Lipids

• It has been difficult to provide a definition for the class of

substances called lipids.

• Early definitions were mainly based on whether the substance is

soluble in organic solvents like ether, benzene, or chloroform and
is not soluble in water.

• Up to 99 percent of the lipids in plant and animal material consist

of esters, known as fats and oils.

• Fats are solid at room temperature, and oils are liquid.

• The fat content of foods can range from very low to very high in
both vegetable and animal products
• Fats and oils may differ considerably in composition, depending on
their origin.

• classified broadly as of animal or vegetable origin

• Animal fats can be further subdivided into mammal depot fat (lard
and tallow) and milk fat (mostly ruminant) and marine oils (fish
and whale oil).

• Vegetable oils and fats can be divided into seed oils (such as
soybean, canola), fruit coat fats (palm and olive oils), and kernel
oils (coconut and palm kernel).

• The scientific name for esters of glycerol and fatty acids is

acylglycerols.
 SHORTHAND DESCRIPTION OF FATTY ACIDS AND GLYCERIDES

• In this convention the composition of a fatty acid can be described

by two numbers separated by a colon.

• The first number indicates the number of carbon atoms in the fatty
acid chain, the second number indicates the number of double
bonds. Thus, 4:0 is short for butyric acid, 16:0 for palmitic acid,
18:1 for oleic acid, etc.

• For unsaturated fatty acids, information about the

• Location of double bonds
– Numbers of double bonds and
• Their stereo isomers can be given
• In some cases polyunsaturated fatty acids are numbered starting at
the methyl end; for instance, linoleic acid is represented as 18:2n-
6 and linolenic acid 18:3n-3.

• These symbols indicate straight-chain, 18-carbon fatty acids with

two and three methylene interrupted cis double bonds that start at
the sixth and third carbon from the methyl end, respectively.

• These have also been described as Ω6 and Ω3.

• Triglycerides can be abbreviated by using the first letters of the

common names of the component fatty acids. SSS indicates
tristearin, PPP tripalmitin, and SOS a triglyceride with two
stearin acid residues in the 1 and 3 positions and oleic acid in
the 2 position
 COMPONENT FATTY ACIDS
• It is customary to divide the fatty acids into different groups, for
example, into saturated and unsaturated ones.

• This particular division is useful in food technology because

saturated fatty acids have a much higher melting point than
unsaturated ones, so the ratio of saturated fatty acids to
unsaturated ones significantly affects the physical properties of a
fat or oil.

• Another common division is into short-chain, medium-chain, and

long-chain fatty acids.

• Generally, short-chain fatty acids have from 4 to 10 carbon atoms;

medium-chain fatty acids, 12 or 14 carbon atoms; and long-chain
fatty acids, 16 or more carbon atoms.
• The naturally occurring unsaturated fatty acids in fats are almost exclusively
in the cis-form,

• Depot fats of higher land animals consist mainly of palmitic, oleic, and stearic
acid and are high in saturated fatty acids

• Ruminant milk fats are characterized by a much greater variety of component

fatty acids.
 Lower saturated acids with 4 to 10 carbon atoms are present in relatively large
amounts.
 The major fatty acids are palmitic, oleic, and stearic

• Marine oils also contain a wide variety of fatty acids.

 They are high in unsaturated fatty acids, with 20 or 22 carbons or more

 Cont..
• Fruit coat fats contain mainly palmitic, oleic, and sometimes
linoleic acids.

• Seedfats are characterized by low contents of saturated fatty acids.

They contain palmitic, oleic, linoleic, and linolenic acids.

• Sometimes unusual fatty acids may be present, such as erucic acid

in rapeseed oil.

• Recent developments in plant breeding have made it possible to

change the fatty acid composition of seed oil dramatically.

• Rapeseed oil in which the erucic acid has been replaced by oleic
acid is known as canola oil.
 COMPONENT GLYCERIDES
• Natural fats can be defined as mixtures of triglycerides.

