Chemistry of lipids

Chemistry of LipidsChemistry of Lipids

Chemistry of LipidsChemistry of Lipids
Definition:
- Lipids are organic compounds formed mainly from
alcohol and fatty acids combined together by ester
linkage.
CH2R
Fattyalcohol
OH C R
Fattyacid
HO
O
+
H2O
CH2R O C R
O
Esterase (lipase) ester (lipid)

- Lipids are insoluble in water, but soluble
in fat or organic solvents (ether,
chloroform, benzene, acetone).
- Lipids include fats, oils, waxes
and related compounds.
They are widely distributed in nature
both in plants and in animals.

Bi ol ogi cal Import ance
of Li pi ds:
1. They are more palatable and storable to unlimited amount
compared to carbohydrates.
2. They have a high-energy value (25% of body needs) and they
provide more energy per gram than carbohydrates and
proteins but carbohydrates are the preferable source of
energy.
3. Supply the essential fatty acids that cannot be synthesized by
the body.
4. Supply the body with fat-soluble vitamins (A, D, E and K).
5. They are important constituents of the nervous system.
6. Tissue fat is an essential constituent of cell membrane and
nervous system. It is mainly phospholipids in nature that are
not affected by starvation.

7-Stored lipids “depot fat” is stored in all human cells acts as:
 A store of energy.
 A pad for the internal organs to protect them from outside
shocks.
 A subcutaneous thermal insulator against loss of body heat.
8-Lipoproteins, which are complex of lipids and proteins, are
important cellular constituents that present both in the
cellular and subcellular membranes.
9-Cholesterol enters in membrane structure and is used for
synthesis of adrenal cortical hormones, vitamin D3 and bile
acids.
10- Lipids provide bases for dealing with diseases such as
obesity, atherosclerosis, lipid-storage diseases, essential
fatty acid deficiency, respiratory distress syndrome

Classification of LipidsClassification of Lipids
1. Si mpl e l i pi ds ( Fat s &
Waxes)
2. Compl ex ( compound or
conj ugat ed l i pi ds)
3. Deri ved Li pi ds
4. Li pi d- associ at i ng
subst ances

Fatty alcoholsFatty alcohols (glycerol &(glycerol &
sphingosine)sphingosine)
Glycerol:
a trihydric alcohol (i.e., containing
three OH groups) and has the popular
name glycerin.
It is synthesized in the body from
glucose.
 It has the following properties:

1. Colorless viscous oily liquid with
sweet taste.
2. On heating with sulfuric acid or
KHSO4 (dehydration) it gives
acrolein that has a bad odor. This
reaction is used for detection of free
glycerol or any compound
containing glycerol.
CH2 OH
CH
CH2 OH
HO
CHO
CH
CH2
2 H2O
Heating, KHSO4
Glycerol Acrolein

3-It combines with three molecules of nitric
acid to form trinitroglycerin (TNT) that is
used as explosive and vasodilator.
4-On esterification with fatty acids it gives:
 Monoglyceride or monoacyl-glycerol: one
fatty acid + glycerol.
 Diglyceride or diacyl-glycerol: two fatty
acids + glycerol.
 Triglyceride or triacyl-glycerol: three fatty
acids + glycerol.
5-It has a nutritive value by conversion into
glucose and enters in structure of
phospholipids.

Uses of Glycerol:Uses of Glycerol:
1. pharmaceutical and cosmetic
preparations.
2. Reduces brain edema in cerebrovascular
disease.
3. Nitroglycerin is used as vasodilator
especially for the coronary arteries, thus it
is used in treatment of angina pectoris.
4. explosives manufacturing.
5. treatment of glaucoma (increased
intraocular pressure)due to its ability to
dehydrate the tissue from its water
content.

Sphingosine:Sphingosine:
- the alcohol(monohydric) present in
sphingolipids.
- synthesized in the body from serine
and palmitic acid.
It is not positive with acrolein test.
CH CH NH2
CH2OH
CHCH(CH2)12CH3
OH
Sphingosine

Fatty AcidsFatty Acids
DefinitionDefinition:
aliphatic mono-carboxylic acids that
are mostly obtained from the
hydrolysis of natural fats and oils.
the general formula R-(CH2)n-COOH
and mostly have straight chain (a few
exceptions have branched and heterocyclic chains).
"n" is mostly an even number of
carbon atoms (2-34)

Classification ofClassification of FATTY ACIDSFATTY ACIDS
According to presence orAccording to presence or
absence of double bondsabsence of double bonds
they are classified intothey are classified into::
>SatURATED FA
>unsatURATED FA

1-Saturated Fatty Acids
no double bonds with 2-24 or more
carbons.
solid at RT except if they are short
chained.
may be even or odd numbered.
molecular formula, CnH2n+1COOH.

Saturated Fatty acids could be:
A-Short chain Saturated F.A.A-Short chain Saturated F.A. (2-10(2-10
carbon).carbon).
a-Short chain Saturated volatile F.A.(2-6 C).
b-Short chain Saturated non volatile F.A.(7-10 C).
B-Long chain Saturated F.AB-Long chain Saturated F.A. (more than. (more than
10 carbon)10 carbon)

A-A- SATurated- short chainSATurated- short chain
VolatileVolatile short-chainshort-chain fattyfatty
acids:acids:
 liquid in nature and containliquid in nature and contain 1-6 C1-6 C
 water-solublewater-soluble
volatile at room temperaturevolatile at room temperature
 e.g., acetic, butyric,& caproic acids.e.g., acetic, butyric,& caproic acids.
Acetic F.A. (2C ) CHAcetic F.A. (2C ) CH33-COOH.-COOH.
Butyric F.A. (4C ) CHButyric F.A. (4C ) CH33-(CH-(CH22))22-COOH.-COOH.
Caproic F.A. (6C ) CHCaproic F.A. (6C ) CH33-(CH-(CH22))44-COOH.-COOH.

A- Saturated- Short chain
Non-volatileNon-volatile short-chainshort-chain fattyfatty
acidsacids:
solids at room temperaturesolids at room temperature
containcontain 7-107-10 carbons.carbons.
water-solublewater-soluble
 non-volatile at RTnon-volatile at RT
include caprylic and capric F.A.include caprylic and capric F.A.
caprylic (8 C ) CHcaprylic (8 C ) CH33-(CH-(CH22))66-COOH.-COOH.
Capric (10 C ) CHCapric (10 C ) CH33-(CH-(CH22))88-COOH.-COOH.

B-B- Saturated- LONG CHAINSaturated- LONG CHAIN
Long-chain fatty acids:
>10 carbon atoms.
in hydrogenated oils, animal fats,
butter and coconut and palm oils.
non-volatile
water-insoluble
E.g. palmitic, stearic, & lignoceric F.A.
 palmitic(16C) CHpalmitic(16C) CH33-(CH-(CH22))1414-COOH-COOH
stearic (18 C ) CHstearic (18 C ) CH33-(CH-(CH22))1616-COOH-COOH
lignoceric (24C ) CHlignoceric (24C ) CH33-(CH-(CH22))2222-COOH-COOH

2-Unsaturated Fatty
Acids
- contain double bond
- TYPES:
A. monounsaturated
they contain one double bond .
(CnH2n-1 COOH)
B. polyunsaturated
they contain more the one double bond
(CnH2n-# COOH).

