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LIPIDS

No concise definition of lipids based on functional group can be given because lipids include
a large number of different types.(For our purpose) a lipid is any substance that meets the
following criteria:
1. insoluble in water but soluble in organic solvents like chloroform,
ether and benzene
2. a constituent of the cell
3. common property of lipids non polar nature
Biological Functions of Lipids
1. structural component of membranes
2. storage form of energy as well as metabolic fuels
3. emulsifiying agents. Like bile acids phospholipids ( serve as major component
system for non plar substances
4. regulators of metabolism : steroid, hormones
5. vitamins : A D E K (fat soluble vitamins)
6. provide insulation for the vital organs , protecting them from mechanical shock and
maintaining optimum body temperature
Major Classes of Lipids

fats and oils


SIMPLE LIPIDS

waxes
undergo hydrolysis

LIPIDS

COMPOUND LIPIDS

DERIVED LIPIDS

phospholipids
sphingolipid
glycolipid

steroid
cholesterol
Vit. D
hormones
bile acids
terpenes
Vit. A,E, K
prostaglandins

do not undergo
hydrolysis

LIPIDS>>>>>>>>>>>> FATTY ACID

ALCOHOL

Fats and oils


Waxes

Fatty acid
Fatty acid

Glycerol
Long chain alcohol

Phospholipids

Fatty acid

glycerol

Sphingolipid

Fatty acid

Glycolipid

Fatty acid

OTHER
COMPOUNDS

Phosphoric acid,
nitrogen contg. Group
Phosphoric acid,
sphingosine. nitrogen
contg. Group
Phosphoric acid,
sphingosine. Neutral
sugar residues

FATTY ACIDS- are RCOOH with long chain HC side group,(unbranched, generally 12-26
carbon atoms in length)
-rarely free in nature, but occur in esterified form as the major components
of the various class of lipids
F.A. obtain from lipids always contain an even number of C atoms

Classes of Fatty Acids


According to Bond Type
Saturated Fatty Acid
Unsaturated Fatty Acid
FATTY ACID
According to Source
Essential
Non- Essential

Saturated Fatty Acid


Name
Molecular
Lauric acid C11H23COOH

Condensed S.F.

CH3( C H2)

10COOH

Myristic
Acid

C 13H27COOH

CH3( C H2)

11COOH

Palmitic
acid

C 15H31COOH

CH3( C H2)

14COOH

C 17H35COOH

CH3( C H2)

16COOH

C 19H39COOH

CH3( C H2)

18COOH

C 23H47COOH

CH3( C H2)

22COOH

Stearic
Acid
Arachidic
acid
Lignoceric
acid

Unsaturated Fatty Acid


NAME
Molecular
Palmitolei
c Acid

5CH=CH(

C H2)

C 17H33COOH

CH3( C H2)

7CH=CH(

C H2)

Linoleic
acid

C 17H31COOH

CH3( C H2)

Linolenic
acid

C 17H29COOH

CH3CH2CH=CHCH2CH=CHCH2CH=CH( CH2)

CH3( C H2)

Eicosapentaenoic acid

Sources
Coconut
oil

C14:0

54

Butterfat
Coconut
oil

C16:0

63

Lard, beef
fat

C18:0

70

Lard, beef

C20:0

77

Peanut oil

Condensed S.F.
CH3( C H2)

Arachidonic Acid

M.Pt.
44

C24:0

C 15H29COOH

Oleic acid

Notation
C12:0

4(

4CH=CHCH2CH=CH(

C H=CHCH2)

CH3( C H2CH=CH)

5(

C H2)

C H2)

7COOH

7COOH

7COOH

7COOH

3CH=CH(

Notatio
n
C16:1
9

M.Pt
.
-0.5

C18: 1
9

16

C18:2
9,12

-5

C18:3
9,12 15

-11.3 Linseed
oil,
corn oil

C H2)

Sources
Cod
liver
oil,
butterfa
t
Lard,
olive
oil
Corn
oil,
soybean
oil

3COOH

3COOH

The melting points of the saturated fatty acids increase with the number of C atoms . Why?
Comparing the C18 fatty acids, we find that their melting points decrease as the degree of
unsaturation increases. Why?
Physical Properties of Fatty Acid

Saturated F.A.