• Simple triglycerides are virtually absent in natural fats, and the distribution of
fatty acids both between and within glycerides is selective rather than
random.

• Glycerol has a plane of symmetry or mirror plane, because two of the four
substituents on the central carbon atom are identical.

• A racemic mixture is a mixture of equal amounts of enantiomers

 .
• In vegetable fats and oils, the saturated fatty acyl groups have a
tendency to occupy the 1- and 3- positions in the glycerides and the
unsaturated acyl groups occupy the 2-position.

• The distribution among the three positions was nonrandom. The

distribution of fatty acids seems to be governed by chain length and
unsaturation.

• In most fats a short chain and unsaturation direct a fatty acid toward
position 2 position.

• In the fats of marine animals, chain length is the directing factor,

with polyunsaturated and short-chain fatty acids accumulated in the
2- position and long chains in the 1- and 3- positions
 PHOSPHOLIPIDS
• All fats and oils and fat-containing foods contain a number of phospholipids.

• The lowest amounts of phospholipid are present in pure animal fats such as
lard and beef tallow.

• In some crude vegetable oils, such as cottonseed, corn, and soybean oils,
phospholipids may be present at levels of 2 to 3 percent.

• Fish, Crustacea, and mollusks contain approximately 0.7 percent of

phospholipids in the muscle tissue.

• Phospholipids are surface active, because they contain a lipophilic and

hydrophilic portion.

• Since they can easily be hydrated, they can be removed from fats and oils
during the refining process.
• After refining of oils, neutralization, bleaching, and deodorization, the
phospholipid content is reduced to virtually zero

• The phospholipids removed from soybean oil are used as emulsifiers in certain
foods, such as chocolate

UNSAPONIFIABLES
• The unsaponifiable fraction of fats consists of sterols, terpenic alcohols,
aliphatic alcohols, squalene, and hydrocarbons

• In most fats the major components of the unsaponifiable fraction are sterols.

• Animal fats contain cholesterol.

• Plant fats and oils contain phytosterols.

• Sterols are compounds containing the perhydro-cyclopenteno-
phenanthrene nucleus, which they have in common with many
other natural compounds, including bile acids, hormones, and
vitamin D.

• The sterols are solids with high melting points. Stereo chemically
they are with trans linkages,

• The sterols provide a method of distinguishing between animal

and vegetable fats by means of their acetates.

• Cholesterol acetate has a melting point of 1140C, whereas

phytosterol acetates melt in the range of 126 to 1370C.
 AUTOXIDATION
• The unsaturated bonds present in all fats and oils represent active centers that, among
other things, may react with oxygen

• This reaction leads to the formation of primary, secondary, and tertiary oxidation
products that may make the fat or fat-containing foods unsuitable for consumption.

• The process of autoxidation and the resulting deterioration in flavor of fats and fatty
foods are often described by the term rancidity

• Factors that affect the rate of oxidation are the following:

 amount of oxygen present,

 degree of unsaturation of the lipids,
 presence of antioxidants ,
 presence of prooxidants, especially copper,
 nature of packaging material,
 light exposure,
 temperature of storage
• The autoxidation reaction can be divided to three parts: initiation,
propagation, and termination.

• In the initiation part, hydrogen is abstracted from an olefmic compound to

yield a free radical.

• The removal of hydrogen takes place at the carbon atom next to the double bond
and can be brought about by the action of, for instance, light or metals.

• This reaction may be repeated up to several thousand times and has the nature of
a chain reaction.
 Cont..
• The propagation can be followed by termination if the free radicals react with
themselves to yield nonactive products, as shown here:

Although even saturated fatty acids may be oxidized, the rate of

oxidation greatly depends on the degree of unsaturation

In the series of 18-carbon-atom fatty acids 18:0, 18:1, 18:2, 18:3, the
relative rate of oxidation has been reported to be in the ratio of
1:100:1200:2500.
 PHOTOOXIDATION
• Oxidation of lipids, in addition to the free radical process, can be brought
about by at least two other mechanisms photooxidation and enzymic oxidation
by lipoxygenase.

