Lipid Chemistry

By
Prof. Dr. Abdellah Ali Omar
M.B.B.Ch, MS, M.D

Professor of Medical Biochemistry

11/02/1443 1
 Lipids are a Heterogeneous Group of
Organic Compounds Related to Fatty Acids
Relatively Insoluble in Water

( Hydrophobic = Water Hating ) due to

Predominance of Hydrocarbon chain &

Soluble in Non-Polar Solvents

Such as Ether, Benzene, Chloroform & Acetone
 Lipids are the

Most Efficient Form of Stored Energy

in Humans

Together with Carbohydrate &

Protein, Form major Diet

Excess lipids is Stored as Fat

 Examples of Lipids
- Fatty acids

- Tri-Acylglycerol

- PhosphoLipids

- GlycoLipids

- SphingoLipids

- Steroids

- Vitamins A, D, E, K
 Lipids
Classified Into
Simple Conjugated Derived
( Compound )
Neutral fat Waxes
Glycerol + FAs Higher Alcohol + FA

Neutral fat ( Because it Carry No Charges )

 Simple Lipids
a – Fats (Acylglycerol):
Esters of Fatty acids with Glycerol
e.g. Triglycerides ( if 3 FA )

b – Waxes:
Esters of Fatty acids with Higher alcohols
( alcohols other than glycerol e.g. beewax, lanolin )
6
II - Complex Lipids
Are Esters of Fatty acids with Alcohol
in addition to Other Groups e.g.

- Phospholipids ( subclassified into )

a - GlyceroPhosphoLipids b - SphingoPhosphoLipids

- SphingoLipids ( With or Without Phosphate )

a Glycolipids b Sulfolipids
c Gangliosides d Mucolipids

- Proteolipids (Lipoprotein) 7
III – Derived Lipids
Any Substance can be Given by
Hydrolysis of Simple or Complex Lipid e.g.

Fatty Acids

Steroids

Fat Soluble Vitamins ( A, D, E, K )

Ketone Bodies

Carotenoids
BioMedical Importance
of Lipids
In diet:
- Source of High Energy
- Contain Fat Soluble Vitamins
- Contain Essential Fatty Acids
- Make Diet Palatable
 In Body:
- Adipose Tissue serve as Storage Form of Energy
- Thermal Insulator in Subcutaneous Tissue
- Electrical Insulator in Nervous Tissue
( allow Rapid Propagation )
- Enter in Lipoprotein Formation
( Enter in Cell Membrane Structure &
Act as Transport form of Energy in Blood )
 Neutral Fats
[ Tri Acyl Glycerol ]
Neutral fat ( Triacylglycerol )
Esters of 3 Fatty acids with Glycerol
Glycerol is Short Chain Alcohol containing 3 OH groups

Types:
Simple : contain Similar Fatty Acids
e.g., Tripalmitin & Triolein

Mixed : contain Different Fatty Acids

e.g., Palmito-Oleio-Stearin & Di-Stearin Palmitin

Either Solid, called Fats or Liquid, called Oils

14
Fatty Acids
(FA)
 Fatty acids are
Long Chain Organic Molecules
Containing Carboxylic end ( COOH )
Either :
1 - Saturated
No Double Bonds, Non Essential

2 - Unsaturated
contain One or More Double Bonds
Either Essential & Non essential
- Water Insoluble Long Chain Hydrocarbons

- May be Saturated or Unsaturated

- Mostly Mono-Carboxylic Acids
- Mostly Aliphatic ( No Branches ) acids
- Occur Mainly as Esters in Neutral fats
- Can Occur Freely in Plasma
- Fatty acids in Neutral Fats contain an
Even ( ‫ ) زوجى‬Number of Carbons
Saturated FA Mono-Un-Saturated FA Poly-Un-Saturated FA
 Saturated FA ( Anoic )
No Double Bonds ( No C=C )

General Formula is

CH3 - (CH2)n - COOH

Where (n) is
Number of Methylene Group (CH2)
 Examples of
Important Saturated FA:
 Butyric acid ( 4C ): CH3 – CH2 – CH2 – COOH

 Caproic acid ( 6C ): CH3 – (CH2)4 – COOH

 Palmitic acid ( 16C ): CH3 – (CH2)14 – COOH

 Stearic acid ( 18C ): CH3 – (CH2)16 – COOH

 Saturated Fatty Acids
Common Name C- Atoms Source & Significance
Butyric Acid 4 Fats, Butter, end product of CHO
Caproic Acid 6 fermentation of rumen organisms
Capyrlic Acid 8
Fats, butter, fats of plant origin. Provide
energy to body.
Capric ( Decanoic) 10

Coconut oil, palm, butter, cinnamon,

Lauric Acid 12
spermaceti provide energy

Mysristic Acid 14 Nuts, Palm, Coconut, butter, provide energy

Palmitic Acid 16 Common in all animal & plant fat.