A-Monounsaturated fatty acids:
1-Palmitoleic acid :
 It is found in all fats.
 It is C16:1∆9, i.e., has 16 carbons
and one double bond located at
carbon number 9 and involving
carbon 10.
CHCH33-( CH-( CH22 ))55CH = CH-(CHCH = CH-(CH22))77 –COOH–COOH

2-Oleic acid
Is the most common fatty acid inIs the most common fatty acid in
natural fats.natural fats.
It isIt is C18:1∆9C18:1∆9, i.e., has 18 carbons and, i.e., has 18 carbons and
one double bond located at carbonone double bond located at carbon
number 9 and involving carbon 10.number 9 and involving carbon 10.
CHCH33-(CH-(CH22))77- CH=CH – (CH- CH=CH – (CH22))77-COOH-COOH

3-Nervonic acid
(Unsaturated lignoceric acid).
 It is found in cerebrosides.
 It is C24:1∆15, i.e., has 24 carbons
and one double bond located at
carbon number 15 and involving
carbon 16.
CHCH33 – (CH– (CH22))77 CH= CH – (CHCH= CH – (CH22))1313- COOH- COOH

B-Polyunsaturated fatty acids :
(Essential fatty acids):
 Definition:
 They are essential fatty acids that
can not be synthesized in the
human body and must be taken in
adequate amounts in the diet.
 They are required for normal growth
and metabolism

Source: vegetable oils such as corn oil,
linseed oil, peanut oil, olive oil, cottonseed
oil, soybean oil and many other plant oils,
cod liver oil and animal fats.
 Deficiency: Their deficiency in the diet leads
to nutrition deficiency disease.
Symptoms:Symptoms: poor growth and health with
susceptibility to infections, dermatitis,
decreased capacity to reproduce, impaired
transport of lipids, fatty liver, and lowered
resistance to stress.

FunctionFunction of Essential Fatty Acids:of Essential Fatty Acids:
1.They are useful in the treatment of atherosclerosis by
help transporting blood cholesterol and lowering it and
transporting triglycerides.
2.The hormones are synthesized from them.
3.They enter in structure of all cellular and subcellular
membranes and the transporting plasma
phospholipids.
4.They are essential for skin integrity, normal growth
and reproduction.
5.They have an important role in blood clotting
(intrinsic factor).
6.Important in preventing and treating fatty liver.
7.Important role in health of the retina and vision.
8.They can be oxidized for energy production.

POLYUnsat FA:
1-Linoleic:1-Linoleic:
C18:2∆9, 12.
 It is the most important since other
essential fatty acids can be
synthesized from it in the body.
CHCH33-(CH-(CH22))44-CH = CH-CH-CH = CH-CH22-CH=CH-(CH-CH=CH-(CH22))77--
COOHCOOH

POLYUnsat FA:
2-Linolenic acid2-Linolenic acid:
C18:3∆9, 12, 15,
in corn, linseed, peanut, olive,
cottonseed and soybean oils.
CHCH33-CH-CH22-CH=CH-CH-CH=CH-CH22-CH=CH-CH-CH=CH-CH22--
CH=CH-(CHCH=CH-(CH22))77-COOH-COOH

POLYUnsat FA:
3-Arachidonic acid3-Arachidonic acid:
C20:4∆5, 8, 11, 14.
 It is an important component of
phospholipids in animal and in peanut
oil from which prostaglandins are
synthesized.
CHCH33-(CH-(CH22))44-CH=CH-CH-CH=CH-CH22-CH=CH-CH-CH=CH-CH22--
CH=CH-CHCH=CH-CH22-CH=CH-(CH-CH=CH-(CH22))33-COOH-COOH

Waxes)
2. Compound or conj ugat ed
l i pi ds
3. Deri ved Li pi ds
4. Li pi d- associ at i ng
subst ances

Waxes)

SimpleLipidsSimpleLipids
A-Neutral Fats and oilsA-Neutral Fats and oils
(Triglycerides)(Triglycerides)
Definition:Definition:
Neutral- uncharged due to absence ofNeutral- uncharged due to absence of
ionizable groups in it.ionizable groups in it.
most abundant lipids in nature.most abundant lipids in nature.
constitute about 98% of the lipids ofconstitute about 98% of the lipids of
adipose tissue, 30% of plasma or liveradipose tissue, 30% of plasma or liver
lipids, less than 10% of erythrocytelipids, less than 10% of erythrocyte
lipids.lipids.

They are esters of glycerol with various fatty acids.They are esters of glycerol with various fatty acids.
Since the 3 hydroxyl groups of glycerol are esterified,Since the 3 hydroxyl groups of glycerol are esterified,
the neutral fats are also calledthe neutral fats are also called “Triglycerides”.“Triglycerides”.
 Esterification of glycerol with one moleculeEsterification of glycerol with one molecule
of fatty acid givesof fatty acid gives monoglyceridemonoglyceride, and that, and that
with 2 molecules giveswith 2 molecules gives diglyceridediglyceride..
H2C O
C HO
H2C
C
C
O C
R1
R3
R2
O
O
O
+
3 H2O
CH2 OH
C HHO
CH2 OH
HO C R1
O
HO C R3
O
HO C R2
O
Fatty acids Glycerol Triglycerides
(Triacylglycerol)

Types of triglyceridesTypes of triglycerides
1-Simple triglycerides1-Simple triglycerides:: If the three fattyIf the three fatty
acids connected to glycerol are of the same type theacids connected to glycerol are of the same type the
triglyceride is called simple triglyceride, e.g.,triglyceride is called simple triglyceride, e.g.,
tripalmitin.tripalmitin.
2-Mixed triglycerides2-Mixed triglycerides:: if they are of differentif they are of different
types, it is called mixed triglycerides, e.g., stearo-types, it is called mixed triglycerides, e.g., stearo-
diolein and palmito-oleo-stearin.diolein and palmito-oleo-stearin.
>> Natural fatsNatural fats are mixtures of mixed triglyceridesare mixtures of mixed triglycerides
with a small amount of simple triglycerides.with a small amount of simple triglycerides.

CH2 O
C HO
CH2
C
C
O C
(CH2)14
O
O
O
Tripalmitin
(simple triacylglycerol)
CH3
(CH2)14CH3
(CH2)14 CH3
CH2 O
C HO
CH2
C
C
O C
(CH2)16
O
O
O
1-Stearo-2,3-diolein
(mixed triacylglycerol)
CH3
(CH2)7CHCH(CH2)7CH3
(CH2)7 CH CH (CH2)7 CH3
CH2 O
C HO
CH2
C
C
O C
(CH2)14
O
O
O
1-palmito-2-oleo-3-stearin
(mixed triacylglycerol)
CH3
(CH2)16 CH3
(CH2)7CHCH(CH2)7CH3

 The commonest fatty acids in animal fatsThe commonest fatty acids in animal fats
areare palmitic, stearic and oleic acids.palmitic, stearic and oleic acids.
The main difference between fats and oilsThe main difference between fats and oils
is foris for oils being liquidoils being liquid at roomat room
temperature, whereas,temperature, whereas, fats are solids.fats are solids.
 This is mainly due to presence of largerThis is mainly due to presence of larger
percentage ofpercentage of unsaturatedunsaturated fatty acids infatty acids in
oils than fats that has mostlyoils than fats that has mostly saturatedsaturated
fatty acids.fatty acids.