1. are highly flexible molecule : wide range of conformations, due to free


rotation about each of their C-C bond
2. fully extended conformation is of minimum energy due to least amount
of stearic interference between neighboring methylene

groups
3. soluble in water(at least for the 1st 4 aliphatic acids, formic to butyric)
due to it can form H-bond with water. Higher member of
are less soluble in water due to the alkane characteristic of
alkyl chain
4. melting points increases with molecular masses due to increased
VanDer Waals

the series
the long

R C=O

OH

extra Vander
Waals

O H

higher
mpt.

H bonding with
water, soluble
Unsaturated F.A.

Stearic
0
mpt. =69.6

1. m.pt. decreases as the degree of unsaturation increases


2. lipid fluidity increases with the degree of unsaturation of the fatty acid
component of the molecule

>

Oleic

1
mpt=13.4

>

Linoleic
2
mpt=-9

Saturated F.A.:
saturated alkyl chain gives orderly zigzag arrangement, making a tightly
packed crystalline structure ( more energy to convert it to liquid)

Unsaturated F.A.
presence of double bond produces 30o rigid bend on the molecule
preventing it to approach to another molecule

rigid bend

TRIGLYCERIDES (FATS AND OILS) esters of fatty acid and glycerol : View it as
esterification
R C=O
OH

In fats and oils :

+ ROH

H+

R C=O +
OR

H2O

OH
R 1 C =O

R1
CH2 O C=O
CH2 OH

OH
R 2 C=O

CH O C=O
R2

CH OH

CH2 OH

OH
R 3 C=O

CH2 O C=O
R3
fat/oil

Example:
CH3( C H2)

14C=O

( C H2)
CH2 O C=O

OH
CH2 OH
CH3( C H2)

14C=O

OH
CH3( C H2)

( C H2)

CH OH

14CH3

14CH3

CH O C=O

CH2 OH

( C H2)
CH2 O C=O

14C=O
OH

14CH3

fat

Types of Triglycerides:
1. Simple- all R groups are the same
2. Mixed- there are 2 or 3 different R groups
Nomenclature
1. Simple Triglycerides:
a. attach the prefix glyceryl to the name of fatty acid
b. name of fatty acid is given by changing ic ending to ate
or simply change ic ending to in
O

O
CH3( C H2)

14C

CH3( C H2)

14C

CH3( C H2)

14C

O
O

O CH2

CH3( C H2)

16C

O CH2

O CH

CH3( C H2)

16C

O CH

CH3( C H2)

16C

O CH2

O CH2

glyceryl tripalimtate or
glyceryl tripalmitin

O
O

glyceryl tristearate or
glyceryl tristearin

O
CH3( C H2)

7CH=CH(

C H2)

7C

O CH2

CH3( C H2)

7CH=CH(

C H2)

7C

O CH

CH3( C H2)

7CH=CH(

C H2)

O
O

7C

O CH2

glyceryl trioleate or
glyceryl triolein

3. Simple and Mixed Triglycerides


a. list the acyl groups in alphabetical order
b. change the ic ending to oyl and add the word glycerol
c. indicate the positions of the acyl groups by numbering the carbons in the
glycerol backbone
d. use prefixes di, tri,if 2 or more acyl groups are the same
e. the first to be named is given the lowest number possible

O
CH3( C H2)

( p)
( l)

14C

CH3( C H2)

( o) CH3( C H2)

7CH=CH(

C H2)

O CH2

O CH

10C

O CH2

7C

1 oleoyl -2-lauroyl -3-palmitoyl glycerol


O
( s)
( s)
CH3( C H2)

( o)

CH3( C H2)

16C

O CH2

CH3( C H2)

16C

O CH

7CH=CH(

O
O

C H2)

O CH2

7C

1 oleoyl -2,3 distearoyl glycerol

Reactions of Fats and Oils


1. Saponification (Alkaline Hydrolysis)
O
CH3( C H2)

14C

O CH2

CH3( C H2)

14C

O CH

CH3( C H2)