Stearic Acid 18 Provide energy and structure.

Arachidic Acid 20 Peanut-arachis oil. Provide energy

Behenic Acid 22 Seeds, nuts. Provide energy

Lignoceric Acid 24 Peanuts, cerebrosides

 Carbon Skeleton of Fatty Acid
Numbered Either
1 - From the Carboxylic Group (COOH)
- ( Delta = ∆ ) or
- Alpha, Beta, Gamma, Delta, Epsilon
∆
6 5 4 3 2 1
CH3-CH2-CH2-CH2-CH2-COOH
ε δ γ β α
ω1 2 3 4 5 6

2 - From the Terminal Methyl Group ( Omega=ώ )

 Non Essential FA:
 They Can be Synthesized in the Body
from Acetyl CoA (Common Metabolic Pool)

 They are the Saturated

&
MonoUnSaturated FA
Unsaturated Fatty Acids (Enoic)
 Fatty acids Containing Double Bond(s)
 They are Either
MonoUnSaturated (one Double Bond) or
PolyUnSaturated (More than One Double Bond)

General Formula is
Cn – H2n-1 – COOH
Where (n) is the Number of Carbon Atoms Without COOH
 Double Bonds are:
Nearly always in
Cic Configuration

Spaced at 3 Carbon Interval

if the Fatty Acid has More than one double bond
 Mono
UnSaturated FA
 MonoUnSaturated FA
MonoEnoic Fatty acids
MonoThenoic Fatty acids

( Non Essential ):
Example
Palmitoleic (16C) is written 16:1 Δ9 , 16:1 ώ7
Oleic = OctaDecaEnoic (18C) is written 18:1 Δ9
PolyUnSaturated
FA
( Essential ):
PolyEnoic fatty acids
PolyThenoic fatty acids
 Essential FA:
Linoleic acid (18C) is written
18: 2 ∆9,12, ώ6,9

Linolenic acid (18C) is written

18:3 ∆9,12,15 , ώ3,6,9
Present in Linseed oil
Arachidonic acid (20C) is written
20: 4 ∆5,8,11,14, ώ6
Present in Peanut Oil
Precursor of Eicosanoids
Component of Phospholipids in Animals

Clupanodonic acid (22C) is written

22: 5 ∆7,10,13,16,19, ώ3
Present in Fish Oil
Component of Phospholipids in Brain
 Essential Fatty acids (EFA)
Must be Supplied in the Diet
because
the Body Can Not Synthesize Them
We Lack Enzymes Required to
Introduce Double Bonds after C9

Our Human Body has Enzyme System that can

‫يضيف بين‬ Form Only One Double Bond at ∆ ‫فى اتجاه ال‬
9 ‫يضيف‬

C 9-10 COOH
 Essential Fatty acids (EFA):
Present Mainly in Vegetable Oils
e.g.
Corn Oil, Soya Bean Oil, Sun Flower Oil & Cotton Seed

Fish oils e.g. Shark Liver Oil & Tuna

Contain ώ3 PUFA

Arachidonic acid (20C)

is formed in the Body from Linoleic acid
Becomes Essential Only If Linoleic acid is Deficient
 Essential Fatty Acids:
Synthesized Only by Plants but Required by Humans

Linoleic (ω-3) & Linolenic acids (ω-6)

Non-Essential Fatty Acids:

Humans Synthesize them
- From Other Fatty Acids or
- From Other Precursors, Derived From Other Foodstuff
 Unsaturated Fatty Acids
Name Source & Significance
Monoenoic. In all fats provide energy
Palmito-Oleic 7
Oleic Acid 9 Most common in natura fats.