PhysicalPhysical properties of fat andproperties of fat and
oils:oils:
1. Freshly prepared fats and oils are colorless,
odorless and tasteless.Any color, or taste is due
to association with other foreign substances, e.g.,
the yellow color of body fat or milk fat is due to
carotene pigments(cow milk).
2. Fats have specific gravity less than 1 (one) and,
therefore, they float on water.
3. Fats are insoluble in water, but soluble in organic
solvents as ether and benzene.
4. Melting points of fats are usually low, but higher
than the solidification point,

ChemicalChemical Properties of fats andProperties of fats and
oilsoils:
1-Hydrolysis:1-Hydrolysis:
 hydrolyzed into their constituents (hydrolyzed into their constituents (fatty acids and glycerol)fatty acids and glycerol) byby
heated steam, acid, alkali or enzyme (e.g., lipase of pancreas).heated steam, acid, alkali or enzyme (e.g., lipase of pancreas).
 - During their enzymatic and acid hydrolysis glycerol and free- During their enzymatic and acid hydrolysis glycerol and free
fatty acids are produced.fatty acids are produced.
CH2 O
C HO
CH2
C
C
O C
R1
R3
R2
O
O
O
3 H2O
H2C OH
C HHO
H2C OH
OHCR1
O
OHCR3
O
+ OHCR2
OLipase or Acid
Triacylglycerol Glycerol Free fatty acids

2-Saponification.
>>Alkaline hydrolysis produces glycerol and salts ofAlkaline hydrolysis produces glycerol and salts of
fatty acids (fatty acids (soapssoaps).).
Soaps cause emulsification of oily material this helpSoaps cause emulsification of oily material this help
easy washing of the fatty materialseasy washing of the fatty materials
CH2 O
C HO
CH2
C
C
O C
R1
R3
R2
O
O
O
H2C OH
C HHO
H2C OH
ONaCR1
O
ONaCR3
O
+ ONaCR2
O
Triacylglycerol Glycerol Sodium salts of
fatty acids (soap)
3 NaOH

3-Halogenation3-Halogenation
 Neutral fats containing unsaturated fatty acids have theNeutral fats containing unsaturated fatty acids have the
ability of adding halogens (e.g., hydrogen or hydrogenationability of adding halogens (e.g., hydrogen or hydrogenation
and iodine or iodination) at the double bonds.and iodine or iodination) at the double bonds.
 very important property to determine the degree ofvery important property to determine the degree of
unsaturation of the fat or oil that determines its biologicalunsaturation of the fat or oil that determines its biological
valuevalue
CH (CH2)7 COOHCHCH2CH
Linoleic acid
CH(CH2)4CH3
2 I2
CH (CH2)7 COOHCHCH2CH
Stearate-tetra-iodinate
CH(CH2)4CH3
II I I

4-Hydrogenation or4-Hydrogenation or
hardening of oilshardening of oils:
It is a type of addition reactions accepting hydrogenIt is a type of addition reactions accepting hydrogen
at the double bonds of unsaturated fatty acids.at the double bonds of unsaturated fatty acids.
The hydrogenation is done under high pressure ofThe hydrogenation is done under high pressure of
hydrogen and is catalyzed by finely divided nickel orhydrogen and is catalyzed by finely divided nickel or
copper and heat.copper and heat.
It is the base of hardening of oils (It is the base of hardening of oils (margarinemargarine
manufacturingmanufacturing), e.g., change of oleic acid of fats), e.g., change of oleic acid of fats
(liquid) into stearic acid (solid).(liquid) into stearic acid (solid).
It is advisable not to saturate all double bonds;It is advisable not to saturate all double bonds;
otherwise margarine produced will be very hard, ofotherwise margarine produced will be very hard, of
very low biological value and difficult to digest.very low biological value and difficult to digest.

Oils
(liquid)
(with unsaturated
fatty acids, e.g., oleic)
Hard fat
(margarine, solid)
(with saturated
fatty acids, e.g., stearic)
Hydrogen, high pressure, nickel
Advantages forAdvantages for
hydrogenatedhydrogenated oil or fatoil or fat
are as followsare as follows::
1.1. It is more pleasant as cooking fat.It is more pleasant as cooking fat.
2.2. It is digestible and utilizable as normal animal fats and oils.It is digestible and utilizable as normal animal fats and oils.
3.3. It is less liable to cause gastric or intestinal irritation.It is less liable to cause gastric or intestinal irritation.
4.4. It is easily stored and transported and less liable toIt is easily stored and transported and less liable to
rancidity.rancidity.
Disadvantages of hydrogenatedDisadvantages of hydrogenated
 fats include lack of fat-soluble vitamins (A, D, E and K) andfats include lack of fat-soluble vitamins (A, D, E and K) and
essential fatty acidsessential fatty acids

5-Oxidation (Rancidity)5-Oxidation (Rancidity)
This toxic reaction of triglycerides leads to
unpleasant odour or taste of oils and fats developing
after oxidation by oxygen of air, bacteria, or
moisture.
Also this is the base of the drying oils after exposure
to atmospheric oxygen.
Example is linseed oil, which is used in paints and
varnishes manufacturing
= RANCID

RancidityRancidity
Definition:Definition:
physico-chemical changephysico-chemical change
development ofdevelopment of unpleasant odor or taste or abnormalunpleasant odor or taste or abnormal
colorcolor particularly on agingparticularly on aging
exposure to atmospheric oxygen, light, moisture,exposure to atmospheric oxygen, light, moisture,
bacterial or fungal contamination and/or heat.bacterial or fungal contamination and/or heat.
 Saturated fats resist rancidity more thanSaturated fats resist rancidity more than
unsaturated fats that have unsaturatedunsaturated fats that have unsaturated
double bonds.double bonds.

Types and causes of RancidityTypes and causes of Rancidity:
1.1. Hydrolytic rancidityHydrolytic rancidity
2.2. Oxidative rancidityOxidative rancidity
3.3. Ketonic rancidityKetonic rancidity
1-Hydrolytic rancidity1-Hydrolytic rancidity:
 from slight hydrolysis of the fat by lipasefrom slight hydrolysis of the fat by lipase
 bacterial contamination leading to thebacterial contamination leading to the liberation ofliberation of
free fatty acids and glycerolfree fatty acids and glycerol at high temp andat high temp and
moisture.moisture.
 Volatile short-chain fatty acids have unpleasantVolatile short-chain fatty acids have unpleasant
odor.odor.

CH2 O
C HO
CH2
C
C
O C
R1
R3
R2
O
O
O
3 H2O
H2C OH
C HHO
H2C OH
OHCR1
O
OHCR3
O
+ OHCR2
OLipase
Triacylglycerol Glycerol Free fatty acids
(volatile, bad odor)

2-Oxidative Rancidity2-Oxidative Rancidity:
oxidation of fat or oiloxidation of fat or oil
by exposure to oxygen, light and/or heat producingby exposure to oxygen, light and/or heat producing
peroxide derivativesperoxide derivatives
e.g.,e.g., peroxides, aldehydes, ketones and dicarboxylicperoxides, aldehydes, ketones and dicarboxylic
acids that are toxic and have bad odor.acids that are toxic and have bad odor.
due to oxidative addition of oxygen at thedue to oxidative addition of oxygen at the
unsaturated double bond of unsaturated fatty acidunsaturated double bond of unsaturated fatty acid
of oils.of oils.

Polyunsaturated fatty acid
Peroxyradical
Oxidant, O2
Hydroperoxide
Hydroxy fatty acid
Cyclic peroxide
Aldehydes
such as malondialdehyde
Other fragments
such as dicarboxylic acids

3-Ketonic Rancidity:
due to the contamination with certain fungi such asdue to the contamination with certain fungi such as
Aspergillus nigerAspergillus niger on fats such ason fats such as coconut oilcoconut oil..
 Ketones, fatty aldehydes, short chain fatty acidsKetones, fatty aldehydes, short chain fatty acids
and fatty alcohols are formed.and fatty alcohols are formed.
Moisture accelerates ketonic rancidity.Moisture accelerates ketonic rancidity.

