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Rajendra Dev Bhatt (PhD Scholar)
Asst. Professor
Clinical Biochemistry & Laboratory Medicine
Fellow: Translational Research (2018-2022) in CVD in Nepal,
NHLBI & NIH USA
Thursday, July 6, 2023 1
LIPID(S)
6/29/2012 1
Thursday, July 6, 2023
6/29/2012 2
The boundaries of all cells are defined by
biological membranes.
These barriers prevent molecules generated
inside the cell from leaking out and unwanted
molecules from diffusing in.
They also contain transport systems that allow
the cell to take up specific molecules and
remove unwanted ones.
 Lipids are a heterogeneous group of
compounds, including fats, oils, steroids,
waxes, and related compounds, that are
related more by their physical than by their
chemical properties.
They have the common property of being
(1) relatively insoluble in water and (2)
soluble in nonpolar solvents such as ether
and chloroform.
Thursday, July 6, 2023 6/29/2012 3
3
 Storage form of energy
 Important dietary components because of their high
energy value and also because of the fat-soluble
vitamins and the essential fatty acids contained in
the fat of natural foods.
 Structural components of biomembranes
 Serve as thermal insulators in the subcutaneous
tissues and around certain organs
 Nonpolar lipids act as electrical insulators,
allowing rapid propagation of depolarization waves
along myelinated nerves
Thursday, July 6, 2023 6/29/2012 4
4
 Provide shape and contour to the body
 Act as metabolic regulators
 Combinations of lipid and protein
(lipoproteins) are important cellular
constituents, occurring both in the cell
membrane and in the mitochondria, and
transporting lipids in the blood.
Thursday, July 6, 2023 6/29/2012 5
5
Following diseases are associated with abnormal
chemistry or metabolism of lipids-
Obesity
Atherosclerosis
Diabetes Mellitus
Hyperlipoproteinemia
Fatty liver
Lipid storage diseases
Thursday, July 6, 2023 6/29/2012 6
6
Simple lipids: Esters of fatty acids with
various alcohols.
a.Fats: Esters of fatty acids with glycerol.
Oils are fats in the liquid state.
b.Waxes: Esters of fatty acids with higher
molecular weight monohydric alcohols.
Thursday, July 6, 2023 6/29/2012 7
7
2.Complex lipids: Esters of fatty acids containing
groups in addition to an alcohol and a fatty acid.
a.Phospholipids: Lipids containing, in addition to fatty
acids and an alcohol, a phosphoric acid residue.
They frequently have nitrogen-containing bases and
other substituents, eg, in glycerophospholipids the
alcohol is glycerol and in sphingophospholipids the
alcohol is sphingosine.
Thursday, July 6, 2023 6/29/2012 8
8
Thursday, July 6, 2023 6/29/2012 9
a.Glycolipids (glycosphingolipids): Lipids
containing a fatty acid, sphingosine, and
carbohydrate.
b.Other complex lipids: Lipids such as
sulfolipids and aminolipids. Lipoproteins
may also be placed in this category.
3) Precursor and derived lipids:
These include-
 fatty acids
 glycerol
 steroids
 other alcohols
 fatty aldehyde
 ketone bodies
 hydrocarbons, lipid-soluble vitamins, and
hormones.
Thursday, July 6, 2023 6/29/2012 10
10
Fatty acids are aliphatic carboxylic acids
Have the general formula R-(CH2)n-COOH
They occur mainly as esters in natural fats
and oils but do occur in the unesterified form
as free fatty acids, a transport form found in
the plasma.
Fatty acids that occur in natural fats are
usually straight-chain derivatives containing
an even number of carbon atoms.
Thursday, July 6, 2023 6/29/2012 11
11
Thursday, July 6, 2023 6/29/2012
Fatty Acids are carboxylic acid
with hydrocarbon side chain
CH3-COOH (Acetic acid)
CH3-CH2-COOH (Propionic acid)
CH3-CH2-CH2-COOH (Butyric acid)
CH3- (CH2)14-COOH (Palmitic acid)
12
Fatty acids can be classified in many ways-
1) According to nature of the hydrophobic
chain-
a) Saturated
b) Unsaturated
Saturated fatty acids do not contain double
bonds, while unsaturated fatty acids contain
double bonds
Thursday, July 6, 2023 6/29/2012 13
13
Saturated fatty acids may be expected based
on acetic acid (CH3 —COOH) as the first
member of the series in which —CH2 — is
progressively added between the terminal CH3
— and —COOH groups.
Fatty acids in biological systems usually
contain an even number of carbon atoms,
typically between 14 and 24. The 16- and 18-
carbon fatty acids are most common.
Thursday, July 6, 2023 6/29/2012 14
14
Number of C
atoms
Common Name Systemic Name Formula
2 Acetic acid Ethanoic acid CH3COOH
4 Butyric acid Butanoic acid CH3(CH2)2COOH
6 Caproic acid Hexanoic acid CH3(CH2)4COOH
8 Caprylic acid Octanoic acid CH3(CH2)6COOH
10 Capric acid Decanoic acid CH3(CH2)8COOH
12 Lauric acid Dodecanoic acid CH3(CH2)10COOH
14 Myristic acid Tetradecanoic
acid
CH3(CH2)12COOH
16 Palmitic acid Hexadecanoic
acid
CH3(CH2)14COOH
18 Stearic acid Octadecanoic
acid
CH3(CH2)16COOH
20 Arachidic acid Eicosanoic acid CH3(CH2)18COOH
22 Behenic acid
Docosaionic acid
C6
/
H2
9
/
2
(0
C1
2
H ) COOH
3 2 20
12
Thursday, July 6, 2023 6/29/2012 15
Unsaturated fatty acids may further be divided as
follows-
(1) Monounsaturated (monoethenoid, monoenoic) acids,
containing one double bond.
(2)Polyunsaturated (polyethenoid, polyenoic) acids,
containing two or more double bonds.
The configuration of the double bonds in most
unsaturated fatty acids is cis.
The double bonds in polyunsaturated fatty acids are
separated by at least one methylene group.
Thursday, July 6, 2023 6/29/2012 16
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The systematic name for a fatty acid is
derived from the name of its parent
hydrocarbon by the substitution of anoic for
saturated and enoic for unsaturated fatty acids.
For example, the C18 saturated fatty acid
is called octadecanoic acid because the
parent hydrocarbon is octadecane.
Thursday, July 6, 2023 6/29/2012 18
Thursday, July 6, 2023 6/29/2012
A C18 fatty acid with one double bond is
called octadecenoic acid; with two double
bonds, octadecadienoic acid; and with three
double bonds, octadecatrienoic acid.
The notation 18:0 denotes a C18 fatty acid
with no double bonds, whereas 18:2 signifies
that there are two double bonds
19
Carbon atoms are numbered from the carboxyl
carbon (carbon No. 1). The carbon atoms adjacent
to the carboxyl carbon (Nos. 2, 3, and 4) are also
known as the α ,β , and carbons, respectively, and
the terminal methyl carbon is known as theω or n-
carbon.
The position of a double bond is represented by the
symbol ∆ followed by a superscript number.
eg, ∆ 9 indicates a double bond between
carbons 9 and 10 of the fatty acid;
Thursday, July 6, 2023 6/29/2012 20
Alternatively, the position of a double bond can be
Thursday, July 6, 2023 6/29/2012
denoted by counting from the distal end, with the ω-
carbon atom (the methyl carbon) as number 1.