Dienoic. Corn, peanut, cotton seed,

Lenoleic 6 Soyabean, EFA.
Trienoic. Linseed oils & others.
 Lenolenic 3
Essential fatty acids (EFA)

 Lenolenic 6 Minor FA in animals.EFA

Arachidonic 6 Tetraenoic. In animal fat &

peanut oil.EFA
Timmodonic 3 Pentaenoic. Fish oil, cod liver, salmon oil.

Hexaenoic. Fish oil & PL in brain

Nervonic 3
Natural Fatty Acids
Almost All Double Bonds have

Cis Configuration
Linear acids with Even Number Carbon
Almost all Fatty acids Present in Mammalian Tissues
are Aliphatic
 Functions of EFA
( BioChemical Role )
1 - Normal Growth

2 - Enter in Structure of Phosholipids &

-

Cholesterol Esters

3 - Formation of Prostaglandins & Leukotrienes

Eicosanoids can be
Derived from Arachidonic acid Precursor
4 - Structural Elements of Cell Membranes &
Tissues.

6 - Maintain Integrity of reproductive system

& Normal skin and Epithelium.

8 - Lower Serum Cholesterol Level ( Protective

against Atherosclerosis & Coronary Heart Disease )
9 – Excessive Intake of EFA can leads to
* Increased CT &
* Increased Fibrinolytic activity

11 – Deficiency of EFA can Produces

* Fatty Liver &
* Retinits Pigmentosa
Properties
of FA
Physical Properties
1 – Solubility:
Short chains FA are Soluble in Water
Long chains FA are Insoluble in water
( Soluble in Non-Polar Solvents )

2 – Melting Point:
Depends on: - Chain Length of FA
- Degree of Saturation
Short chains & UnSaturated FA are
Liquid at Room Temperature
Long chains & Saturated FA are
Solid at Room Temperature
Animal Triacylglycerols ( Other than Fish )
Contain: 40 - 60% of Unsaturated Fatty Acids
Fish: 75 – 80% Unsaturated & More PolyUnsaturated
Plant Triacylglycerols: 85 – 90% Unsaturated

• Coconut: 92% Saturated

Higher Content of UnSaturated Fatty acid

Lower Melting Point
• Plant Triacylglycerol: Liquid at Room Temp.→ Oils
• Animal Triacylglycerol: Solid at Room Temp → fats
Saturated FA Mono-Un-Saturated FA Poly-Un-Saturated FA
 Chemical Properties
Hydrogenation ( addition of Hydrogen )
Convert UnSaturated ( Yes = ) Into Saturated FA ( No = )
in the Presence of Heat & Nickel

Halogenations ( addition of Hallogen e.g. Cl, F )

convert UnSaturated ( Yes = ) Into Saturated FA ( No = )

Oxidation ( addition of Oxygen )

Convert UnSaturated ( Yes = ) into Peroxide
 Hydrogenation
• Margarine is Produced by
Hardening of Vegetable Oils by
Partial Hydrogenation into Semisolid or Solid Product

• Margarine considered Healthier than Butter

• Fatty acids with Trans Double Bonds

have Physical Properties more like Saturated
FA, also Raising Blood Cholesterol
2 – Salt (Soap) Formation:
FA + Alkalies (e.g. Na hydroxide)
Soap (Na salt) + H2O

3 – Ester Formation:
FA + Alcohol Ester + H2O
FA + Glycerol Neutral Fats (Triacylglycerol)

FA + Higher alcohols Waxes

 Classification of FAs
I - Based on Saturation
1. Saturated: Single bonded - Palmitic acid.

2. Unsaturated: Double bonded –

Oleic acid, linoleic acid, linolenic acid, arachidonic acid

II - Based on Nutrition
1. Essential: Linoleic acid, Linolenic acid, Arachidonic acid.

2. Non essential: Remaining all other fatty acids.

 III - Based on Length of Chain

1. Short Chain Fatty acids ( SCFA )

up to 8C atoms Butyric acid (4C), Caproic acid (6C)

2. Medium Chain Fatty acid ( MCFA )

8-12 C atoms Caprylic acid (8C),
Decanoic acid (10C)

3. Long chain Fatty acids ( LCFA )

> 12 C atoms Myristic acid (14C )
Palmitic acid (16C )
Stearic acid (18C ) 47
 III - Based on Esterification

1. Esterified: ( 95% )
make Esters with Alcohols.
Percentage of Esterification of Fatty acids is as follows:
a. 45 %  with Triglycerides.
b. 35 %  with Phospholipids.
c. 15 %  with Cholesterol.

