Lipids

• Lipids consist of a broad group of compounds that are generally

soluble in organic solvents but only sparingly soluble in water.

• They are major components of adipose tissue, and together with

proteins and carbohydrates, they constitute the principal structural
components of all living cells.

• Glycerol esters of fatty acids, which make up to 99% of the lipids

of plant and animal origin, have been traditionally called fats and oils.

1
 Cont’d
• Lipids either consumed in the form of:

– “Visible” fats, which have been separated from the original plant
or animal sources, such as:
• butter,
• lard, and
• shortening, or
– as constituents of basic foods, such as:
• milk,
• cheese, and
• meat.

2
 Cont’d
• Vegetable oil comes from the seeds of:
• soybean, sesame, niger,
• cottonseed, and peanut, and
• the oil-bearing trees of palm, coconut, and olive.
– their composition,
– crystalline structure,
– melting properties, and
– ability to associate with water and other non lipid molecules.
are especially important to their functional properties in
many foods.

3
 Cont’d
• Dietary lipids play an important role in nutrition:
– supply calories, and essential fatty acids
– act as vitamin carriers, and
– increase the palatability of food.

• But for decades they have been at the center of controversy with
respect to;
– toxicity,
– obesity, and
– disease.

4
Nomenclature

1. Fatty acids
• refer to any aliphatic monocarboxylic acid that can be liberated
by hydrolysis from naturally occurring fats.
a. Saturated fatty acids
• The IUPAC have standardized systematic descriptions of fatty
acids.
• The IUPAC system names the parent hydrocarbon of the fatty
acid on the basis of the number of carbons (e.g., ten carbons
would be decane).
• Since fatty acids contain a carboxylic acid group, the terminal e
in the hydrocarbon’s name is replaced by oic (e.g., decanoic).
• Many of the common names originate from the source that the
fatty acid was commonly or traditionally isolated (e.g., palmitic
acids and palm oil). 5
 Cont’d
• A numerical system can be used for abbreviated names.

• The first number in this system designates the number of carbons in the
fatty acids while the second number designates the number of double
bonds (e.g.hexadecanoic=palmitic=16:0).

b. Unsaturated fatty acids

• It can be named after the parent unsaturated hydrocarbons.

• Replacement of the terminal anoic by enoic indicates unsaturation, and
the di, tri, and so on represent the number of double bonds present.

• The simplest way to specify the location of double bonds is to put,

before the name of the acid, one number for each unsaturated linkage.
6
 Cont’d
Eg.1
O
8 7 6 5 4 3 2 1
CH3 CH2 CH2 CH2 CH CH CH2 C OH
3-octenic acid

Eg.2
O
8 7 6 5 4 3 2 1
CH3 CH CH CH2 CH CH CH2 C OH
3,6-octadienoic acid

Short hand: 8:1(∆3)

8:2(∆3,6)
7
Acylglycerols (glycerides)

• Over 99% of the fatty acids found in plants and animals are esterified to
glycerol (to form glycerides).

• Free fatty acids are not common in living tissues because they are cytotoxic
owing to their ability to disrupt cell membrane organization.

• Neutral fats are: mono-, di-, and triesters of glycerol with fatty acids, and
are termed;
– monoacyl-glycerols, diacylglycerols, and triacylglycerols,
respectively. But Triacylglycerols are the most common of the three in
foods.

8
 Cont’d
O
O
H2 C O C R
H2C OH HO C R O
O
HC OH HC O C R + 3 H2O
+ HO C R
H2 C OH O
O
HO C R H2 C O C R

Glycerol 3 fatty acids triglycerides

9
Sterols

• Sterols are derivatives of steroids.

• These non-polar lipids all have three six-carbon rings and a five
carbon ring that is attached to an aliphatic chain. Sterols have a
hydroxyl group attached to carbon 3 of the A ring.
• Sterols are found in both plants (phytosterols) and animals
(zoosterols).

• Cholesterol is the major sterol found in animal lipids.

• Plant lipids contain numerous sterols with β-sitosterol and
stigmasterol predominating.