ω9 indicates a double bond on the ninth carbon counting
from the ω-carbon.
In animals, additional double bonds are introduced only
between the existing double bond (eg, 9, 6, or 3) and the
carboxyl carbon, leading to three series of fatty acids known
as the ω9, ω6, and ω3 families, respectively.
6/ 9/2012
Biochemistry for medics
21
S.No. Number of C
atoms,
number and
location of
double bonds
Family Common
Name
Systemic
Name
[A] Monoenoic
acids (one
double bond)
1. 16:1;9 ω 7 Palmitoleic
acid
cis-9-
Hexadecenoic
2. 18:1;9 ω 9 Oleic Acid cis-9-
Octadecenoic
3. 18:1;9 ω 9 Elaidic acid trans 9-
Octadecanoic
[B] Dienoic acids
(two double
bonds)
1. 18:2;9,12 ω 6 Linoleic acid all-cis-9,12-
6/29/201
O2
ctadecadie1
n8
o
h
Thursday, July 6, 2023 6/29/2012 22
Arachidonic acid All cis
S.No. Number of C
atoms,
number and
location of
double bonds
Family Common
Name
Systemic
Name
[c] Trienoic acids
(three double
bonds)
1. 18:3;6,9,12 ω 6 Y- Linolenic
acid
all-cis-
6,9,12-
Octadecatrien
oic
2. 18:3;9,12,15 ω 3 α-Linolenic all-cis-
9,12,15Octad
ecatrienoic
[D] Tetraenoic
acid(Four
double bonds)
20:4;5,8,11, ω6 19
Thursday, July 6, 2023
S.No. Number of C
atoms,
number and
location of
Thursday, July 6, 2023 6/29/2012
double bonds
Family Common
Name
Systemic
Name
[E] Pentaenoic
acids (Five
double
bonds)
1. 20:5;5,8,11,1
4,17
ω 3 Timnodonic
acid
all-cis-
5,8,11,14,17-
Eicosapenta
enoic
[F] Hexaenoic
acid(Four
double bonds)
22:6;4,7,10,1
3,16,19
ω3 Cervonic acid all-cis-
19-
6/29/201
42
,7,10,13,1620
,
h
24
Thursday, July 6, 2023 6/29/2012 25
Depending upon the orientation of the
radicals around the axis of the double
bond-
Cis- If the radicals are on the same
side of the double bond
Trans- If the radicals are on the
opposite side
Oleic acid and Elaidic acid have the
same formula but Oleic acid is cis while
Elaidic acid is Trans Fatty acid
Thursday, July 6, 2023 6/29/2012 26
The hydrocarbon chains in saturated fatty acids are,
fairly straight and can pack closely together, making
these fats solid at room temperature.
Oils, mostly from plant sources, have some double
bonds between some of the carbons in the hydrocarbon
tail.
Increase in the number of cis double bonds in a fatty
acid leads to a variety of possible spatial configurations
of the molecule—eg, Arachidonic acid,
with four cis double bonds, has "kinks" or a U shape.
Thursday, July 6, 2023 6/29/2012 27
Because of the kinks (sharp curve) in the
hydrocarbon tails, unsaturated
fats can't pack closely together, making them liquid
at room temperature.
The membrane lipids, which must be fluid at all
environmental temperatures, are more unsaturated
than storage lipids.
The carbon chains of saturated fatty acids
form a zigzag pattern when extended, as at low
temperatures. 6/29/2012 28
 Trans fatty acids are present in certain foods,
arising as a by-product of the saturation of fatty
acids during hydrogenation, or "hardening," of
natural oils in the manufacture of margarine.
An additional small contribution comes from the
ingestion of ruminant fat that contains trans fatty
acids arising from the action of microorganisms in
the rumen.
Naturally-occurring unsaturated vegetable oils
have almost all cis bonds, but using oil for frying
causes some of the cis bonds to convert to trans
bonds.
Thursday, July 6, 2023 6/29/2012 29
Thursday, July 6, 2023 6/29/2012 30
Properties of Fatty Acids
Hydrogenation :The Good Gone Bad
Hydrogenation is a chemical process that adds hydrogen to
the unsaturated bonds on the FA chains attached to the
TAG backbone.
In this way, an unsaturated fat can be turned into a
saturated fat and increase its melting point.
Recall that the addition of hydrogen to an alkene
(unsaturated) results in an alkane (saturated). A simple
hydrogenation reaction is:
H2C=CH2+H2→CH3CH3
alkene plus hydrogen yields an alkane
Thursday, July 6, 2023 6/29/2012 31
Processing naturally occurring fats to modify their
texture from liquid to semisolid and solid forms results
in the development of trans fats, which have been
linked to an increased risk for heart disease.
Trans fats are used in many processed foods such as
cookies, cakes, chips, doughnuts, and snack foods to
give them their crispy texture and increased shelf life.
The AHA states that, like saturated fats, trans fats raise
LDL “bad cholesterol,” but unlike saturated fats, trans
fats lower HDL “good cholesterol.”
Properties of Fatty Acids
Thursday, July 6, 2023 6/29/2012 32
Halogenation:
When treated with halogens under mild conditions, the
unsaturated fatty acids can take up two halogen atoms, at
each double bond to form the halogenated derivative of
the fatty acid.
For example, Oleic acid + I2 → Di-iodo oleic acid The
number of halogen atoms taken up will depend on the
number of double bonds and is an index of the degree of
unsaturation.
Properties of Fatty Acids
Thursday, July 6, 2023 6/29/2012 33
Melting Point:
The short and medium chain fatty acids are liquids,
whereas long chain fatty acids are solids at 25
degree . The solubility in water decreases, while
melting and boiling points increase, with increase in
chain length.
The unsaturated fatty acids have lower melting point
compared to saturated fatty acids with the same
chain length.
Properties of Fatty Acids
Thursday, July 6, 2023 6/29/2012 34
Salt Formation:
Saturated and unsaturated fatty acids form salts with
alkali.
CH3—COOH + NaOH → CH3—COONa + H2O
Sodium and potassium salts of long chain fatty acids
are called soaps. Calcium and magnesium soaps are
insoluble.
The saponification number indicates how much
potassium hydroxide is needed to saponify 1g fat.
Properties of Fatty Acids
Thursday, July 6, 2023 6/29/2012 35
Ester Formation:
Both saturated and unsaturated fatty acids form
esters with alcohols, especially with glycerol.
Fatty acids can form mono-, di- or tri- esters with
alcohol groups of glycerol.
Triglycerides or triacylglycerols are also known as
neutral fat.
Properties of Fatty Acids
Thursday, July 6, 2023 6/29/2012 36
Oxidation of Fatty Acids:
All fatty acids undergo oxidation in the body to
give energy.
Beta-oxidation is the major process by which acids
are oxidized.
However, the unsaturated fatty acids can undergo
auto oxidation, due to the presence of the highly
reactive double bonds and a variety of products.
Properties of Fatty Acids
Short chain-with 2-6 carbon atoms
Medium chain- with 8-14 carbon atoms
Long chain- with 16-18 carbon atoms
Very long chain fatty acids- with 20 or
more carbon atoms
Thursday, July 6, 2023 6/29/2012 37
Polyunsaturated fatty acids such as Linoleic and
Linolenic acids are essential for normal life
functions. They are therefore characterized as
essential fatty acids.