2. Un-esterified: ( 5% )= Free
TransPorted by albumin
Plasma Level is 10-15 mg/dl
 IV- Based on Isomerism

1. In case of Saturated FA
a. Straight chain: Butyric acid.
b. Branched: Isobutyric acid.

2. In case of Unsaturated FA
a. Cis - Oleic acid
b. Trans - Oleic acid 49
 VI - Based on Number of Double Bonds
1. Monounsaturated ( MonoEthenoid, MonoEnoic )
One Double Bond e.g. Palmito-oleic acid, Oleic acid

2. Polyunsaturated ( PolyEthenoid, PolyEnoic )

2 or more double bonds e.g. Linoleic & arachidonic

3. Eicosanoids:
These are Derivatives of 20 C Polyenoic acids:
Prostaglandins (PGs) Leukotriens (LTs)
Prostacyclins (PCI) & Thromboxanesm (TXs)
 VII - Based on Solubility Degree

1. Soluble:
Short chain Fatty acids &
Usually Polyunsaturated F.A

2. Insoluble:
Long chain fatty acids
Usually Saturated
 VIII - Based on Melting Points
1. High Melting Point: Saturated Fatty Acids
2. Low Melting Point: Unsaturated Fatty Acids

IX - Clinical Classification
1. Atherogenic: e.g. Saturated FA
Cause atherosclerosis narrowing of BV

2. Atheroprotective: Prevent Atherosclerosis

e.g. Polyunsaturated FA ( PUFA )
 Saturated UnSaturated
Fatty Acids Fatty Acids
1 - Single Bonds Double Bonds
2 - Less Abundant More Abundant

3 - Less Soluble More Soluble

4 - Melting Point High Melting Point Low

5 - May be Straight or May be Cis or Trans forms

Branched
6. They are PolyUnSaturated are
Non-Essential Essential
 Saturated UnSaturated
Fatty Acids Fatty Acids
7. Synthesized in Body Synthesized in Body
Excluding the Essentials
8. Oxidized in the More Rapidly Oxidized in
Body
the Body
9. Elevate Cholesterol Lower Cholesterol Level.
level
10. Don`t form
Prostaglandins
20 Carbons Arachidonic acid forms
& Leucotriens
them.
 Eicosanoids
Are Cyclic Compounds that Derived from
Arachidonic acid after its Cyclization
( 20 C Unsaturated with 4 Double Bonds )

Two Groups:

1 - Prostanoides
2 - Leukotrienes ( LT )
 1- Prostanoides:
A - ProstaGlandins (PG):
- Their Types are A, B, D, E, F, G, H & I
- have Hormonal Like Action
- Can cause Vasodilation, Uterine & Intestinal Contraction

B - ProstaCyclines
- can Cause Vasodilation.
- Inhibit Platelet Aggregation
C- Thromboxans
- can Cause Platelet Aggregation.

2 - Leukotrienes (LT)
- Present in Leucocytes, Platelets & Mast Cells
- Can Cause Chemotaxis
(i.e. WBCs Collection at Site of inflamation)
59
Alcohols
( R.OH )
 Alcohols Associated with Lipids
Include:

Glycerol, Cholesterol
in Our Diet & Body
But
Higher alcohols are found in Wax
 Glycerol
- TriHydric Alcohol
(Contain 3-OH groups)
- Colorless, Odorless,
- Hygroscopic & has Sweet Test
- Souble in Water & Alcohols
( Not in Fat Solvents )
form Esters with FA
Dehydration of Glycerol
( Removal two molecules of water in presence of conc. Sulphuric acid )

Leads to Acrolein Formation

( Aldehyde with Characteristic Odor )

Glycerol can be Used in

Manufacuring of Cream & Lotions.
used as a
Drug ( Nitroglycerol ) for Coronary Dilation.
Still in
Simple
Lipids
Triacylglycerol
Triacylglycerides makes ~90% of Our lipid diet
All animal Fats and all Plant Oils
O
O
OH C R1
H2C OH O H2C O C R1
O
-3 H2O
HC OH + OH C R2 HC O R2
O
H2C OH H2C O R3
OH C R3
Glycerol Triacylglycerol O
Fatty acids
 Body Triacylglycerols
TG are Stored mainly in Cytoplasm of Fat cells
( Located Subcutaniously, around Kidney & other Organs)
Body Fat is Important Source of Energy
( i.e. Each Gram can give 9.3 Kcal )
Human Fat is Liquid at Room Temp.