14C

O CH2

O
+

3 CH3( C H2)

3NaOH

14C

CH2 O H
ONa

CH O H
CH2 OH

The products of saponification are 3 fatty acid salts and glycerol


Since each molecule of fat or oil contains 3 ester linkages, it needs 3 units of NaOH or
KOH
Write the equation for the following saponification reaction:
Glyceryl stearate + 3 NaOH = 3 sodium stearate + glycerol

sodium stearate is the principal active component in household soap


sodium salt of fatty acid is hard soap. Potassium salt of the fatty acid is soft soap.
It is more soluble in water, thus it is used in liquid soap and shaving creams.
2. Acid Catalyzed hydrolysis
Recall: RCO OR + HOH >> H+>> RCO OH + ROH
O
CH3( C H2)

14C

O CH2

CH3( C H2)

14C

O CH

CH3( C H2)

14C

O CH2

O
O

+ HOH

CH2 OH

O
3 CH3( C H2)

14C

OH

CH OH
CH2 OH

Digestion of fats and oil is an instance of hydrolysis. Here the catalyst is the
enzyme lipase.
3. Hydrogenation /hardening of oils
Involves the addition of hydrogen in the presence of a catalyst to an alkene
Recall:

CH2=CH2 + H2

CH3CH3

Unsaturated oil + H2 >>>> saturated fat


Write the equation for the hydrogenation of olein.
Unsaturated vegetable oils are partially hydrogenated to yield solid vegetable
shortening like margarine and other butter substitutes
4. Hydrogenolysis: Reduction of C=O to CH2OH
RA may be LiAlH4 or H2 , CuCrO4
Recall:
O
R C OR

O H

LiAlH4

R C

R C O R
-

H /H

+ ROH

LiAlH4

RCH2OH
O
CH3( C H2)

14C

O CH2

CH3( C H2)

14C

O CH

CH3( C H2)

14C

O CH2

LiAlH4

CH2 O H
3 CH3( C H2)

14CH2OH

CH O H
CH2 O H

Thus, triglyceride + LiAlH4 = 3 high MW ROH + glycerol


Write the equation for the reaction . laurin + LiAlH4 = lauryl alcohol + glycerol

CH3( CH2)

11OH

+ HOSO3H

CH3( C H2)

11OSO3H

+ H2O

NaOH
CH3( C H2)

11O SO3 Na

+ H2O

sodium lauryl sulfate


( a detergent)

The lauryl alcohol can be esterified with H2SO4 to produce lauryl hydrogen sulfate whose
sodium salt is a detergent.
Laury alcohol >> HOSO3H>> lauryl bisulfate >>NaOH>> sodium lauryl sulfate (a detergent)
4. Acrolein Formation
a. a qualitative test for detecting fats and oils- detects the glycerol component of fats
and oil
b. when fats and oils are strongly heated acrolein is formed.The reaction involves
the removal of H2O. In the lab KHSO4 is used as a dehydrating agent.

CH2 OH

KHSO4

CH OH
CH2 OH

C=O
C H

H2O

acrolein ( acrid smelling gas)

CH2

5. Oxidation ( oxidative rancidity)


FATs and oils undergo chemical changes when exposed to air light and heat.
Oxygen in air attacks unsaturated glycerides at the double bond.
The oxidation process is somewhat complicated and results in the eventual breaking of the
double bonds forming, aldehydes, ketones and fatty acids of low molecular weight.
CH2 O C=O
R1
RCOOH

CH O C=O
R2

Aldehydes +ketones

CH2 O C=O
R3

These volatile products cause unpleasant odor and taste of rancid butter . Rancid oils are
those in which the oxidation process has occurred.
Antioxidants such as hydroquinone may be added to prevent rancidity. Vegetable fats
contain natural antioxidants like tocopherol(Vitamin E) and ascorbic acid (Vitamin C). Two
synthetic antioxidants are BHA and BHT. In the presence of air, antioxidants are oxidized
instead of the food.
OH

hydroquinonne
OH
OH
C( C H3)

OH
C( C H3)

H3C

CH3

C( C H3)