Arachidonic acid is considered as semi essential
fatty acid since it can be synthesized from Linoleic
acid .
Essential polyunsaturated fatty acids can be
classified as belonging to one of two "families",
the omega-6 family or the omega-3 family.
Fatty acids belonging to these two families differ
not only in their chemistry, but also in their natural
occurrence and biological functions.
Thursday, July 6, 2023 6/29/2012 38
Components of cell membranes, structural
elements of gonads and mitochondrial membrane
Required for brain growth and development
Precursors of Eicosanoids
Play important role in vision
They have a cardio protective role- Lower
serum cholesterol and increase HDLlevels
Prevent fatty liver formation
Deficiencies of essential polyunsaturated fatty
acids may cause a wide variety of symptoms,
including retarded growth in children, reduced
fertility and pathologic changes in the skin.
Thursday, July 6, 2023 6/29/2012 39
Thursday, July 6, 2023 6/29/2012
Most commonly occurring fatty acids in nature are :
a. Even number of un-branched chain of 12-24 carbons
b. Odd number of un-branched chain of 12-24 carbons
c. Even number of branched chain of 12-24 carbons
d. Odd number of branched chain of 12-24 carbons
Answer: a. Even number of un-branched chain of
12-24 carbons
40
Thursday, July 6, 2023 6/29/2012
In most of the naturally occurring mono-
unsaturated fatty acids , the double bond will
be placed between:
a.C6-C7
b.C7-C8
c.C8-C9
d.C9-C10
Answer: d.C9-C10
41
Thursday, July 6, 2023 6/29/2012
The best source of trans fatty acid in our diet is:
a. Vegetables
b. Ground nut
c. Dairy products
d. Fruits
Answer: c. Dairy products
42
Thursday, July 6, 2023 6/29/2012
In naturally occurring fatty acids, the bond are in
conformation :
a. Cis conformation
b. Trans conformation
c. Mixture of Cis and Trans
d. Cis and Trans conformation alternatively
Answer: a. Cis conformation
43
Most important sterol in
human body
Molecular formula-C27H45
OH
Possesses a cyclo pentano
perhydrophenatherene ring
nucleus
Has an -OH group at C3
A double bond between C5
and C6
Two- CH3 groups at C10
and C13
And eight carbon side chain
attached to C17
Thursday, July 6, 2023 6/29/2012 44
Cholesterol: Structure
Cholesterol
Perhydrocyclopentanophenanthrene
Cholesterol occurs both as free form or in ester form
In cholesteryl ester, the hydroxyl group on position 3 is
esterified with a long-chain fatty acid.
Cholesterol esters are formed by the transfer of acyl group
by Acyl transferases- Lecithin Cholesterol
Acyltransferase (LCAT) & Acyl-CoA Cholesterol O-
Acyltransferase (ACAT)
In plasma, both forms are transported in lipoproteins
Plasma low-density lipoprotein (LDL) is the vehicle of
uptakeof cholesterol and cholesteryl ester into many tissues.
Thursday, July 6, 2023 6/29/2012 46
Thursday, July 6, 2023 6/29/2012
Free cholesterol is removed from tissues by
plasma high-density lipoprotein (HDL) and
transported to the liver, where it is eliminated
from the body either unchanged or after
conversion to bile acids in the process known as
reverse cholesterol transport
A sum total of free and ester cholesterol in serum
is called serum total cholesterol
47
Cholesterol is widely distributed in all cells of the body
but particularly in nervous tissue.
It is a major constituent of the plasma membrane
and of plasma lipoproteins.
It is synthesized in many tissues from acetyl-CoA and is
the precursor of all other steroids in the body, including
corticosteroids, sex hormones, bile acids, and vitamin D.
Cholesterol is a major constituent of gallstones.
Its chief role in pathologic processes is as a factor in the
genesis of atherosclerosis of vital arteries, causing
cerebrovascular, coronary, and peripheral vascular
disease.
Thursday, July 6, 2023 6/29/2012 48
Desirable level of serum total cholesterol is
200 mg/dL
 Physiological variations-
Low at the time of birth, increases with
advancing age.
The level is increased during pregnancy
Pathological Variations-
a) Low cholesterol (Hypocholesterolemia)-
Thyrotoxicosis, anemia, hemolytic jaundice, wasting
diseases and malabsorption syndrome.
Thursday, July 6, 2023 6/29/2012 49
B) Hypercholesterolemia-
 Nephrotic syndrome
Diabetes Mellitus
Obstructive Jaundice
Myxoedema/ Hypothyroidism
Xanthomatous biliary cirrhosis/
Hyperlipoproteinemia due to liver diseases
Hypopituitarism
Familial Hypercholesterolemia
Idiopathic
Thursday, July 6, 2023 6/29/2012 50
7- dehydrocholesterol- also called as
Provitamin D3 (Precursor of vitamin
D)
Ergo sterol-plant sterol (First isolated from
Ergot- Fungus of Rye)
Other steroids- Bile acids, adrenocortical
hormones, gonadal hormones, D vitamins and
Cardiac glycosides.
Thursday, July 6, 2023 6/29/2012 51
 Neutral fats or Triacylglycerol
The triacylglycerols are esters of the
trihydric alcohol, glycerol and fatty acids.
Mono- and Diacylglycerol, wherein one
or two fatty acids are esterified with
glycerol, are also found in the tissues.
Naturally occurring fats and oils are
mixtures of triglycerides.
If all the OH groups are esterified to
same fatty acids- It is Simple Triglyceride
If different fatty acids are esterified- it is
known as Mixed triglyceride.
Thursday, July 6, 2023 6/29/2012 52
Colourless, odourless and tasteless
Insoluble in water
Specific gravity is less than 1.0,
consequently all fats float in water
Oils are liquids at 200C, they contain higher
proportion of Unsaturated fatty acids
Fats are solid at room temperature and
contain saturated long chain fatty acids
Triglycerides are the storage form of energy in
adipose tissue
Triglycerides in the body are hydrolyzed by Lipases
40
Biochemistry for medics 6/29/2012
6/29/2012
Thursday, July 6, 2023 53
Saponification-When the triglycerides are hydrolyzed
by alkali the process is known as Saponification.
Rancidity-Fats and oils have a tendency to become rancid.
Rancidity refers to the appearance of unpleasant taste and
smell of fats.
Hydrolytic rancidity is due to partial hydrolysis of
triglycerides due to traces of lipases present in the given fat
Oxidative rancidity is due to partial oxidation of
unsaturated fatty acids with the resultant formation of
epoxides and peroxides by free radicals.
Preserving the fats with antioxidants can prevent rancidity
Thursday, July 6, 2023 6/29/2012 54
They are esters of higher fatty acids with higher
mono hydroxy aliphatic alcohols(e.g. Cetyl
alcohol)
 Have very long straight chain of 60-100 carbon
atoms
They can take up water without getting dissolved
in it
Used as bases for the preparation of cosmetics,
ointments, polishes, lubricants and candles.
In nature, they are found on the surface of plants
and insects.
Thursday, July 6, 2023 6/29/2012 55
Lipid index Details Significance
Saponification number Number of mg of KOH
required to saponify the
free and combined fatty
acids in 1G. of a given fat
Indicates molecular
weight and is inversely
proportional to it.