Dietary Sources Includes:

Animal Sources; Butter, Lard
Plant Sources; Oils as Cotton Seed, Linseed, Sesame & Olive
Marine Oils; e.g. Cod Liver Oil, Shark Liver Oil
- All TG are Water Insoluble (soluble in Fat solvents)

- T.G. rich in Unsaturated FA are:

Liquid at Room Temperature (Oils)

- T.G. rich in Saturated FA are:

Solid at Room Temperature (Fats)

- T.G. Floats on Surface of Water so,

its Specific Gravity < than 1
- All TG can Give +ve Grease Stain Test
 Rancidity
It is Toxic Reaction of T.G.
Due to Oxidation of its Unsaturated FA by
Oxygen of air, Bacteria or Moisture.

Leads to Unpleasant Odor or Taste of oils & fats

3 Types :
- Oxidative Rancidity
- Ketonic Rancidity
- Hydrolytic Rancidity
Complex
( Conjugated )
or

( Compound )
Lipids
 Are Esters of
Fatty acids with Alcohol in addition to Other groups

I - Phospholipids ( Subclassified into )

a GlyceroPhospho Lipids b SphingoPhospho Lipids

II - Sphingolipids (may be with or without Phosphate)

a Glycolipids b Sulfolipids
c Gangliosides d Mucolipid

II - Glycolipid
IV - Proteolipids (Lipoprotein) 73
PhosphoLipids
Types

GlyceroPhosphoLipids
e.g. Phosphotidic acid
Lecithin
Cephalin
Plasmalogens
Cardiolipin

SphingoPhosphoLipids
74
e.g. SphingoMyelins
 I- GlyceroPhosphoLipids:
Phospholipids Containing Glycerol
These contain Glycerol, Fatty acid, H3PO4 and
in many cases a Nitrogenous base which may be

Choline, Ethanolamine, Serine or Inositol

e.g. Lecithins, Cephalins, Phosphatidic acid.

• Have Fatty acid Ester Groups at First Two Carbons of Glycerol

• At Third Carbon: PhosphoDiester Group 75

 Glycero Phospho Lipids
Phosphatidyl Choline
Phosphatidyl Serine
( Lecithin )

Phosphatidic acid
Phosphatidyl Ethanolamine Phosphatidyl Inositol
( Cephalin ) ( Lipositol )
1- Phosphatidic acid:
DiAcylGlycerol Phosphate
the Parent & Precursor
of All Other Types Formed of Glycerol
Esterified
at C1 (  ) with Saturated F.A
at C2 (  ) with Unsaturated F.A
at C3 (  ) with Phosphoric acid
2 - Cardiolipin:
( Di Phosphatidyl Glycerol )

Two Phosphatidic Acids

Linked Together by
Glycerol.
Is the Major Lipid Mitochondrial Membrane
It is Antigenic (Stimulate Antibody Formation)
3 - Phosphatidyl Choline
( Lecithin )
Phosphatidic acid
+
Choline Attached at Phosphoric acid at C3 ()
( TriMethylated Decarboxylated Serine )
- Lecithin enter in Cell Membrane Structure

- Lecithin act as Lipotropic Factor

- Lecithin Can Form Cholesterol Ester

(Transported to Liver to be Execreted into Bile)
& Lysolythesin when React with Cholesterol
by enzyme called LCAT & ACAT
ACAT
Lecithin + Cholesterol Cholesterol Ester + Lysolythesin
LCAT
Lecithin act as Store of Choline
Cholin is Important for
Nerve Transmission &
Methyl Donor in Transmethylation Reactions

Lecithin
Prevent Cholesterol Gall Stones
through
Solublization of Cholesterol
Di-Palmityl-Lecithin is
Continuously Secreted by alveolar Cells of Lung
to act as