Prevention of rancidityPrevention of rancidity
Avoidance of the causes (Avoidance of the causes ( exposure to light,exposure to light,
oxygen, moisture, high temperature andoxygen, moisture, high temperature and
bacteria or fungal contaminationbacteria or fungal contamination ).).
By keeping fats or oils in well-closed containers in cold, darkBy keeping fats or oils in well-closed containers in cold, dark
and dry place (i.e.,and dry place (i.e., good storage conditions).good storage conditions).
Removal of catalysts such as lead andRemoval of catalysts such as lead and
copper that catalyze rancidity.copper that catalyze rancidity.
Addition ofAddition of anti-oxidantsanti-oxidants to prevent peroxidation in fat (i.e.,to prevent peroxidation in fat (i.e.,
rancidity). They include phenols, naphthols, tannins andrancidity). They include phenols, naphthols, tannins and
hydroquinones.hydroquinones. The most common natural antioxidant is vitaminThe most common natural antioxidant is vitamin
E that is importantE that is important in vitroin vitro andand in vivoin vivo..

Hazards of Rancid Fats:
1.1. The products of rancidity areThe products of rancidity are toxic,toxic, i.e.,i.e.,
causescauses food poisoning and cancerfood poisoning and cancer..
2.2. Rancidity destroys the fat-solubleRancidity destroys the fat-soluble
vitamins (vitamins (vitamins A, D, K and Evitamins A, D, K and E).).
3.3. Rancidity destroys theRancidity destroys the polyunsaturatedpolyunsaturated
essential fatty acidsessential fatty acids..
4.4. Rancidity causesRancidity causes economical losseconomical loss
because rancid fat is inedible.because rancid fat is inedible.

B-WaxesB-Waxes
DefinitionDefinition: Waxes are solid simple lipidsWaxes are solid simple lipids
containing a monohydric alcohol (with acontaining a monohydric alcohol (with a
higher molecular weight than glycerol)higher molecular weight than glycerol)
esterified to long-chain fatty acids.esterified to long-chain fatty acids.
Examples of these alcohols areExamples of these alcohols are palmitoylpalmitoyl
alcohol, cholesterol, vitamin A or D.alcohol, cholesterol, vitamin A or D.
Properties of waxesProperties of waxes: Waxes are: Waxes are
insoluble in water, but soluble in fatinsoluble in water, but soluble in fat
solvents and are negative for acroleinsolvents and are negative for acrolein
test.test.
Waxes are not easily hydrolyzed as theWaxes are not easily hydrolyzed as the
fats and are indigestible by lipases andfats and are indigestible by lipases and
are very resistant to rancidity.are very resistant to rancidity.
Thus they are of no nutritional value.Thus they are of no nutritional value.

Type of WaxesType of Waxes:
- Waxes are widely distributed in nature
such as the secretion of certain insects as
bees-wax, protective coatings of the skins
and furs of animals and leaves and fruits
of plants. They are classified into true-
waxes and wax-like compounds as
follows:
A-True waxesA-True waxes: include:
Bees-waxBees-wax is secreted by the honeybees
that use it to form the combs. It is a
mixture of waxes with the chief
constituent is mericyl palmitate.

C15H31 C OH
O
+C30H61OH C15H31 C O
O
C30H61
H2OPalmitic
acid
Mericyl
alcohol
Mericyl
palmitate
B-Wax-like compounds:
 Cholesterol estersCholesterol esters: Lanolin (or woolLanolin (or wool
fat) is prepared from the wool-fat) is prepared from the wool-
associated skin glands and isassociated skin glands and is
secreted by sebaceous glands of thesecreted by sebaceous glands of the
skin.skin.
 It is very complex mixture, containsIt is very complex mixture, contains
both free and esterified cholesterol,both free and esterified cholesterol,
e.g., cholesterol-palmitate and othere.g., cholesterol-palmitate and other
sterolssterols.

Differences between neutral lipids and waxes:
Waxes Neutral lipidsNeutral lipids
1.1.Digestibility:Digestibility: Indigestible (notIndigestible (not
hydrolyzed by lipase).hydrolyzed by lipase).
Digestible (hydrolyzed by lipase).Digestible (hydrolyzed by lipase).
2-Type of2-Type of
alcoholalcohol::
Long-chain monohydricLong-chain monohydric
alcohol + one fatty acid.alcohol + one fatty acid.
Glycerol (trihydric) + 3 fatty acidsGlycerol (trihydric) + 3 fatty acids
3-Type of fatty3-Type of fatty
acidsacids::
Fatty acid mainly palmiticFatty acid mainly palmitic
or stearic acid.or stearic acid.
Long and short chain fatty acids.Long and short chain fatty acids.
4-Acrolein test4-Acrolein test: Negative.Negative. Positive.Positive.
5-Rancidability:5-Rancidability: Never get rancid.Never get rancid. Rancidible.Rancidible.
6-Nature at6-Nature at
roomroom
temperaturetemperature.
Hard solid.Hard solid. Soft solid or liquid.Soft solid or liquid.
7-Saponification7-Saponification Nonsaponifiable.Nonsaponifiable. Saponifiable.Saponifiable.
8-Nutritive8-Nutritive
valuevalue:
No nutritive value.No nutritive value. Nutritive.Nutritive.
9-Example:9-Example: Bee & carnuba waxes.Bee & carnuba waxes. Butter and vegetable oils.Butter and vegetable oils.

2-Compound Lipids2-Compound Lipids
DefinitionDefinition:
 They are lipids that containThey are lipids that contain
additional substances, e.g., sulfur,additional substances, e.g., sulfur,
phosphorus, amino group,phosphorus, amino group,
carbohydrate, or proteins besidecarbohydrate, or proteins beside
fatty acid and alcohol.fatty acid and alcohol.
 Compound or conjugated lipids areCompound or conjugated lipids are
classified into the following typesclassified into the following types
according to the nature of theaccording to the nature of the
additional group:additional group:
1.1. PhospholipidsPhospholipids
2.2. Glycolipids.Glycolipids.
3.3. LipoproteinsLipoproteins
4.4. Sulfolipids and amino lipids.Sulfolipids and amino lipids.

A-PhospholipidsA-Phospholipids
Definition:Definition: Phospholipids or phosphatides arePhospholipids or phosphatides are
compound lipids, which contain phosphoriccompound lipids, which contain phosphoric
acid group in their structureacid group in their structure..
ImportanceImportance:
1.1.They are present in large amounts in theThey are present in large amounts in the
liver and brain as well as blood. Everyliver and brain as well as blood. Every
animal and plant cell containsanimal and plant cell contains
phospholipids.phospholipids.
2.2.The membranes bounding cells andThe membranes bounding cells and
subcellular organelles are composed mainlysubcellular organelles are composed mainly
of phospholipids. Thus, the transfer ofof phospholipids. Thus, the transfer of
substances through these membranes issubstances through these membranes is
controlled by properties of phospholipids.controlled by properties of phospholipids.
3.3.They are important components of theThey are important components of the
lipoprotein coat essential for secretion andlipoprotein coat essential for secretion and
transport of plasma lipoprotein complexes.transport of plasma lipoprotein complexes.
Thus, they are lipotropic agents thatThus, they are lipotropic agents that preventprevent
fatty liverfatty liver..
4.4.Myelin sheath of nerves is rich withMyelin sheath of nerves is rich with
phospholipids.phospholipids.