Iodine number Number of grams of
iodine absorbed by 100
gm of fat
It is a measure of degree
of unsaturation of a fat
Acid number Number of mg of KOH
required to neutralize the
fatty acids in a gram of a
fat
Indicates the degree of
rancidity of a fat
Thursday, July 6, 2023 6/29/2012 56
a)Phospholipids-
Contain in addition to fatty acids and
glycerol/or other alcohol, a phosphoric acid
residue, nitrogen containing base and other
substituents.
Phospholipids may be regarded as derivatives
of phosphatidic acid , in which the phosphate is
esterified with the —OH of a suitable alcohol.
They are amphipathic molecules containing a
polar head and a hydrophobic portion
Thursday, July 6, 2023 6/29/2012 57
Based on nature of alcohol-
1) Glycerophospholipids- Glycerol is the alcohol group.
Examples-
o Phosphatidyl choline
o Phosphatidyl ethanolamine
o Phosphatidyl serine
o Phosphatidyl inositol
o Phosphatidic acid
o Cardiolipin
o Plasmalogen
o Platelet activating factor
o Phosphatidyl Glycerol
2) Sphingophospholipids- Sphingol is the alcohol group
Example- Sphingomyelin
Thursday, July 6, 2023 6/29/2012 58
1) Phosphatidylcholines (Lecithins )
Phosphoacylglycerols containing choline are the
most abundant phospholipids of the cell membrane
Are present a large proportion of the body's store
of choline. Choline is important in nervous
transmission, as acetylcholine, and as a store of
labile methyl groups
Dipalmitoyl lecithin is a very effective surface-
active agent and a major constituent of the
surfactant preventing adherence, by reducing
surface tension, of the inner surfaces of the lungs.
Its absence from the lungs of premature infants
causes respiratory distress syndrome.
Thursday, July 6, 2023 6/29/2012 59
2) Phosphatidyl ethanolamine (cephalin)-
Structurally similar to Lecithin with the exception that
the base Ethanolamine replaces choline
Brain and nervous tissue are rich in Cephalin
3)Phosphatidyl Serine-(found in most tissues) differ from
phosphatidylcholine only in that serine replaces choline
4) Cardiolipin –
Abundantly found in mitochondrial membrane.
This is the only phospholipid with antigenic
properties.
Thursday, July 6, 2023 6/29/2012 60
5) Platelet activating factor (PAF)-
PAF activates inflammatory cells and mediates
hypersensitivity,
acute inflammatory and anaphylactic reactions
Causes platelets to aggregate and degranulate and
neutrophils and alveolar macrophages to generate
superoxide radicals
6) Phosphatidyl Glycerol-
Formed by esterification of phosphatidic acid with glycerol
Diphosphatidyl glycerol, cardiolipin is found in the
mitochondrial membrane
Thursday, July 6, 2023 6/29/2012 61
Sphingomyelin-
Backbone is sphingosine (amino
alcohol)
A long chain fatty acid is attached to
amino group of sphingosine to form
Ceramide
The alcohol group at carbon- 1
of sphingosine is esterified to phosphoryl
choline, producing sphingomyelin
Sphingomyelin is an important
component of myelin of nerve
fibers
Thursday, July 6, 2023 6/29/2012 62
Components of cell membrane, mitochondrial membrane and
lipoproteins
Participate in lipid absorption and transportation from intestine
Play important role in blood coagulation
Required for enzyme action- especially in mitochondrial
electron transport chain
Choline acts as a lipotropic agent
Membrane phospholipids acts as source of Arachidonic acid
Act as reservoir of second messenger- Phosphatidyl Inositol
Act as cofactor for the activity of Lipoprotein lipase
Phospholipids of myelin sheath provide insulation around the
nerve fobers
Dipalmitoyl lecithin acts as a surfactant
Thursday, July 6, 2023 6/29/2012 63
L/S Ratio in amniotic fluid is used for the
evaluation of fetal lung maturity
Prior to 34 weeks gestation, lecithin and
sphingomyelin concentrations are equal but
afterwards there is marked increase in Lecithin
concentration.
A L/S ratio of > 2 indicates adequate fetal lung
maturity
Delivery of a premature,low birth weight baby
with low L/S ratio (1 or<1) predisposes the child to
respiratory distress syndrome
Thursday, July 6, 2023 6/29/2012 64
Thursday, July 6, 2023 6/29/2012
Lipoproteins
Chylomicrons
VLDL
IDL
LDL
HDL
67
General Structure of Lipo proteins
Lipoproteins consist of a nonpolar core and asingle
surface layer of amphipathic lipids
 T h e nonpolar lipid core consists of mainly
triacylglycerol and cholesteryl ester and is
surrounded by a single surface layer of
amphipathic phospholipid and cholesterol
molecules
These are oriented so that their polar groups face
outward to the aqueous medium.
 Theprotein moiety of a lipoprotein is known as an
apolipoprotein or apoprotein.
Classification of Lipoproteins
Lipoproteins can be classified on the basis of density
Based on density- They are separated by
Ultracentrifugation. Five major groups of lipoproteins
have been identified which are important physiologically
and in clinical diagnosis.
(i) Chylomicons, derived from intestinal absorption of
triacylglycerol and other lipids; Density is generally less
than 0.95 while the mean diameter lies between 100- 500
nm
Classification of Lipoproteins
(ii)Very low density lipoproteins (VLDL), derived
from the liver for the export of triacylglycerol;
density lies between 0.95- 1.006 and the mean
diameter lies between 30-80 nm.
(iii)Intermediate density lipoproteins (IDL) are
derived from the catabolism of VLDL,with a density
ranging intermediate between Very low density and
Low density lipoproteins i.e. ranging between 1.006-
1.019 and the mean diameter ranges between 25-
50nm.
Classification of Lipoproteins
iv) Low-density lipoproteins (LDL), representing a
final stage in the catabolism of VLDL; density lies
between 1.019-1.063 and mean diameter lies between
18-28 nm
(iv) High-density lipoproteins (HDL), involved in
cholesterol transport and also in VLDL and
chylomicron metabolism. Density ranges between
1.063-1.121 and the mean diameter varies between 5-15
nm.
Classification of Lipoproteins
Lipoproteins with high lipid content will have low density, larger
size and so float on centrifugation. Those with high protein content
sediment easily, have compact size and have a high density.
8
Thursday, July 6, 2023 6/29/2012
The cholesterol serves as the precursor for the
following biosynthetic pathways EXCEPT
a. Bile acid synthesis
b. Steroid hormone synthesis
c. Aldosterone synthesis
d. Thyroid hormone synthesis
d. Thyroid hormone synthesis
73
Thursday, July 6, 2023 6/29/2012
Which of the following lipids act as lungs
surfactants?
a. Phosphatidylcholine
b. Phosphatidylethanolamine
c. Ceramide
d. Phosphatidylinositol
a. Phosphatidylcholine
74
Thursday, July 6, 2023 6/29/2012
All of the following are complex lipids, except
a. Phosphatidic acid
b. Cerebroside
c. Cardiolipin
d. Cholesterol
d. Cholesterol
75
Thursday, July 6, 2023 6/29/2012
Which of the following is an essential fatty acid?
a. Linolenic acid
b. Arachidonic acid
c. Oleic acid
d. Palmitic acid
a. Linolenic acid
76
Thursday, July 6, 2023 6/29/2012
Besides high cholesterol, which of these can
make it more likely that you will get heart
disease?
