcohol in
the head group. Phosphatidylcholine and phosphatidylethanolamine, for example,
have choline and ethanolamine as their polar head groups. In all these compounds,
the head group is joined to glycerol through a phosphodiester bond, in which the
phosphate group bears a negative charge at neutral pH. The polar alcohol may be
negatively charged (phosphatidylinositol 4,5-bisphosphate), neutral
(phosphatidylserine), or positively charged (phosphatidylcholine
phosphatidylethanolamine). The charges of the head groups contribute greatly to the
surface properties of membranes.

The distribution of molecular species is specific for different organisms, different

tissues of the same organism, and different glycerophospholipids in the same cell or

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tissue. In general, animal glycerophospholipids contain a C16 or C18 saturated fatty

acid at C-1 of glycerol, and a C18 or C20 unsaturated fatty acid at C-2.

2. Cardiolipin: Two molecules of PA esterified through their phosphate groups to an

additional molecule of glycerol is called cardiolipin (diphosphatidylglycerol,
Figure). Cardiolipin is found in bacteria and eukaryotes. In eukaryotes, cardiolipin is
virtually exclusive to the inner mitochondrial membrane, where it appears to be
required for the maintenance of certain respiratory complexes of the electron
transport chain.

Ether Lipids

Plasmalogens

When the fatty acid at carbon 1 of a glycero - phospholipid is replaced by an

unsaturated alkyl group attached by an ether (rather than by an ester) linkage to the
core glycerol molecule, a plasmalogen is produced. The membranes of vertebrate
heart tissue are enriched in ether lipids

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Platelet-activating factor

This is an unusual ether glycero - phospholipid, with a saturated alkyl group in an

ether link to carbon 1 and an acetyl residue (rather than a fatty acid) at carbon 2 of
the glycerol backbone (Figure). PAF is synthesized and released by a variety of cell
types. It binds to surface receptors, triggering potent thrombotic and acute
inflammatory events. For example, PAF activates inflammatory cells and mediates
hypersensitivity, acute inflammatory, and anaphylactic reactions. It causes platelets
to aggregate and degranulate, and neutrophils and alveolar macrophages to generate
superoxide radicals

Sphingolipids

Sphingolipids are a large class of membrane lipids that have a polar head group and
two nonpolar tails. Unlike glycerophospholipids and galactolipids they contain no
glycerol. Instead, sphingolipids are composed of one molecule of the long-chain
amino alcohol sphingosine (also called 4-sphingenine) or one of its derivatives, one
molecule of a long-chain fatty acid, and a polar head group that is joined by a
glycosidic linkage in some cases and by a phosphodiester bond in others (Fig. ).

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Carbons C-1, C-2, and C-3 of the sphingosine molecule are structurally analogous to
the three carbons of glycerol in glycerophospholipids. When a fatty acid is attached
in amide linkage to the -NH2 on C-2 of sphingosine, the resulting compound is a

ceramide.

There are three subclasses of sphingolipids, which are all derivatives of ceramide,
but differ in their head groups. These are the sphingomyelins, neutral (uncharged)
glycosphingolipids, and gangliosides (Fig. ). Sphingomyelins contain
phosphocholine as their polar head groups and are therefore classified along with
glycerophospholipids as phospholipids (Fig ). As shown in the next slide,
sphingomyelins are structurally very similar to glycerophospholipids.
Sphingomyelins are present in the plasma membranes of animal cells and are
especially prominent in myelin, a membraneous sheath that surrounds and insulates
the axons of some neurons--thus the name “sphingomyelins.”

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 Structure of Sphingomyelin
Sphingomyelins resemble phosphatidylcholines in their general properties and
three-dimensional structure, and in having no net charge on their head groups (Fig).
While their dimensions and physical properties are similar, they presumably play
different roles in membranes

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