5-Important in digestion and5-Important in digestion and
absorption of neutral lipids andabsorption of neutral lipids and
excretion of cholesterol in the bile.excretion of cholesterol in the bile.
6-Important function in blood clotting6-Important function in blood clotting
and platelet aggregation.and platelet aggregation.
7-They provide lung alveoli with7-They provide lung alveoli with
surfactants that prevent itssurfactants that prevent its
irreversible collapseirreversible collapse..
8-Important role in signal transduction8-Important role in signal transduction
across the cell membrane.across the cell membrane.
9-Phospholipase A2 in snake venom9-Phospholipase A2 in snake venom
hydrolyses membrane phospholipidshydrolyses membrane phospholipids
into hemolytic lysolecithin orinto hemolytic lysolecithin or
lysocephalin.lysocephalin.
10-They are source of polyunsaturated10-They are source of polyunsaturated
fatty acids for synthesis offatty acids for synthesis of
eicosanoids.eicosanoids.

Sources:Sources: They are found in all cellsThey are found in all cells
(plant and animal), milk and egg-(plant and animal), milk and egg-
yolk in the form of lecithins.yolk in the form of lecithins.
StructureStructure: phospholipids are composedphospholipids are composed
of:of:
1.1. Fatty acidsFatty acids (a saturated and an(a saturated and an
unsaturated fatty acid).unsaturated fatty acid).
2.2. Nitrogenous baseNitrogenous base (choline, serine,(choline, serine,
threonine, or ethanolamine).threonine, or ethanolamine).
3.3. Phosphoric acid.Phosphoric acid.
4.4. Fatty alcoholsFatty alcohols (glycerol, inositol or(glycerol, inositol or
sphingosine).sphingosine).

 Classification of PhospholipidsClassification of Phospholipids areare
classified into 2 groups according toclassified into 2 groups according to
the type of thethe type of the alcoholalcohol present intopresent into
two types:two types:
A-A-GlycerophospholipidsGlycerophospholipids: They areThey are
regarded as derivatives of phosphatidicregarded as derivatives of phosphatidic
acids that are the simplest type ofacids that are the simplest type of
phospholipids and include:phospholipids and include:
1.1. Phosphatidic acidsPhosphatidic acids..
2.2. LecithinsLecithins
3.3. CephalinsCephalins..
4.4. PlasmalogensPlasmalogens..
5.5. InositidesInositides..
6.6. CardiolipinCardiolipin.
B-SphingophospholipidsB-Sphingophospholipids: They containThey contain
sphingosine as an alcohol and are namedsphingosine as an alcohol and are named
SphingomyelinsSphingomyelins.

A-GlycerophospholipidsA-Glycerophospholipids
1-Phosphatidic acids:1-Phosphatidic acids:They are metabolicThey are metabolic
intermediates in synthesis of triglyceridesintermediates in synthesis of triglycerides
and glycerophospholipids in the body andand glycerophospholipids in the body and
may have function as amay have function as a second messengersecond messenger..
They exist in two forms according to theThey exist in two forms according to the
position of the phosphateposition of the phosphate
CH2 O
C HO
CH2
C
C
O P
R1
R2
O
O
α-Phosphatidic acid
OH
OH
O
Saturated
fatty acidPolyunsaturated
fatty acid
Phosphate
CH2 O
C H
CH2
C
O
R1
O
β-Phosphatidic acid
Saturated
fatty acid
Polyunsaturated
fatty acid
Phosphate PHO
OH
O
C R2
O
β
β
α
α
α
α
O

2-Lecithins:2-Lecithins:
DefinitionDefinition: Lecithins areLecithins are
glycerophospholipids that containglycerophospholipids that contain
choline as a base beside phosphatidiccholine as a base beside phosphatidic
acid. They exist in 2 formsacid. They exist in 2 forms αα- and- and ββ--
lecithins. Lecithins are a common celllecithins. Lecithins are a common cell
constituent obtained from brain (constituent obtained from brain (αα--
type), egg yolk (type), egg yolk (ββ-type), or liver (both-type), or liver (both
types). Lecithins are important in thetypes). Lecithins are important in the
metabolism of fat by the liver.metabolism of fat by the liver.
Structure:Structure: Glycerol is connected at C2 orGlycerol is connected at C2 or
C3 with a polyunsaturated fatty acid, atC3 with a polyunsaturated fatty acid, at
C1 with a saturated fatty acid, at C3 orC1 with a saturated fatty acid, at C3 or
C2 by phosphate to which the cholineC2 by phosphate to which the choline
base is connected. The common fattybase is connected. The common fatty
acids in lecithins are stearic, palmitic,acids in lecithins are stearic, palmitic,
oleic, linoleic, linolenic, clupandonic oroleic, linoleic, linolenic, clupandonic or
arachidonic acids.arachidonic acids.

LysolecithinLysolecithin causes hemolysis of RBCs. Thiscauses hemolysis of RBCs. This
partially explains toxic effect of snakepartially explains toxic effect of snake
venom,. The venom containsvenom,. The venom contains lecithinaselecithinase,,
which hydrolyzes the polyunsaturatedwhich hydrolyzes the polyunsaturated
fatty converting lecithin into lysolecithin.fatty converting lecithin into lysolecithin.
Lysolecithins are intermediates inLysolecithins are intermediates in
metabolism of phospholipidsmetabolism of phospholipids.
CH2 O
C HO
CH2
C
C
O P
R1
R2
O
O
α-Lecithin
O
OH
O
CH2 O
C H
CH2
C
O
R1
O
β-Lecithin
P
OH
O
C R2
O
CH2 CH2 N
CH3
CH3
CH3
+
OCH2CH2N
CH3
CH3
CH3
+
Choline
Choline
O

 Lung surfactantLung surfactant
 Is a complex of dipalmitoyl-lecithin,Is a complex of dipalmitoyl-lecithin,
sphingomyelin and a group of apoproteinssphingomyelin and a group of apoproteins
called apoprotein A, B, C, and D.called apoprotein A, B, C, and D.
 It is produced by type II alveolar cells andIt is produced by type II alveolar cells and
is anchored to the alveolar surface of typeis anchored to the alveolar surface of type
II and I cells.II and I cells.
 It lowers alveolar surface tension andIt lowers alveolar surface tension and
improves gas exchange besides activatingimproves gas exchange besides activating
macrophages to kill pathogens.macrophages to kill pathogens.
 In premature babies, this surfactant isIn premature babies, this surfactant is
deficient and they suffer fromdeficient and they suffer from respiratoryrespiratory
distress syndromedistress syndrome..
 Glucocorticoids increase the synthesis ofGlucocorticoids increase the synthesis of
the surfactant complex and promotethe surfactant complex and promote
differentiation of lung cells.differentiation of lung cells.

3-Cephalins (or Kephalins):3-Cephalins (or Kephalins):
DefinitionDefinition: They are phosphatidyl-They are phosphatidyl-
ethanolamine or serine. Cephalinsethanolamine or serine. Cephalins
occur in association with lecithins inoccur in association with lecithins in
tissues and are isolated from thetissues and are isolated from the
brain (brain (Kephale = head).Kephale = head).
StructureStructure: Cephalins resemble: Cephalins resemble
lecithins in structure except thatlecithins in structure except that
choline is replaced by ethanolamine,choline is replaced by ethanolamine,
serine or threonine amino acids.serine or threonine amino acids.