A. Cigarette smoking
B. High blood pressure
C. Family history of heart disease
D. Age
E. All of the above
E. All of the above
77

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Biochemistry of Lipids_MBBS_BDS-Lab.Med.pptx

  • 1. Rajendra Dev Bhatt (PhD Scholar) Asst. Professor Clinical Biochemistry & Laboratory Medicine Fellow: Translational Research (2018-2022) in CVD in Nepal, NHLBI & NIH USA Thursday, July 6, 2023 1 LIPID(S) 6/29/2012 1
  • 2. Thursday, July 6, 2023 6/29/2012 2 The boundaries of all cells are defined by biological membranes. These barriers prevent molecules generated inside the cell from leaking out and unwanted molecules from diffusing in. They also contain transport systems that allow the cell to take up specific molecules and remove unwanted ones.
  • 3.  Lipids are a heterogeneous group of compounds, including fats, oils, steroids, waxes, and related compounds, that are related more by their physical than by their chemical properties. They have the common property of being (1) relatively insoluble in water and (2) soluble in nonpolar solvents such as ether and chloroform. Thursday, July 6, 2023 6/29/2012 3 3
  • 4.  Storage form of energy  Important dietary components because of their high energy value and also because of the fat-soluble vitamins and the essential fatty acids contained in the fat of natural foods.  Structural components of biomembranes  Serve as thermal insulators in the subcutaneous tissues and around certain organs  Nonpolar lipids act as electrical insulators, allowing rapid propagation of depolarization waves along myelinated nerves Thursday, July 6, 2023 6/29/2012 4 4
  • 5.  Provide shape and contour to the body  Act as metabolic regulators  Combinations of lipid and protein (lipoproteins) are important cellular constituents, occurring both in the cell membrane and in the mitochondria, and transporting lipids in the blood. Thursday, July 6, 2023 6/29/2012 5 5
  • 6. Following diseases are associated with abnormal chemistry or metabolism of lipids- Obesity Atherosclerosis Diabetes Mellitus Hyperlipoproteinemia Fatty liver Lipid storage diseases Thursday, July 6, 2023 6/29/2012 6 6
  • 7. Simple lipids: Esters of fatty acids with various alcohols. a.Fats: Esters of fatty acids with glycerol. Oils are fats in the liquid state. b.Waxes: Esters of fatty acids with higher molecular weight monohydric alcohols. Thursday, July 6, 2023 6/29/2012 7 7
  • 8. 2.Complex lipids: Esters of fatty acids containing groups in addition to an alcohol and a fatty acid. a.Phospholipids: Lipids containing, in addition to fatty acids and an alcohol, a phosphoric acid residue. They frequently have nitrogen-containing bases and other substituents, eg, in glycerophospholipids the alcohol is glycerol and in sphingophospholipids the alcohol is sphingosine. Thursday, July 6, 2023 6/29/2012 8 8
  • 9. Thursday, July 6, 2023 6/29/2012 9 a.Glycolipids (glycosphingolipids): Lipids containing a fatty acid, sphingosine, and carbohydrate. b.Other complex lipids: Lipids such as sulfolipids and aminolipids. Lipoproteins may also be placed in this category.
  • 10. 3) Precursor and derived lipids: These include-  fatty acids  glycerol  steroids  other alcohols  fatty aldehyde  ketone bodies  hydrocarbons, lipid-soluble vitamins, and hormones. Thursday, July 6, 2023 6/29/2012 10 10
  • 11. Fatty acids are aliphatic carboxylic acids Have the general formula R-(CH2)n-COOH They occur mainly as esters in natural fats and oils but do occur in the unesterified form as free fatty acids, a transport form found in the plasma. Fatty acids that occur in natural fats are usually straight-chain derivatives containing an even number of carbon atoms. Thursday, July 6, 2023 6/29/2012 11 11
  • 12. Thursday, July 6, 2023 6/29/2012 Fatty Acids are carboxylic acid with hydrocarbon side chain CH3-COOH (Acetic acid) CH3-CH2-COOH (Propionic acid) CH3-CH2-CH2-COOH (Butyric acid) CH3- (CH2)14-COOH (Palmitic acid) 12
  • 13. Fatty acids can be classified in many ways- 1) According to nature of the hydrophobic chain- a) Saturated b) Unsaturated Saturated fatty acids do not contain double bonds, while unsaturated fatty acids contain double bonds Thursday, July 6, 2023 6/29/2012 13 13
  • 14. Saturated fatty acids may be expected based on acetic acid (CH3 —COOH) as the first member of the series in which —CH2 — is progressively added between the terminal CH3 — and —COOH groups. Fatty acids in biological systems usually contain an even number of carbon atoms, typically between 14 and 24. The 16- and 18- carbon fatty acids are most common. Thursday, July 6, 2023 6/29/2012 14 14
  • 15. Number of C atoms Common Name Systemic Name Formula 2 Acetic acid Ethanoic acid CH3COOH 4 Butyric acid Butanoic acid CH3(CH2)2COOH 6 Caproic acid Hexanoic acid CH3(CH2)4COOH 8 Caprylic acid Octanoic acid CH3(CH2)6COOH 10 Capric acid Decanoic acid CH3(CH2)8COOH 12 Lauric acid Dodecanoic acid CH3(CH2)10COOH 14 Myristic acid Tetradecanoic acid CH3(CH2)12COOH 16 Palmitic acid Hexadecanoic acid CH3(CH2)14COOH 18 Stearic acid Octadecanoic acid CH3(CH2)16COOH 20 Arachidic acid Eicosanoic acid CH3(CH2)18COOH 22 Behenic acid Docosaionic acid C6 / H2 9 / 2 (0 C1 2 H ) COOH 3 2 20 12 Thursday, July 6, 2023 6/29/2012 15
  • 16. Unsaturated fatty acids may further be divided as follows- (1) Monounsaturated (monoethenoid, monoenoic) acids, containing one double bond. (2)Polyunsaturated (polyethenoid, polyenoic) acids, containing two or more double bonds. The configuration of the double bonds in most unsaturated fatty acids is cis. The double bonds in polyunsaturated fatty acids are separated by at least one methylene group. Thursday, July 6, 2023 6/29/2012 16
  • 17. Thursday, July 6, 2023 6/29/2012 17
  • 18. The systematic name for a fatty acid is derived from the name of its parent hydrocarbon by the substitution of anoic for saturated and enoic for unsaturated fatty acids. For example, the C18 saturated fatty acid is called octadecanoic acid because the parent hydrocarbon is octadecane. Thursday, July 6, 2023 6/29/2012 18
  • 19. Thursday, July 6, 2023 6/29/2012 A C18 fatty acid with one double bond is called octadecenoic acid; with two double bonds, octadecadienoic acid; and with three double bonds, octadecatrienoic acid. The notation 18:0 denotes a C18 fatty acid with no double bonds, whereas 18:2 signifies that there are two double bonds 19
  • 20. Carbon atoms are numbered from the carboxyl carbon (carbon No. 1). The carbon atoms adjacent to the carboxyl carbon (Nos. 2, 3, and 4) are also known as the α ,β , and carbons, respectively, and the terminal methyl carbon is known as theω or n- carbon. The position of a double bond is represented by the symbol ∆ followed by a superscript number. eg, ∆ 9 indicates a double bond between carbons 9 and 10 of the fatty acid; Thursday, July 6, 2023 6/29/2012 20