• Light induced oxidation or photooxidation results from the reactivity of an

excited state of oxygen, known as singlet oxygen.

• Singlet-state oxygen production requires the presence of a sensitizer.

• The sensitizer is activated by light, and can then either react directly with the
substrate (type I sensitizer) or activate oxygen to the singlet state (type II
sensitizer)

• In both cases unsaturated fatty acid residues are converted into

hydroperoxides.
 Cont..
• The reactivity of singlet oxygen is 1,500 greater than that of
ground-state oxygen

• Compounds that can act as sensitizers are widely occurring food

components, including chlorophyll, myoglobin, riboflavin, and
heavy metals
 Cont..
HEATED FATS—FRYING
• Fats and oils are heated during commercial processing and during
frying.

• Heating during processing mainly involves hydrogenation, physical

refining, and deodorization.

• Temperature used in these processes may range from 12O0C to 27O0C.

• The oil is not in contact with air, which eliminates the possibility of
oxidation.

• At the high temperatures used in physical refining and deodorization,

several chemical changes may take place.
Trans Isomer Formation in Sunflower Oil as a Function of Deodorization
Temperature.
 HYDROGENATION
• Hydrogenation of fats is a chemical reaction consisting of
addition of hydrogen at double bonds of unsaturated acyl
groups.

• it permits the conversion of liquid oils into production of

margarine and shortening.

• the process also results in a decreased susceptibility to oxidative

deterioration

• In the hydrogenation reaction, gaseous hydrogen, liquid oil, and

solid catalyst participate under agitation in a closed vessel
• When hydrogen is added the result depends on many factors, if the
reaction is not carried to completion.

• Generally, hydrogenation of fats is not carried to completion and

fats are hydrogenated only partially.

• Under these conditions, hydrogenation may be selective or

nonselective. Selectivity means that hydrogen is added first to the
most unsaturated fatty acids.

• Selectivity is increased by increasing hydrogenation temperature

and decreased by increasing pressure and agitation
• Another important factor in hydrogenation is the formation of positional and
geometrical isomers. Formation of trans isomers is rapid and extensive.

• Nickel catalysts are poisoned by sulfur and phosphorous

compounds, free fatty acids,

• Oils are refined and sometimes bleached before hydrogenation.

Sulfur compounds are not easily removed from the oil

• When catalysts are poisoned by sulfur the hydrogenation reaction is

slowed down and the formation of trans isomers is increased
 FRACTIONATION
• Fats can be separated into fractions with different physical
characteristics by fractional crystallization from a solvent or by
fractionation from the melt.

• uses of fractional crystallization

1. To remove small quantities of high melting components that might

result in cloudiness of an oil.

2. To change a fat or oil into two or more fractions with different

melting characteristics.

3. To produce well-defined fractions with special physical properties

that can be used as specialty fats or confectionery fats.
 FATS AND OILS
Identification and Compositional Analysis

1. Acid Value (AV)

• This value is important for determination of free fatty acids (FFA) in
crude and refined oils and fats.

• It is the number of milligrams of KOH needed to neutralize the organic

acids present in 1 g of oil or fat.

2. Saponification Number (SN)

 This is the weight of KOH (in mg) needed to hydrolyze a one-gram

sample of an oil or fat.

 The higher the SN, the lower the average molecular weight of the
fatty acid in the triglycerides.
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3. Composition of Fatty Acids

 The saturated and unsaturated fatty acids with 8 to 24 carbon

atoms in animal fats, vegetable oils, marine oils and fatty acids
are quantitatively determined by gas chromatography (GC)
after conversion to their methyl ester forms.

 Free fatty acid analysis is also possible by using specially

selected stationary solid phases.

 A capillary gas liquid chromatographic method is also used to

measure fatty acid composition and levels of trans unsaturation
and cis.

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