OCH3
BHA

BHT

Analysis of Fats and Oils


In order to control over the raw material used in the manufacture of soaps, synthetic
detergent , drying oil, etc, many analytical methods have been advised. Some of the
important ones are:
1. Saponificaton Number- number of mg of KOH required to hydrolyze 1 g of fat/oil
Varies inversely with the average MW of fat/oil
R1

R 1COOK

CH2O C=O
CH O C=O
R2
CH2
O C=O
R3
1 g fat/oil

+ 3 KOH

R 2COOK
R 3COOK

CH2OH
+

CHOH
CH2OH

The greater the % of Low MW glycerides the fat contains, the ________ is the amount of
KOH needed to hydrolyze per gram of fat, therefore the ______the saponification number.
The greater the % of high MW glycerides the fat contains, the _______ is the amount of
KOH needed for hydrolysis, therefore the ______ the saponification number .
Which of the ff: will have the highest percentage of low MW glycerides?
Lard, SN=195-203 Buttter, SN=210-230 Olive oil, SN = 187-196
2. Iodine Number-number of grams of I2 that reacts with 100 g fat/oil sample.
Iodine reacts with the double bond ( 1 molecule of I2 per double bond.) Thus the iodine
number is a measure of the degree of unsaturation of the fat/oil. The higher the iodine
number, the ______ the number of double bonds and the _______ the degree of
unsaturation.
Which is the most unsaturated ?
Lard, IN=46-70 Butter, IN=26-28

Oilve oil, IN= 79-90

3. Acid Number- the number of mg of KOH needed to neutralize the free fatty acids in 1 g
of fat/oil . The more rancid the fat/oil, the ______ is the degree of oxidation, the ______
the number of free fatty acids formed, the _____ amount of KOH needed, the _____ the
acid number . Thus a good quality fat/oil has ______ acid number.
WAXES = esters of long chain monohydric alcohol and fatty acid
= found in both plants and animals
= not easily hydrolyzed and are useful as protective coatings
Plant Waxes= found on the surface of leaves and stems
=protect plants from dehydration and invasion of harmful organisms
Eg. Carnauba wax-myricyl cerotate=from leaves of Brazilian palm
trees
=used as floor and automobile wax
Animal Waxes= found on the surface of feathers, skin and hair and help to keep these
surfaces soft and pliable
Eg. Bees wax- myricyl palmitate- secreted by wax glands of bees
Spermaceti-cetyl palmitate-found in the head cavities and blubber
of sperm whale= used in cosmetics, candles, ointments
Lanolin=from wool= used as base for creams, ointments
COMPOUND LIPIDS
Kinds:
Phospholipid =major component of biological membranes
=consists of glycerol phosphate esterified at C1& C2 to FA and its
phosphoryl group to a group X

1 CH2 O H

R
CH2 O C=O

2 CH O H

CH O C=O
R

CH2 O P O
HO OH

CH2 O P =O
O
HO

R
CH2 O C=O
If X=H

CH O C=O
R

glycerol phosphate
phospholipid

CH2 O P=O
HO O

phosphatidic acid

USES OF
Phosphatidyl ethanolamine
Phosphatidyl serine
(cephalins)
-plays an important role in blood clotting

R
CH2 O C=O
CH O C=O
R

If X = CH2CH2NH3
( ethanolamine)

CH2 O P=O
O
HO

CH2CH2NH3

phosphatidyl ethanolamine

Lecithin
- emulsifying agent
- antioxidant in food products
- dissolves fats
- supplies H3PO4 to build new tissues

R
CH2 O C=O

+
3

If X=CH2CH2N( C H3)

CH O C=O
R

( choline)

CH2 O P =O
HO O

CH2CH2N( C H3)

+
3

phosphatidyl choline ( lecithin)

R
CH2 O C=O
If X = CH2CH( NH3)

CH O C=O
R

COO

( serine)

CH2 O P=O
HO O

CH2CH( NH3)

COO

phosphatidyl serine

Sphingolipid- present in large amounts in brain and nerve tissues


-occur in membranes of both plants and animals

OH
CH3 ( C H2)

12 CH=CH

CH

OH
CH3 ( C H2)

CH NH2
CH2OH
sphingosine

12 CH=CH

CH

H C N C=O
R
HOCH2
H
ceramide

Niemann-Pick Disease-lipid storage


disease due to accumulation of
sphingomyelin in the brain, liver and
Spleen, resulting in mental retardation
and early death.