  • 21. Alternatively, the position of a double bond can be Thursday, July 6, 2023 6/29/2012 denoted by counting from the distal end, with the ω- carbon atom (the methyl carbon) as number 1. ω9 indicates a double bond on the ninth carbon counting from the ω-carbon. In animals, additional double bonds are introduced only between the existing double bond (eg, 9, 6, or 3) and the carboxyl carbon, leading to three series of fatty acids known as the ω9, ω6, and ω3 families, respectively. 6/ 9/2012 Biochemistry for medics 21
  • 22. S.No. Number of C atoms, number and location of double bonds Family Common Name Systemic Name [A] Monoenoic acids (one double bond) 1. 16:1;9 ω 7 Palmitoleic acid cis-9- Hexadecenoic 2. 18:1;9 ω 9 Oleic Acid cis-9- Octadecenoic 3. 18:1;9 ω 9 Elaidic acid trans 9- Octadecanoic [B] Dienoic acids (two double bonds) 1. 18:2;9,12 ω 6 Linoleic acid all-cis-9,12- 6/29/201 O2 ctadecadie1 n8 o h Thursday, July 6, 2023 6/29/2012 22
  • 23. Arachidonic acid All cis S.No. Number of C atoms, number and location of double bonds Family Common Name Systemic Name [c] Trienoic acids (three double bonds) 1. 18:3;6,9,12 ω 6 Y- Linolenic acid all-cis- 6,9,12- Octadecatrien oic 2. 18:3;9,12,15 ω 3 α-Linolenic all-cis- 9,12,15Octad ecatrienoic [D] Tetraenoic acid(Four double bonds) 20:4;5,8,11, ω6 19 Thursday, July 6, 2023
  • 24. S.No. Number of C atoms, number and location of Thursday, July 6, 2023 6/29/2012 double bonds Family Common Name Systemic Name [E] Pentaenoic acids (Five double bonds) 1. 20:5;5,8,11,1 4,17 ω 3 Timnodonic acid all-cis- 5,8,11,14,17- Eicosapenta enoic [F] Hexaenoic acid(Four double bonds) 22:6;4,7,10,1 3,16,19 ω3 Cervonic acid all-cis- 19- 6/29/201 42 ,7,10,13,1620 , h 24
  • 25. Thursday, July 6, 2023 6/29/2012 25
  • 26. Depending upon the orientation of the radicals around the axis of the double bond- Cis- If the radicals are on the same side of the double bond Trans- If the radicals are on the opposite side Oleic acid and Elaidic acid have the same formula but Oleic acid is cis while Elaidic acid is Trans Fatty acid Thursday, July 6, 2023 6/29/2012 26
  • 27. The hydrocarbon chains in saturated fatty acids are, fairly straight and can pack closely together, making these fats solid at room temperature. Oils, mostly from plant sources, have some double bonds between some of the carbons in the hydrocarbon tail. Increase in the number of cis double bonds in a fatty acid leads to a variety of possible spatial configurations of the molecule—eg, Arachidonic acid, with four cis double bonds, has "kinks" or a U shape. Thursday, July 6, 2023 6/29/2012 27
  • 28. Because of the kinks (sharp curve) in the hydrocarbon tails, unsaturated fats can't pack closely together, making them liquid at room temperature. The membrane lipids, which must be fluid at all environmental temperatures, are more unsaturated than storage lipids. The carbon chains of saturated fatty acids form a zigzag pattern when extended, as at low temperatures. 6/29/2012 28
  • 29.  Trans fatty acids are present in certain foods, arising as a by-product of the saturation of fatty acids during hydrogenation, or "hardening," of natural oils in the manufacture of margarine. An additional small contribution comes from the ingestion of ruminant fat that contains trans fatty acids arising from the action of microorganisms in the rumen. Naturally-occurring unsaturated vegetable oils have almost all cis bonds, but using oil for frying causes some of the cis bonds to convert to trans bonds. Thursday, July 6, 2023 6/29/2012 29
  • 30. Thursday, July 6, 2023 6/29/2012 30 Properties of Fatty Acids Hydrogenation :The Good Gone Bad Hydrogenation is a chemical process that adds hydrogen to the unsaturated bonds on the FA chains attached to the TAG backbone. In this way, an unsaturated fat can be turned into a saturated fat and increase its melting point. Recall that the addition of hydrogen to an alkene (unsaturated) results in an alkane (saturated). A simple hydrogenation reaction is: H2C=CH2+H2→CH3CH3 alkene plus hydrogen yields an alkane
  • 31. Thursday, July 6, 2023 6/29/2012 31 Processing naturally occurring fats to modify their texture from liquid to semisolid and solid forms results in the development of trans fats, which have been linked to an increased risk for heart disease. Trans fats are used in many processed foods such as cookies, cakes, chips, doughnuts, and snack foods to give them their crispy texture and increased shelf life. The AHA states that, like saturated fats, trans fats raise LDL “bad cholesterol,” but unlike saturated fats, trans fats lower HDL “good cholesterol.” Properties of Fatty Acids
  • 32. Thursday, July 6, 2023 6/29/2012 32 Halogenation: When treated with halogens under mild conditions, the unsaturated fatty acids can take up two halogen atoms, at each double bond to form the halogenated derivative of the fatty acid. For example, Oleic acid + I2 → Di-iodo oleic acid The number of halogen atoms taken up will depend on the number of double bonds and is an index of the degree of unsaturation. Properties of Fatty Acids
  • 33. Thursday, July 6, 2023 6/29/2012 33 Melting Point: The short and medium chain fatty acids are liquids, whereas long chain fatty acids are solids at 25 degree . The solubility in water decreases, while melting and boiling points increase, with increase in chain length. The unsaturated fatty acids have lower melting point compared to saturated fatty acids with the same chain length. Properties of Fatty Acids
  • 34. Thursday, July 6, 2023 6/29/2012 34 Salt Formation: Saturated and unsaturated fatty acids form salts with alkali. CH3—COOH + NaOH → CH3—COONa + H2O Sodium and potassium salts of long chain fatty acids are called soaps. Calcium and magnesium soaps are insoluble. The saponification number indicates how much potassium hydroxide is needed to saponify 1g fat. Properties of Fatty Acids
  • 35. Thursday, July 6, 2023 6/29/2012 35 Ester Formation: Both saturated and unsaturated fatty acids form esters with alcohols, especially with glycerol. Fatty acids can form mono-, di- or tri- esters with alcohol groups of glycerol. Triglycerides or triacylglycerols are also known as neutral fat. Properties of Fatty Acids
  • 36. Thursday, July 6, 2023 6/29/2012 36 Oxidation of Fatty Acids: All fatty acids undergo oxidation in the body to give energy. Beta-oxidation is the major process by which acids are oxidized. However, the unsaturated fatty acids can undergo auto oxidation, due to the presence of the highly reactive double bonds and a variety of products. Properties of Fatty Acids
  • 37. Short chain-with 2-6 carbon atoms Medium chain- with 8-14 carbon atoms Long chain- with 16-18 carbon atoms Very long chain fatty acids- with 20 or more carbon atoms Thursday, July 6, 2023 6/29/2012 37
  • 38. Polyunsaturated fatty acids such as Linoleic and Linolenic acids are essential for normal life functions. They are therefore characterized as essential fatty acids. Arachidonic acid is considered as semi essential fatty acid since it can be synthesized from Linoleic acid . Essential polyunsaturated fatty acids can be classified as belonging to one of two "families", the omega-6 family or the omega-3 family. Fatty acids belonging to these two families differ not only in their chemistry, but also in their natural occurrence and biological functions. Thursday, July 6, 2023 6/29/2012 38
