Lipids – Part 1- Simple Lipids

Why are they important?

The lipids are a heterogeneous group of compounds, including fats, oils, steroids, waxes, and related
compounds, which are related more by their physical than by their chemical properties. They have the common
property of being (1) relatively insoluble in water and (2) soluble in nonpolar solvents such as ether and chloroform.
They are important dietary constituents not only because of their high energy value but also because of the
fat-soluble vitamins and the essential fatty acids contained in the fat of natural foods. Fat serves as a thermal
insulator in tissues and around certain organs.
Nonpolar lipids act as electrical insulators, allowing rapid propagation of depolarization waves along
myelinated nerves. Combinations of lipid and protein (lipoproteins) are important cellular constituents, occurring
both in the cell membrane and in the mitochondria, and serving also as the means of transporting lipids in the blood.
Knowledge of lipid biochemistry is necessary in understanding many important biomedical areas, eg, obesity,
diabetes mellitus, atherosclerosis, and the role of various polyunsaturated fatty acids in nutrition and health.

Introduction

 Lipids are compounds of biological origin that dissolve in nonpolar solvents such as
chloroform and diethyl ether
o Lipids are defined by the physical operation used to isolate them
o Lipids include a variety of structural types, represented by the following
examples:

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Simple lipids:
Esters of fatty acids with various alcohols.
 Fats: Esters of fatty acids with glycerol. Oils are fats in the liquid state.
 Waxes: Esters of fatty acids with higher molecular weight alcohols.

Complex lipids: Esters of fatty acids containing groups in addition to an alcohol and a fatty acid.
 Phospholipids: Lipids containing, in addition to fatty acids and an alcohol, a phosphoric
acid residue. They frequently have nitrogen containing bases and other substituents, eg,
in glycerophospholipids the alcohol is glycerol and in sphingophospholipids the alcohol
is sphingosine.
 Glycolipids (glycosphingolipids): Lipids containing a fatty acid, sphingosine, and
carbohydrate.
 Other complex lipids: Lipids such as sulfolipids and aminolipids. Lipoproteins may also
be placed in this category.
 Precursor and derived lipids: These include fatty acids, glycerol, steroids, other alcohols,
fatty aldehydes, and ketone bodies, hydrocarbons, lipid-soluble vitamins, and hormones.
Because they are uncharged, acylglycerols (glycerides), cholesterol, and cholesteryl
esters are termed neutral lipids.

 Most long-chain carboxylic acids of biological origin are found as esters of glycerol
o Oils from plants and fats of animal origin are triacylglycerols
o Oils are generally liquids at room temperature, fats are solid
 Saturated fatty acids have higher melting points than unsaturated fatty acids

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o Saturated fatty acids adopt a fully extended conformation, pack well, and have
strong van der Waals attractions between molecules
o Cis double bonds in unsaturated fatty acids put bends in the chain
o Unsaturated fatty acid chains pack poorly and have weaker van der Waals
attractions between molecules than saturated fatty acids
o Unsaturated fatty acids have lower melting points than saturated fatty acids with
the same number of carbons

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  Triacylglycerols with a higher content of saturated fatty acids have higher melting points
 Triacylglycerols in animal fats contain mostly saturated fatty acids and are solids are
room temperature
 Triacylglycerols in oils have a large proportion of unsaturated and polyunsaturated fatty
acids and are therefore liquids are room temperature

Application:

The sperm whale’s head is very large, accounting for over one-third of its total body weight. About 90% of
the weight of the head is made up of the spermaceti organ, a blubbery mass that contains up to 3,600 kg (about 4
tons) of spermaceti oil, a mixture of triacylglycerols and waxes containing an abundance of unsaturated fatty acids.
This mixture is liquid at the normal resting body temperature of the whale, about 37 , ut it egins to crystalli e at
a out C and becomes solid when the temperature drops several more degrees.
The probable biological function of spermaceti oil has been deduced from research on the anatomy and
feeding behavior of the sperm whale. These mammals feed almost exclusively on squid in very deep water. In their
feeding dives they descend 1,000 m or more; the deepest recorded dive is 3,000 m (almost 2 miles). At these depths,
there are no competitors for the very plentiful squid; the sperm whale rests quietly, waiting for schools of squid to
pass.
For a marine animal to remain at a given depth without a constant swimming effort, it must have the same
density as the surrounding water. The sperm whale undergoes changes in buoyancy to match the density of its
surroundings—from the tropical ocean surface to great depths where the water is much colder and thus denser. The
key is the freezing point of spermaceti oil. When the temperature of the oil is lowered several degrees during a deep
dive, it congeals or crystallizes and becomes denser. Thus the buoyancy of the whale changes to match the density
of seawater. Various physiological mechanisms promote rapid cooling of the oil during a dive. During the return to
the surface, the congealed spermaceti oil warms and melts, decreasing its density to match that of the surface water.
The triacylglycerols and waxes synthesized by the sperm whale contain fatty acids of the necessary chain length and
degree of unsaturation to give the spermaceti oil the proper melting point for the animal’s diving ha its.

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Chemistry of simple lipids:
Hydrogenation of Triacylglycerols
 Liquid vegetable oils can be partially hydrogenated to yield solid cooking fats
 Partial hydrogenation isomerizes some of the cis double bonds to trans double bonds
o “Trans” fats have een associated with increased risk of cardiovascular disease
o

Hydrolysis of tracylglyerols yields fatty acids

 Most natural fatty acids have unbranched chains with an even number of carbon atoms
 In natural unsaturated fatty acids the double bonds are all cis and are usually not
conjugated

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  Salts of long-chain carboxylic acids are called soaps
o In water, soaps exist in soluble spherical clusters called micelles
 Micelles have the hydrophilic carboxylate group of the fatty acid salt on the outside
exposed to water
o The nonpolar hydrophobic hydrocarbon chains of the fatty acids are oriented
toward the interior of the micelle (away from water)

The polar groups of most synthetic detergents are sodium sulfonates or sodium sulfates
 Regular soaps tend to precipitate in hard water (water that contains the divalent and
trivalent cations Ca2+ , Fe2+, Fe3+ and Mg2+)
 The soap exchanges its sodium cations for these di- and trivalent metal cations and these
salts tend not to be water insoluble
 In contrast, the di- and trivalent metal ion salts of synthetic detergents are more water
soluble

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Waxes
Waxes are esters of long-chain fatty acids