Certain cephalins are constituents of theCertain cephalins are constituents of the
complex mixture of phospholipids,complex mixture of phospholipids,
cholesterol and fat that constitute the lipidcholesterol and fat that constitute the lipid
component of the lipoproteincomponent of the lipoprotein
““thromboplastinthromboplastin” which accelerates the” which accelerates the
clotting of blood by activation ofclotting of blood by activation of
prothrombin to thrombin in presence ofprothrombin to thrombin in presence of
calcium ionscalcium ions.
CH2 O
C HO
CH2
C
C
O P
R1
R2
O
O
α-Cephalin
O
OH
O
CH2 CH2 NH2 Ethanolamine
HO CH2 CH COOH Serine
NH2
HO CH CH COOH Threonine
NH2CH3

4-Plasmalogens:4-Plasmalogens:
Definition:Definition: Plasmalogens are found inPlasmalogens are found in
the cell membrane phospholipidsthe cell membrane phospholipids
fraction of brain and muscle (10% offraction of brain and muscle (10% of
it is plasmalogens), liver, semen andit is plasmalogens), liver, semen and
eggs.eggs.
StructureStructure: Plasmalogens resemblePlasmalogens resemble
lecithins and cephalins in structurelecithins and cephalins in structure
but differ in the presence ofbut differ in the presence of αα,,ββ--
unsaturated fatty alcoholunsaturated fatty alcohol rather thanrather than
a fatty acid at C1 of the glycerola fatty acid at C1 of the glycerol
connected by ether bond.connected by ether bond.
 At C2 there is an unsaturated long-At C2 there is an unsaturated long-
chain fatty acid, however, it may be achain fatty acid, however, it may be a
very short-chain fatty acidvery short-chain fatty acid

Properties: Similar to lecithinsSimilar to lecithins.
CH2
C HO
CH2
C
O P
R2
O
α-Plasmalogen
O
OH
O
CH2 CH2 N
CH3
CH3
CH3
+
α,β-Unsaturated
fatty alcoholCH CH R1O

5-Inositides5-Inositides:
 DefinitionDefinition::
- They are phosphatidyl inositol.They are phosphatidyl inositol.
 StructureStructure: They are similar to lecithins orThey are similar to lecithins or
cephalins but they have the cyclic sugarcephalins but they have the cyclic sugar
alcohol,alcohol, inositolinositol as the base. They areas the base. They are
formed of glycerol, one saturated fatty acid,formed of glycerol, one saturated fatty acid,
one unsaturated fatty acid, phosphoric acidone unsaturated fatty acid, phosphoric acid
and inositoland inositol
CH2
C HO
CH2
C
O P
R2
O
α-Phosphatidylinositol
O
OH
O
C R1O
O
H
H
OH
OH
HOH
H
OHOH
H H
1
2 3
4
56

SourceSource: Brain tissuesBrain tissues.
FunctionFunction:
Phosphatidyl inositol is a majorPhosphatidyl inositol is a major
component of cell membranecomponent of cell membrane
phospholipids particularly at the innerphospholipids particularly at the inner
leaflet of it.leaflet of it.
 They play a major role as secondThey play a major role as second
messengers during signalmessengers during signal
transduction for certain hormone..transduction for certain hormone..
On hydrolysis by phospholipase C,On hydrolysis by phospholipase C,
phosphatidyl-inositol-4,5-diphosphatephosphatidyl-inositol-4,5-diphosphate
producesproduces diacyl-glycerol and inositol-diacyl-glycerol and inositol-
triphosphatetriphosphate both act to liberateboth act to liberate
calcium from its intracellular stores tocalcium from its intracellular stores to
mediate the hormone effects.mediate the hormone effects.

6-Cardiolipins:6-Cardiolipins:
DefinitionDefinition: They are diphosphatidyl-They are diphosphatidyl-
glycerol. They are found in the innerglycerol. They are found in the inner
membrane of mitochondria initially isolatedmembrane of mitochondria initially isolated
from heart muscle (cardio). It is formed of 3from heart muscle (cardio). It is formed of 3
molecules of glycerol, 4 fatty acids and 2molecules of glycerol, 4 fatty acids and 2
phosphate groupsphosphate groups..
FunctionFunction:: Used in serological diagnosis ofUsed in serological diagnosis of
autoimmunity diseases.autoimmunity diseases.
CH2
C HO
CH2
C
O P
R2
O
Cardiolipin
O
OH
O
C R1O
O
CH2
CH OH
CH2 CH2
CH O
CH2
C
OP
R3
O
O
OH
O
CR4 O
O

B-SphingophospholipidsB-Sphingophospholipids
1-Sphingomyelins1-Sphingomyelins
 Definition:Definition: Sphingomyelins are found inSphingomyelins are found in
large amounts in brain and nerves and inlarge amounts in brain and nerves and in
smaller amounts in lung, spleen, kidney,smaller amounts in lung, spleen, kidney,
liver and bloodliver and blood.
 Structure:Structure: Sphingomyelins differ fromSphingomyelins differ from
lecithins and cephalins in that they containlecithins and cephalins in that they contain
sphingosine as the alcohol instead ofsphingosine as the alcohol instead of
glycerol, they contain two nitrogenousglycerol, they contain two nitrogenous
bases: sphingosine itself and choline.bases: sphingosine itself and choline.
 Thus, sphingomyelins contain sphingosineThus, sphingomyelins contain sphingosine
base, one long-chain fatty acid, choline andbase, one long-chain fatty acid, choline and
phosphoric acid.phosphoric acid.
 To the amino group of sphingosine the fattyTo the amino group of sphingosine the fatty
acid is attached by an amide linkage.acid is attached by an amide linkage.

Ceramide This part of sphingomyelin inThis part of sphingomyelin in
which the amino group of sphingosine iswhich the amino group of sphingosine is
attached to the fatty acid by an amideattached to the fatty acid by an amide
linkage.linkage.
 Ceramides have been found in the free stateCeramides have been found in the free state
in the spleen, liver and red cells.in the spleen, liver and red cells.
CH CH NH
CH2
CHCH(CH2)12CH3
OH
Sphingosine
C R1
O
O
P O
OH
O CH2 CH2 N
CH3
CH3
CH3
+
Choline
Fatty acid
Phosphate
Ceramide
Sphingomyelin

B-GlycolipidsB-Glycolipids
 DefinitionDefinition: They are lipids that containThey are lipids that contain
carbohydrate residues with sphingosinecarbohydrate residues with sphingosine
as the alcohol and a very long-chain fattyas the alcohol and a very long-chain fatty
acid (24 carbon series).acid (24 carbon series).
 They are present in cerebral tissue,They are present in cerebral tissue,
therefore are calledtherefore are called cerebrosidescerebrosides
 ClassificationClassification: According to the numberAccording to the number
and nature of the carbohydrate residue(s)and nature of the carbohydrate residue(s)
present in the glycolipids the following arepresent in the glycolipids the following are
1. Cerebrosides. They have one galactoseThey have one galactose
molecule (galactosides).molecule (galactosides).
2. Sulfatides. They are cerebrosides withThey are cerebrosides with
sulfate on the sugar (sulfatedsulfate on the sugar (sulfated
cerebrosides).cerebrosides).
3. Gangliosides. They have several sugarThey have several sugar
and sugaramine residues.and sugaramine residues.