  • 39. Components of cell membranes, structural elements of gonads and mitochondrial membrane Required for brain growth and development Precursors of Eicosanoids Play important role in vision They have a cardio protective role- Lower serum cholesterol and increase HDLlevels Prevent fatty liver formation Deficiencies of essential polyunsaturated fatty acids may cause a wide variety of symptoms, including retarded growth in children, reduced fertility and pathologic changes in the skin. Thursday, July 6, 2023 6/29/2012 39
  • 40. Thursday, July 6, 2023 6/29/2012 Most commonly occurring fatty acids in nature are : a. Even number of un-branched chain of 12-24 carbons b. Odd number of un-branched chain of 12-24 carbons c. Even number of branched chain of 12-24 carbons d. Odd number of branched chain of 12-24 carbons Answer: a. Even number of un-branched chain of 12-24 carbons 40
  • 41. Thursday, July 6, 2023 6/29/2012 In most of the naturally occurring mono- unsaturated fatty acids , the double bond will be placed between: a.C6-C7 b.C7-C8 c.C8-C9 d.C9-C10 Answer: d.C9-C10 41
  • 42. Thursday, July 6, 2023 6/29/2012 The best source of trans fatty acid in our diet is: a. Vegetables b. Ground nut c. Dairy products d. Fruits Answer: c. Dairy products 42
  • 43. Thursday, July 6, 2023 6/29/2012 In naturally occurring fatty acids, the bond are in conformation : a. Cis conformation b. Trans conformation c. Mixture of Cis and Trans d. Cis and Trans conformation alternatively Answer: a. Cis conformation 43
  • 44. Most important sterol in human body Molecular formula-C27H45 OH Possesses a cyclo pentano perhydrophenatherene ring nucleus Has an -OH group at C3 A double bond between C5 and C6 Two- CH3 groups at C10 and C13 And eight carbon side chain attached to C17 Thursday, July 6, 2023 6/29/2012 44
  • 46. Cholesterol occurs both as free form or in ester form In cholesteryl ester, the hydroxyl group on position 3 is esterified with a long-chain fatty acid. Cholesterol esters are formed by the transfer of acyl group by Acyl transferases- Lecithin Cholesterol Acyltransferase (LCAT) & Acyl-CoA Cholesterol O- Acyltransferase (ACAT) In plasma, both forms are transported in lipoproteins Plasma low-density lipoprotein (LDL) is the vehicle of uptakeof cholesterol and cholesteryl ester into many tissues. Thursday, July 6, 2023 6/29/2012 46
  • 47. Thursday, July 6, 2023 6/29/2012 Free cholesterol is removed from tissues by plasma high-density lipoprotein (HDL) and transported to the liver, where it is eliminated from the body either unchanged or after conversion to bile acids in the process known as reverse cholesterol transport A sum total of free and ester cholesterol in serum is called serum total cholesterol 47
  • 48. Cholesterol is widely distributed in all cells of the body but particularly in nervous tissue. It is a major constituent of the plasma membrane and of plasma lipoproteins. It is synthesized in many tissues from acetyl-CoA and is the precursor of all other steroids in the body, including corticosteroids, sex hormones, bile acids, and vitamin D. Cholesterol is a major constituent of gallstones. Its chief role in pathologic processes is as a factor in the genesis of atherosclerosis of vital arteries, causing cerebrovascular, coronary, and peripheral vascular disease. Thursday, July 6, 2023 6/29/2012 48
  • 49. Desirable level of serum total cholesterol is 200 mg/dL  Physiological variations- Low at the time of birth, increases with advancing age. The level is increased during pregnancy Pathological Variations- a) Low cholesterol (Hypocholesterolemia)- Thyrotoxicosis, anemia, hemolytic jaundice, wasting diseases and malabsorption syndrome. Thursday, July 6, 2023 6/29/2012 49
  • 50. B) Hypercholesterolemia-  Nephrotic syndrome Diabetes Mellitus Obstructive Jaundice Myxoedema/ Hypothyroidism Xanthomatous biliary cirrhosis/ Hyperlipoproteinemia due to liver diseases Hypopituitarism Familial Hypercholesterolemia Idiopathic Thursday, July 6, 2023 6/29/2012 50
  • 51. 7- dehydrocholesterol- also called as Provitamin D3 (Precursor of vitamin D) Ergo sterol-plant sterol (First isolated from Ergot- Fungus of Rye) Other steroids- Bile acids, adrenocortical hormones, gonadal hormones, D vitamins and Cardiac glycosides. Thursday, July 6, 2023 6/29/2012 51
  • 52.  Neutral fats or Triacylglycerol The triacylglycerols are esters of the trihydric alcohol, glycerol and fatty acids. Mono- and Diacylglycerol, wherein one or two fatty acids are esterified with glycerol, are also found in the tissues. Naturally occurring fats and oils are mixtures of triglycerides. If all the OH groups are esterified to same fatty acids- It is Simple Triglyceride If different fatty acids are esterified- it is known as Mixed triglyceride. Thursday, July 6, 2023 6/29/2012 52
  • 53. Colourless, odourless and tasteless Insoluble in water Specific gravity is less than 1.0, consequently all fats float in water Oils are liquids at 200C, they contain higher proportion of Unsaturated fatty acids Fats are solid at room temperature and contain saturated long chain fatty acids Triglycerides are the storage form of energy in adipose tissue Triglycerides in the body are hydrolyzed by Lipases 40 Biochemistry for medics 6/29/2012 6/29/2012 Thursday, July 6, 2023 53
  • 54. Saponification-When the triglycerides are hydrolyzed by alkali the process is known as Saponification. Rancidity-Fats and oils have a tendency to become rancid. Rancidity refers to the appearance of unpleasant taste and smell of fats. Hydrolytic rancidity is due to partial hydrolysis of triglycerides due to traces of lipases present in the given fat Oxidative rancidity is due to partial oxidation of unsaturated fatty acids with the resultant formation of epoxides and peroxides by free radicals. Preserving the fats with antioxidants can prevent rancidity Thursday, July 6, 2023 6/29/2012 54
  • 55. They are esters of higher fatty acids with higher mono hydroxy aliphatic alcohols(e.g. Cetyl alcohol)  Have very long straight chain of 60-100 carbon atoms They can take up water without getting dissolved in it Used as bases for the preparation of cosmetics, ointments, polishes, lubricants and candles. In nature, they are found on the surface of plants and insects. Thursday, July 6, 2023 6/29/2012 55
  • 56. Lipid index Details Significance Saponification number Number of mg of KOH required to saponify the free and combined fatty acids in 1G. of a given fat Indicates molecular weight and is inversely proportional to it. Iodine number Number of grams of iodine absorbed by 100 gm of fat It is a measure of degree of unsaturation of a fat Acid number Number of mg of KOH required to neutralize the fatty acids in a gram of a fat Indicates the degree of rancidity of a fat Thursday, July 6, 2023 6/29/2012 56