10
 Cont’d

Structures of sterols commonly found in foods

11
Classification of lipids

• A general classification of lipids based on their structural components

can be generally classified as:

– Simple lipids- acylglycerols, waxes

– Compound lipids- phosphoacylglycerols, etc.
– Derived lipids- carotenoids, steroids, fat soluble vitamins
Such a classification, however, is possibly too rigid for a group
of compounds as diverse as lipids, and should be used only as
a guide.

 The most abundant class of food lipids is the acylglycerols, which

dominate the composition of depot fats in animals and plants.
 In some plants, glycolipids constitute the major polar lipids in cell
membranes.
 Waxes are found as protective coatings on skin, leaves, and fruits.12
Chemical properties of lipids

1. Lipolysis (Hydrolysis of ester bonds in lipids):

• may occur by:
• enzyme action or
• by heat and moisture resulting in the liberation of free fatty
acids.
• Free fatty acids are virtually absent in fat of living animal tissue.
• They can form, however, by enzyme action after the animal is killed.
• The release of short-chain fatty acids by hydrolysis is responsible for
the:
development of an undesirable rancid flavor (hydrolytic
rancidity) in raw milk.

13
 Cont’d
• Controlled and selective lipolysis is also used:
in the manufacture of other food items, such as yogurt and
bread.

• In contrast to animal fats,

oils in mature oil seeds may have undergone substantial hydrolysis
by the time they are harvested giving rise to significant amounts of
free fatty acids.
• Neutralization with alkali is thus required for most vegetable oils after
they are extracted.

• Lipolysis is a major rxn occurring during deep-fat frying due to:

• the large amounts of water introduced from the food, and
• the relatively high temperatures used. 14
 Cont’d
• Development of high levels of free fatty acids during frying is usually
associated with:
• decreases in smoke point and
• surface tension of the oil and a reduction in quality of the fried
food.

• Enzymatic lipolysis is used extensively as an analytical tool in lipid

research.

15
2. Oxidative reactions

• Lipid oxidation: is a general term that is used to describe a complex

sequence of chemical changes that result from the interaction of lipids
with oxygen. It is:
• one of the major causes of food spoilage,
• great economic concern to the food industry because it leads to
the development of various off flavors and off odors generally
called rancid (oxidative rancidity)—decreases acceptability,
• decrease the nutritional quality of food, and
• Produce toxic substances.

• On the other hand, a limited degree of lipid oxidation is sometimes

desirable, as in aged cheeses and some fried foods.
16
 Cont’d
Mechanisms of lipid oxidation
• The centerpiece of these reactions is the molecular species known as
free radicals.
• Free radicals are molecules or atoms that have unpaired electrons.
Free radical species can vary greatly in their energy.
• Radicals such as the hydroxyl radical (•OH) have very high energy
and can oxidize virtually any molecule by causing hydrogen
abstraction.

• The kinetics of lipid oxidation in foods often has a lag phase followed
by an exponential increase in oxidation rate

17
 Cont’d
• The length of the lag phase is very important to food processors
since this is the period where rancidity is not detected and the quality
of the food is high.
• Once the exponential phase is reached,
lipid oxidation proceeds quickly and off-aroma development
occurs rapidly.

18
 Factors influencing rate of lipid oxidation in foods
• Food lipids contain a variety of fatty acids that differ in:
– chemical,
– physical properties and
– also in their susceptibility to oxidation.
• In addition, foods contain numerous non lipid components that may co-
oxidize and/or interact with:
– the oxidizing lipids and
– their oxidation products.
• Thus, oxidation of lipids in food is:
– a dynamic,
– multifaceted series of events,
– often overlapping and continually interacting
which makes accurate description of oxidation kinetics almost
19
impossible.
3. Thermal decomposition
•. Heating of food produces various chemical changes, some of which
can be important to:
– flavor,
– appearance,
– nutritive value, and
– toxicity.
• Not only do the different nutrients in food undergo decomposition
rxns, but these nutrients also interact among themselves in extremely
complex ways to form a very large number of new compounds.

20
 Cont’d
• The chemistry of lipid oxidation at high temperatures is complicated
by the fact that:
– both thermolytic and
– oxidative reactions are simultaneously involved.
• Both saturated and unsaturated fatty acids undergo chemical
decomposition when exposed to heat in the presence of oxygen.

21
Generalized schemes for thermal decomposition of lipids

22