1-Cerebrosides:1-Cerebrosides:
 Occurrence: They occur in myelin sheath of nerves and
white matter of the brain tissues and cellular
membranes. They are important for nerve conductance.
 Structure: They contain sugar, usually β-galactose and
may be glucose or lactose, sphingosine and fatty acid,
but no phosphoric acid.
CH CH NH
CH2
CHCH(CH2)12CH3
OH
Sphingosine
C R1
O
O
Psychosin
Fatty acid
Ceramide
Cerebroside
OOH
H H
H
OHH
OH
CH2OH
H
Galactose

3-Gangliosides:3-Gangliosides:
 They are more complex glycolipids thatThey are more complex glycolipids that
occur in the gray matter of the brain,occur in the gray matter of the brain,
ganglion cells, and RBCs. They transferganglion cells, and RBCs. They transfer
biogenic amines across the cell membranebiogenic amines across the cell membrane
and act as a cell membrane receptor.and act as a cell membrane receptor.
 GangliosidesGangliosides containcontain sialic acid (N-sialic acid (N-
acetylneuraminicacetylneuraminic acid),acid), ceramideceramide
(sphingosine + fatty acid of 18-24 carbon(sphingosine + fatty acid of 18-24 carbon
atom length), 3 molecules of hexoses (1atom length), 3 molecules of hexoses (1
glucose + 2 galactose) and hexosamine. Theglucose + 2 galactose) and hexosamine. The
most simple type of it themost simple type of it the
monosialoganglioside,. It works as amonosialoganglioside,. It works as a
receptor for cholera toxin in the humanreceptor for cholera toxin in the human
intestine.intestine.
Ceramide-Glucose-Galactose-N-acetylgalactosamine-Galactose
Monosialoganglioside
Sialic acid

C-LipoproteinsC-Lipoproteins
 DefinitionDefinition: Lipoproteins are lipids combinedLipoproteins are lipids combined
with proteins in the tissues. The lipidwith proteins in the tissues. The lipid
component is phospholipid, cholesterol orcomponent is phospholipid, cholesterol or
triglycerides. The holding bonds aretriglycerides. The holding bonds are
secondary bonds.secondary bonds.
 They include:They include:
1.1. Structural lipoproteinsStructural lipoproteins: These are widely: These are widely
distributed in tissues being present indistributed in tissues being present in
cellular and subcellular membranes. In lungcellular and subcellular membranes. In lung
tissues acting as a surfactant in a complextissues acting as a surfactant in a complex
of a protein and lecithin. In the eye,of a protein and lecithin. In the eye,
rhodopsin of rods is a lipoprotein complex.rhodopsin of rods is a lipoprotein complex.
 Transport lipoproteinsTransport lipoproteins::
 These are the forms present in bloodThese are the forms present in blood
plasma. They are composed of a proteinplasma. They are composed of a protein
calledcalled apolipoproteinapolipoprotein and different types ofand different types of
lipids. (Cholesterol, cholesterol esters,lipids. (Cholesterol, cholesterol esters,
phospholipids and triglycerides). As thephospholipids and triglycerides). As the
lipid content increases, the density oflipid content increases, the density of
plasma lipoproteins decreasesplasma lipoproteins decreases

 Plasma lipoproteins can be separated byPlasma lipoproteins can be separated by
two methodstwo methods:
1.1. Ultra-centrifugationUltra-centrifugation: Using the rate of: Using the rate of
floatation in sodium chloride solutionfloatation in sodium chloride solution
leading to their sequential separation intoleading to their sequential separation into
chylomicronschylomicrons, very low density, very low density
lipoproteins (lipoproteins (VLDL or pre-VLDL or pre-ββ-lipoproteins-lipoproteins),),
low density lipoproteins (low density lipoproteins (LDL orLDL or ββ--
lipoproteinslipoproteins), high density lipoproteins), high density lipoproteins
((HDL orHDL or αα-lipoproteins-lipoproteins) and) and albumin-freealbumin-free
fattyfatty acids complex.acids complex.
2.2. ElectrophoresisElectrophoresis:: is the migration ofis the migration of
charged particles in an electric field eithercharged particles in an electric field either
to the anode or to the cathode. Itto the anode or to the cathode. It
sequentially separates the lipoproteinssequentially separates the lipoproteins
intointo chylomicronschylomicrons,, pre-pre-ββ-,-, ββ-, and-, and αα--
lipoprotein andlipoprotein and albumin-free fattyalbumin-free fatty acidsacids
complexcomplex.
Polar lipids
(phospholipids)
Nonpolar lipids
(cholesterol and its esters
and triacylglycerols)
Structure of a plasma lipoprotein complex
Polar apolipoproteins

a) Chylomicronsa) Chylomicrons: They have the largestThey have the largest
diameter and the least density. They containdiameter and the least density. They contain 1-1-
2% protein2% protein only andonly and 98-99% fat98-99% fat. The main lipid. The main lipid
fraction is triglycerides absorbed from thefraction is triglycerides absorbed from the
intestine and they containintestine and they contain small amountssmall amounts of theof the
absorbed cholesterol and phospholipids.absorbed cholesterol and phospholipids.
b) Very low-density lipoproteins (VLDL) orb) Very low-density lipoproteins (VLDL) or
pre-pre-ββ-lipoproteins-lipoproteins: Their diameter is smallerTheir diameter is smaller
than chylomicrons. They contain aboutthan chylomicrons. They contain about 7-10%7-10%
proteinprotein andand 90-93% lipid90-93% lipid. The lipid content is. The lipid content is
mainly triglycerides formed in the liver. Theymainly triglycerides formed in the liver. They
contain phospholipid and cholesterolcontain phospholipid and cholesterol more thanmore than
chylomicrons.chylomicrons.
c) Low-density lipoproteins (LDL) or) Low-density lipoproteins (LDL) or ββ--
lipoproteinslipoproteins: They containThey contain 10-20% proteins10-20% proteins inin
the form of apolipoprotein B. Theirthe form of apolipoprotein B. Their lipidlipid
content varies from 80-90%.content varies from 80-90%. They contain aboutThey contain about
60% of total blood cholesterol and 40% of total60% of total blood cholesterol and 40% of total
blood phospholipids. As their percentageblood phospholipids. As their percentage
increases, the liability to atherosclerosisincreases, the liability to atherosclerosis
increases.increases.

d) High-density lipoproteins (HDL) ord) High-density lipoproteins (HDL) or αα--
LipoproteinsLipoproteins: They containThey contain 35-55%35-55%
proteinsproteins in the form of apolipoprotein A.in the form of apolipoprotein A.
They containThey contain 45-65% lipids45-65% lipids formed offormed of
cholesterol (cholesterol (40% of40% of total blood contenttotal blood content))
and phospholipids (and phospholipids (60%60% of total bloodof total blood
contentcontent). They act as cholesterol). They act as cholesterol
scavengersscavengers, as their percentage, as their percentage
increases, the liability to atherosclerosisincreases, the liability to atherosclerosis
decreases. They are higher in femalesdecreases. They are higher in females
than in males. Due to their high proteinthan in males. Due to their high protein
content they possess the highestcontent they possess the highest
density.density.
e) Albumin-free fatty acids complex:e) Albumin-free fatty acids complex: It isIt is
a proteolipid complex witha proteolipid complex with 99% protein99% protein
content associated with long-chain freecontent associated with long-chain free
fatty acids for transporting them.fatty acids for transporting them.