  • 57. a)Phospholipids- Contain in addition to fatty acids and glycerol/or other alcohol, a phosphoric acid residue, nitrogen containing base and other substituents. Phospholipids may be regarded as derivatives of phosphatidic acid , in which the phosphate is esterified with the —OH of a suitable alcohol. They are amphipathic molecules containing a polar head and a hydrophobic portion Thursday, July 6, 2023 6/29/2012 57
  • 58. Based on nature of alcohol- 1) Glycerophospholipids- Glycerol is the alcohol group. Examples- o Phosphatidyl choline o Phosphatidyl ethanolamine o Phosphatidyl serine o Phosphatidyl inositol o Phosphatidic acid o Cardiolipin o Plasmalogen o Platelet activating factor o Phosphatidyl Glycerol 2) Sphingophospholipids- Sphingol is the alcohol group Example- Sphingomyelin Thursday, July 6, 2023 6/29/2012 58
  • 59. 1) Phosphatidylcholines (Lecithins ) Phosphoacylglycerols containing choline are the most abundant phospholipids of the cell membrane Are present a large proportion of the body's store of choline. Choline is important in nervous transmission, as acetylcholine, and as a store of labile methyl groups Dipalmitoyl lecithin is a very effective surface- active agent and a major constituent of the surfactant preventing adherence, by reducing surface tension, of the inner surfaces of the lungs. Its absence from the lungs of premature infants causes respiratory distress syndrome. Thursday, July 6, 2023 6/29/2012 59
  • 60. 2) Phosphatidyl ethanolamine (cephalin)- Structurally similar to Lecithin with the exception that the base Ethanolamine replaces choline Brain and nervous tissue are rich in Cephalin 3)Phosphatidyl Serine-(found in most tissues) differ from phosphatidylcholine only in that serine replaces choline 4) Cardiolipin – Abundantly found in mitochondrial membrane. This is the only phospholipid with antigenic properties. Thursday, July 6, 2023 6/29/2012 60
  • 61. 5) Platelet activating factor (PAF)- PAF activates inflammatory cells and mediates hypersensitivity, acute inflammatory and anaphylactic reactions Causes platelets to aggregate and degranulate and neutrophils and alveolar macrophages to generate superoxide radicals 6) Phosphatidyl Glycerol- Formed by esterification of phosphatidic acid with glycerol Diphosphatidyl glycerol, cardiolipin is found in the mitochondrial membrane Thursday, July 6, 2023 6/29/2012 61
  • 62. Sphingomyelin- Backbone is sphingosine (amino alcohol) A long chain fatty acid is attached to amino group of sphingosine to form Ceramide The alcohol group at carbon- 1 of sphingosine is esterified to phosphoryl choline, producing sphingomyelin Sphingomyelin is an important component of myelin of nerve fibers Thursday, July 6, 2023 6/29/2012 62
  • 63. Components of cell membrane, mitochondrial membrane and lipoproteins Participate in lipid absorption and transportation from intestine Play important role in blood coagulation Required for enzyme action- especially in mitochondrial electron transport chain Choline acts as a lipotropic agent Membrane phospholipids acts as source of Arachidonic acid Act as reservoir of second messenger- Phosphatidyl Inositol Act as cofactor for the activity of Lipoprotein lipase Phospholipids of myelin sheath provide insulation around the nerve fobers Dipalmitoyl lecithin acts as a surfactant Thursday, July 6, 2023 6/29/2012 63
  • 64. L/S Ratio in amniotic fluid is used for the evaluation of fetal lung maturity Prior to 34 weeks gestation, lecithin and sphingomyelin concentrations are equal but afterwards there is marked increase in Lecithin concentration. A L/S ratio of > 2 indicates adequate fetal lung maturity Delivery of a premature,low birth weight baby with low L/S ratio (1 or<1) predisposes the child to respiratory distress syndrome Thursday, July 6, 2023 6/29/2012 64
  • 65. Thursday, July 6, 2023 6/29/2012 Lipoproteins Chylomicrons VLDL IDL LDL HDL 67
  • 66. General Structure of Lipo proteins Lipoproteins consist of a nonpolar core and asingle surface layer of amphipathic lipids  T h e nonpolar lipid core consists of mainly triacylglycerol and cholesteryl ester and is surrounded by a single surface layer of amphipathic phospholipid and cholesterol molecules These are oriented so that their polar groups face outward to the aqueous medium.  Theprotein moiety of a lipoprotein is known as an apolipoprotein or apoprotein.
  • 67. Classification of Lipoproteins Lipoproteins can be classified on the basis of density Based on density- They are separated by Ultracentrifugation. Five major groups of lipoproteins have been identified which are important physiologically and in clinical diagnosis. (i) Chylomicons, derived from intestinal absorption of triacylglycerol and other lipids; Density is generally less than 0.95 while the mean diameter lies between 100- 500 nm
  • 68. Classification of Lipoproteins (ii)Very low density lipoproteins (VLDL), derived from the liver for the export of triacylglycerol; density lies between 0.95- 1.006 and the mean diameter lies between 30-80 nm. (iii)Intermediate density lipoproteins (IDL) are derived from the catabolism of VLDL,with a density ranging intermediate between Very low density and Low density lipoproteins i.e. ranging between 1.006- 1.019 and the mean diameter ranges between 25- 50nm.
  • 69. Classification of Lipoproteins iv) Low-density lipoproteins (LDL), representing a final stage in the catabolism of VLDL; density lies between 1.019-1.063 and mean diameter lies between 18-28 nm (iv) High-density lipoproteins (HDL), involved in cholesterol transport and also in VLDL and chylomicron metabolism. Density ranges between 1.063-1.121 and the mean diameter varies between 5-15 nm.
  • 70. Classification of Lipoproteins Lipoproteins with high lipid content will have low density, larger size and so float on centrifugation. Those with high protein content sediment easily, have compact size and have a high density. 8
  • 71. Thursday, July 6, 2023 6/29/2012 The cholesterol serves as the precursor for the following biosynthetic pathways EXCEPT a. Bile acid synthesis b. Steroid hormone synthesis c. Aldosterone synthesis d. Thyroid hormone synthesis d. Thyroid hormone synthesis 73
  • 72. Thursday, July 6, 2023 6/29/2012 Which of the following lipids act as lungs surfactants? a. Phosphatidylcholine b. Phosphatidylethanolamine c. Ceramide d. Phosphatidylinositol a. Phosphatidylcholine 74
  • 73. Thursday, July 6, 2023 6/29/2012 All of the following are complex lipids, except a. Phosphatidic acid b. Cerebroside c. Cardiolipin d. Cholesterol d. Cholesterol 75
  • 74. Thursday, July 6, 2023 6/29/2012 Which of the following is an essential fatty acid? a. Linolenic acid b. Arachidonic acid c. Oleic acid d. Palmitic acid a. Linolenic acid 76
  • 75. Thursday, July 6, 2023 6/29/2012 Besides high cholesterol, which of these can make it more likely that you will get heart disease? A. Cigarette smoking B. High blood pressure C. Family history of heart disease D. Age E. All of the above E. All of the above 77