Sem-2, Paper- CC3, Unit-3

Lipids
Instructed by
Dr Sekhar Pal
Dept of Microbiology
RKMVC College
 Introduction
• The term ‘lipid’ was first used by the German biochemist Walter Bloor
in 1943 for a major class of tissue components and foodstuffs.
According to him, these are substances of biological origin, insoluble
in water but soluble in “fat” solvents.
• The lipids are a heterogeneous group of compounds related to fatty
acids and include fats, oils, waxes and other related substances.
• These are oily or greasy organic substances, relatively insoluble in
water and considerably soluble in organic solvents like ether,
chloroform and benzene. They are, thus, hydrophobic in nature.
• Generally, the fats exist as the esters of glycerol and fatty acids or as
the triglycerides of fatty acids as well as other sterol-containing
metabolites such as cholesterol
 Classification
-Bloor (1943)
A. Simple lipids or Homolipids: Esters of fatty acid with various alcohols.
• 1. Fats and oils (triglycerides or triacylglycerols) are esters of fatty acids with a
trihydroxy alcohol, glycerol. A fat is solid at ordinary room temperature whereas an oil
is liquid.
• 2. Waxes. These are esters of fatty acids with high molecular weight monohydroxy
alcohols.
B. Compound lipids or Heterolipids: Esters of fatty acids with alcohol and possess
additional group(s).
• 1. Phospholipids (phosphatides) are compounds containing, in addition to fatty acids
and glycerol, a phosphoric acid, nitrogenous groups and other substituents.
• 2. Glycolipids (cerebrosides) are the compounds of fatty acids with carbohydrates and
contain nitrogen but no phosphoric acid. The glycolipids also include certain
structurally-related compounds comprising the groups, gangliosides, sulfolipids and
sulfatids.
C. Derived lipids: These are the substances derived from simple and compound lipids by
hydrolysis. These include fatty acids, alcohols, mono- and diglycerides, steroids, terpenes
and carotenoids.
-Conn and Stumpf (1976)
• 1. Acyl glycerols
• 2. Waxes
• 3. Phospholipids
• 4. Sphingolipids
• 5. Glycolipids
• 6. Terpenoid lipids including carotenoids and steroids
 Storage Lipids
• The fats and oils used almost universally as stored forms of energy in living organisms are
made of fatty acids.
• The fatty acids are hydrocarbon derivatives, at about the same low oxidation state (that is,
as highly reduced) as the hydrocarbons in fossil fuels. The cellular oxidation of fatty acids
(to CO2 and H2O), like the controlled, rapid burning of fossil fuels in internal combustion
engines, is highly exergonic.
• Two types of fatty acid–containing compounds, triacylglycerols and waxes, describes the
diversity of structure and physical properties in this family of compounds.
• Triacylglycerol (TAG) is found in all organs of the human body, particularly in adipose
tissue, in which droplets of triacylglycerols may represent more than 90% of the
cytoplasm of the cells. The Arctic and Antarctic animals such as whales, seals, walruses,
penguins are amply padded with triglycerides to serve both as energy storage depots and
as an insulation against very low temperatures.
• Most fats and oils, upon hydrolysis, yield several fatty acids as well as glycerol.
 Fatty Acids
• Fatty acids are carboxylic acids with hydrocarbon
chains ranging from 4 to 36 carbons long (C4 to
C36). A few contain three-carbon rings, hydroxyl
groups, or methyl group branches.
• They usually occur in esterified form as major
components of the various lipids.
• In higher plants and animals, the predominant fatty
acid residues are those of the C16 and C18 species:
palmitic, oleic, linoleic, and stearic acids. Fatty
acids with <14 or >20 carbon atoms are
uncommon. Most fatty acids have an even number
of carbon atoms because they are biosynthesized
by the concatenation of C2 units.
• Over half of the fatty acid residues of plant and
animal lipids are unsaturated and are often
polyunsaturated. Bacterial fatty acids are rarely
polyunsaturated but are commonly branched,
hydroxylated, or contain cyclopropane rings.
• A simplified nomenclature for these compounds specifies the chain length and number of
double bonds, separated by a colon.
• The positions of any double bonds are specified by superscript numbers following Δ (delta); e.g.
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 first double bond of an unsaturated fatty acid commonly occurs between its C9 and C10
atoms counting from the carboxyl C atom. Further double bonds, if present, tend to occur at
every third carbon atom and so are not conjugated (alternating single and double bonds).
• In nearly all naturally occurring unsaturated fatty acids, the double bonds are in the cis
configuration (e.g. vegetable oils such as olive oil, mustard oil, fish oils such as ray, shark and
cod). Trans fatty acids are produced by fermentation in the rumen of dairy animals and are
obtained from dairy products, meat and also produced during hydrogenation of fish or
vegetable oils (margarine, fried foods, baked goods etc.).
• Diets high in trans fatty acids (Doughnuts, cookies, muffins, pies, cakes, french fries etc.)
correlate with increased blood levels of LDL (bad cholesterol) and decreased HDL (good
cholesterol).
• Two important classes of polyunsaturated fatty acids are designated as ω–3 or ω–6 fatty acids
(dietary sources include mackerel, salmon, cod liver oil, corn, sunflower, nuts) a nomenclature
that identifies the last double-bonded carbon atom as counted from the methyl terminal (ω)
end of the chain. They are important cell component, energy source and help keep heart, lungs,
blood vessels, and immune system in good working condition.
• Saturated fatty acids (which are fully reduced or “saturated” with
hydrogen) are highly flexible molecules that can assume a wide range of
conformations because there is relatively free rotation around each of their
C—C bonds. Nevertheless, their lowest energy conformation is the fully
extended conformation, which has the least amount of steric interference
between neighboring methylene groups. The melting points (mp) of
saturated fatty acids, like those of most substances, increase with their
molecular mass.
• Fatty acid double bonds having the cis configuration puts a rigid 30° bend
in the hydrocarbon chain. Consequently, unsaturated fatty acids pack
together less efficiently than saturated fatty acids. The reduced van der
Waals interactions of unsaturated fatty acids cause their melting points to
decrease with the degree of unsaturation.
• The fluidity of lipids containing fatty acid residues likewise increases with
the degree of unsaturation of the fatty acids. This phenomenon has
important consequences for biological membranes.
 References and further reading
• Lehninger Principles of Biochemistry: International Edition by Nelson
& Cox. W H Freeman & Co.
• Fundamentals of Biochemistry. Voet & Voet. John Wiley & Sons, Inc.
• Biochemistry. Stryer et al.