Cholesterol:Cholesterol:
Importance:Importance: --
 It is the most important sterol in animalIt is the most important sterol in animal
tissues astissues as free alcoholfree alcohol or in an esterifiedor in an esterified
form (form (with linoleicwith linoleic,, oleic, palmitic acids oroleic, palmitic acids or
other fatty acidsother fatty acids).).
 Steroid hormones, bile salts and vitamin DSteroid hormones, bile salts and vitamin D
are derivatives from it.are derivatives from it.
 Tissues contain different amounts of it thatTissues contain different amounts of it that
serve a structural and metabolic role, e.g.,serve a structural and metabolic role, e.g.,
adrenal cortexadrenal cortex content is 10%,content is 10%, whereas,whereas,
brain is 2%,brain is 2%, others 0.2-0.3%.others 0.2-0.3%.
SourceSource:: - It is synthesized in the body fromIt is synthesized in the body from
acetyl-CoA (1gm/day, cholesterol does notacetyl-CoA (1gm/day, cholesterol does not
exist in plants) and is also taken in the dietexist in plants) and is also taken in the diet
((0.3 gm/day as in, butter, milk, egg yolk,0.3 gm/day as in, butter, milk, egg yolk,
brain, meat and animal fat).brain, meat and animal fat).

Physical propeties:Physical propeties:It has a hydroxyl group
on C3, a double bond between C5 and C6, 8
asymmetric carbon atoms and a side chain
of 8 carbon atoms.
It is found in all animal cells, corpus luteum
and adrenal cortex, human brain (17% of
the solids).
In the blood (the total cholesterol amounts
about 200 mg/dL of which 2/3 is esterified,
chiefly to unsaturated fatty acids while the
remainder occurs as the free cholesterol.
CH3
CH3
HO
CH3
CH3
CH3
Cholesterol

Chemical propertiesChemical properties Intestinal bacteriaIntestinal bacteria
reduce cholesterol intoreduce cholesterol into coprosterol andcoprosterol and
dihydrocholesteroldihydrocholesterol..
- It is also oxidized into- It is also oxidized into 7-7-
DehydrocholesterolDehydrocholesterol and further unsaturatedand further unsaturated
cholesterol with a second double bondcholesterol with a second double bond
betweenbetween C7 and C8.C7 and C8. When the skin isWhen the skin is
irradiated with ultraviolet light 7-irradiated with ultraviolet light 7-
dehydrocholesterol is converted to vitamindehydrocholesterol is converted to vitamin
D3.D3. This explains the value of sun light inThis explains the value of sun light in
preventingpreventing ricketsrickets..
CH3
CH3
HO
CH3
CH3
CH3
Coprosterol,
in feces
H
CH3
CH3
HO
CH3
CH3
CH3
Dihydrocholesterol,
in blood and other tissues
H

ErgosterolErgosterol differs from 7-differs from 7-
dehydrocholesterol in the side chain.dehydrocholesterol in the side chain.
Ergosterol is converted to vitamin D2 byErgosterol is converted to vitamin D2 by
irradiation with UV Ergosterol and 7-irradiation with UV Ergosterol and 7-
dehydrocholesterol are called Pro-vitaminsdehydrocholesterol are called Pro-vitamins
D or precursors of vitamin D.D or precursors of vitamin D.
 - It was first isolated from ergot, a fungus- It was first isolated from ergot, a fungus
then from yeast. Ergosterol is less stablethen from yeast. Ergosterol is less stable
than cholesterol (than cholesterol (because of having 3because of having 3
double bondsdouble bonds).).
CH3
CH3
HO
CH3
CH3
CH3
7-dehydrocholesterol
CH3
CH3
HO
CH3
CH3
CH3
Ergosterol
CH3

SteroidsSteroids
 Steroids constitute an importantSteroids constitute an important
class of biological compounds.class of biological compounds.
 Steroids are usually found inSteroids are usually found in
association with fat. They can beassociation with fat. They can be
separated from fats afterseparated from fats after
saponification since they occur in thesaponification since they occur in the
unsaponifiable residue.unsaponifiable residue.
 They areThey are derivatives of cholesterolderivatives of cholesterol
that is formed of steroid ring orthat is formed of steroid ring or
nucleus.nucleus.
 Biologically important groups ofBiologically important groups of
substances, which contain this ring, are:substances, which contain this ring, are:
1.1. Sterols.Sterols.
2.2. Adrenal cortical hormones.Adrenal cortical hormones.
3.3. Male and female sex hormones.Male and female sex hormones.
4.4. Vitamin D group.Vitamin D group.
5.5. Bile acids.Bile acids.
6.6. Cardiac glycosides.Cardiac glycosides.

 General consideration about naturally occurringGeneral consideration about naturally occurring
steroidssteroids:
A typical member of this groupA typical member of this group is cholesterolis cholesterol..
Certain facts have to be considered when drawingCertain facts have to be considered when drawing
steroid formulasteroid formula:
1) There is always oxygen in the form of1) There is always oxygen in the form of hydroxyl orhydroxyl or
ketone on C3ketone on C3..
2) Rings2) Rings C and D are saturatedC and D are saturated (stable).(stable).
3) Methyl groups at3) Methyl groups at C18 C19C18 C19. In case of vitamin D,. In case of vitamin D,
the CH3the CH3 group at C19 becomes a methylene groupgroup at C19 becomes a methylene group
(=CH2) and the ring B is opened, whereas,(=CH2) and the ring B is opened, whereas, thisthis
methyl group is absent in female sex hormonesmethyl group is absent in female sex hormones
(estrogens).(estrogens).
4) In estrogens (female sex hormones) ring A is4) In estrogens (female sex hormones) ring A is
aromatic and there isaromatic and there is no methyl group on C10.no methyl group on C10.
CH3
CH3
HO
Steroid ring
1
2
3 4
5
6 7
8
9
10
11
12
13
14 15
1617
18
19
A B
C D

Bile acidsBile acids:
 They are produced from oxidation ofThey are produced from oxidation of
cholesterol in the liver producingcholesterol in the liver producing cholic andcholic and
chenodeoxycholic acidschenodeoxycholic acids that are conjugatedthat are conjugated
withwith glycine or taurineglycine or taurine to produceto produce
glycocholic,glycocholic, glycochenodeoxycholic,glycochenodeoxycholic,
taurocholictaurocholic and taurochenodeoxycholicand taurochenodeoxycholic
acids. They react with sodium or potassiumacids. They react with sodium or potassium
to produceto produce sodiumsodium oror potassium bile saltspotassium bile salts..
 Their function is as followsTheir function is as follows:
1.1.Emulsification of lipids during digestion.Emulsification of lipids during digestion.
2.2.Help in digestion of the other foodstuffs.Help in digestion of the other foodstuffs.
3.3.Activation of pancreatic lipase.Activation of pancreatic lipase.
4.4.Help digestion and absorption of fat-solubleHelp digestion and absorption of fat-soluble
vitamins.vitamins.
5.5.Solubilizing cholesterol in bile and preventSolubilizing cholesterol in bile and prevent
gall stone formation.gall stone formation.
6.6.Choleretic action (stimulate their ownCholeretic action (stimulate their own
secretion).secretion).
7.7.Intestinal antiseptic that preventIntestinal antiseptic that prevent
putrefactionputrefaction

CH3
CH3
HO
CH3
C
Sodium-tauro or
glyco-cholate
CH3
CH3
HO
CH3
C
Sodium-tauro or
glyco-chenodeoxycholate
OH
OH OH
O O
R1 or R2 R1 or R2
(CH2)2 SO3
-Na+H2NCH2 COO-Na+H2N
Sodium taurateSodium glycate
R1 R2

Chemistry of lipids

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