H
CH3 ( C H2)

12 CH=CH

C OH

H C

H2

N C=O
R
H
O
O

P=O
OCH2CH3N( C H3)

sphingomyelin
Glycolipid(glycosphingolipid) derivative of ceramide
Contain one or more neutral sugar residues as their polar
head groups

OH
CH3 ( C H2)

12 CH=CH

CH

H C N C=O
R
HOCH2
H

galactose or glucose

ceramide

Examples:
1. Cerebrosides simplest sphingolipid consisting of a simple sugar residue as its head
group
2. Galactocerebrosides have a B-D galactose head group
Prevalent in the neuronal cell membranes of the brain
3. Gangliosides- ceramide oligosaccharides
Most complex group of glycolipid
Uses:
1. Act as specific receptors for certain pituitary glycoprotein hormone
2. receptors for bacterial protein toxins such as cholera toxins
3. serves as specific cell-cell recognition probably having an important role in the
growth and differentiation of tissues
Tay-Sachs Disease- lacks enzymes that break down glycolipid so they accumulate in the tissues
of the brain and eyes.
DERIVED LIPIDS
Kinds
1. Steroids- are high MW tetracyclic compounds that exist in a great variety of structural
forms all of them consist of the steroid nucleus .

C
A

D
cyclopentano perhydrophenanthrene

steroid nucleus
A. Cholesterol
does not occur in plants but in most meats and animal products (E.g
butter, cheese, creams)
most abundant steroid in the human body , high occurrence in
brain and nerve tissues
-most of it is converted into cholic acid which is used in the formation of
bile salts
- normally eliminated in the bile
-principally constituent of gallstones
Precipitation of cholesterol in the bile liquid forms gallstones.
-gallstones are very painful and may block the normal bile liquid flow
resulting jaundice condition
Precipitation in the blood serum leads to constriction of blood vessels which in
turn reduces the blood flow resulting to high blood pressure. (atheriosclerosis )
Arteriosclerosis hardening of the arteries that produces degenerative heart
disease, stroke and other aterial diseases.
Uses:

1. precursor of bile acids


2. important precursor in the biosynthesis of Vit. D, sex hormones
3. aids in the absorption of fatty acids in the small intestines

sex hormones
testosterone
estrogens
progesterone

CH3

male
female

CH3

CH3
CH3

bile acids
help in the digestion
of fatty materials

CH3

HO

metabolic hormones
regulate sugars, proteins
salt, and water

cholesterol

2. Vitamins A, D, E, K
E= antioxidant
K= coenzyme
A= (called retinol) plays an important role in vision
D= The body synthesizes vitamin D from 7 dehydrocholesterol , a steroid found
in the skin , in a series of reactions that requires UV.
A deficiency in Vit. D which can be prevented by getting enough sun causes a disease
known as rickets. Rickets is characterized by deformed bones and stunted growth. Too much
Vit. D is also harmful because it causes the calcification of soft tissues. It is thought that skin
pigmentation evolved to protect the skin from the suns UV rays in order to prevent the
synthesis of too much Vit. D. This agrees to the observation that people close to the equator
have greater skin pigmentation.
3. Terpenes have been used as spices, perfumes, and medicines for thousand of years
Classes
a. monoterpenes ( 2) isoprene units ( 10 carbons)
b. sesquiterpenes (3) ---------------- fragrances and flavorings found in
plants called essential oils
c. triterpenes (6) --------------------d. tetraterpenes (8) ------------------

isoprene unit ( 5 C's)

HO
carvone
spearmint oil
a monoterpene

menthol
peppermint oil

farnesene a sesquiterpene found in the waxy coating on apple skins

Carotenoids are tetraterpenes


Lycopene compound responsible for the red color of tomatoes and watermelon
B carotene orange coloring of carrots and apricots

lycopene