Lung Surfactant
Prevent
Lung Collapse (Adherence of Alveolar Wall)
so,
Help Expiration & Inspiration
( Makes Lung Easier to Expand )
Respiratory Distress
Syndrome
( Hyaline Membrane Disease )
Occurred in
Premature Babies where
Lungs Not Secrete Enough Surfactant
Leading to Lung Collapse & Respiratory Failure
4 - Phosphatidyl Ethanolamine
( Cephalin ):
Phosphatidic acid
+
Ethanolamine
( Decarboxylated Serine )
One of
Activating Factors of Coagulation Mechanism
5. LysoPhosphoLipids
( LysoLecithin & LysoCephalin ):

Like Lecithins & Cephalins

but
i.e. Without FA in Position ( C2 =  ) which is
Usually Unsaturated
LysoLecithin is Important in
Metabolism & InterConversion of Phospholipids
LysoCephalin ( Strong Surface Acting Substance ) is
used for Chocolate Manufacturing.
6. Phosphatidyl Serine:
Phosphatidic acid
+
Serine
(  amino,  hydroxy Propionate )
N.B. Threonine May be also Present
7 - Phosphatidyl Inositol:
(Lipositol)
Phosphatidic acid
+
Inositol (Alcohol Cyclic Sugar)
Present in Cell Membrane,
Precursor of 2nd Messenger Inositol Triphosphate
( Mediate Hormonal Action )
8- Plasmalogen:
as Lecithin
But
contain Unsaturated Alcohol attached to
Glycerol at C1 ( Instead of Saturated FA )

Contribute about 10% of Phospholipids

Present in Brain & Muscles
89
 Glycerol Fatty acids Phosphatidic acid Glycerophospholipid
O O O

H2C OH OH C R 3 H2C O C R3 H2C O C R3

O O O

-3 H2O
HC OH +
+ OH C R 2
HC O C R 2 HC O C R2
O O O

HOR1
H2C OH OH P OH H2C O P OH H2C O P OR1
- H2O

O- O- O-
Phosphoric acid Phosphodiester group
 Decarboxylated Seine

TriMethylated Ethanolamine

α-Amino β-Hydroxy Propionate

Cyclic Alcohol Sugar

II- SphingoPhosphoLipids
These contain Sphingosine (Higher alcohol
Containing one OH group), Fatty acids, H3PO4
& Nitrogenous base ( Choline or Ethanolamine )

e.g. SphingoMyelins
the Only Lipids that
Contain Both Sphingosine & H3 PO4
 SphingoMyelin:
formed of

Ceramide + Phosphoric acid + Choline

i.e.
Sphingosine + Fatty acid + Phosphoric acid + Choline

ceramide
 SphingoMyelins
Present in High concentration in Brain & Nerve tissues

Niemann Pick`s Disease

due to Deficiency of Sphingomyelinase Enzyme
Lead to
Accumulation of Large Amounts of Sphingomyelin
which Cause

Mental retardation & Death in Early Life

 Ceramide
Not Phospholipids ( Parent Compound )
it is formed of Sphingosine + Fatty acid (Usually PUFA)

ceramide
 H 18 C alchohol
HO C C CH(CH2)12CH3
H

HC NH2

H2C OH
18 C
Sphingosine alchohol
 18 C alchohol

97
 Function of Phospholipids
 occurred in Every Body Cell ( e.g. Brain, Muscles & Nerves )

 Form Cell Membrane, Mitochondria & Golgi

 Important for Absorption of Lipids from intestine

 Important Component of Lipoproteins

 act as Lipotropic Factor ( Protect against Fatty
Liver )
 Phospholipids containing Cholin act as Methyl
Donor in Transmethylation Reactions
 Solubilize Cholesterol in Bile
 Acts as Signal Transmission across Cell Membranes
 Certain Enzymes require PL for their actions

 Play Role in Blood Coagulation Process

 Lecithin Lower Surface Tension & Emulsification
in GIT.
 Have a Role in Transport of Lipids from Liver

 Have role in Electron Transport & Oxidative

Phosphorylation 99
 Sphingophospholipid
SphingoPhosphoLipid & Sphingoglycolipid
H H
HO C C CH(CH2)12CH3 SphingoGlycoLipids
HO C C CH(CH2)12CH3
H H
O O
H H
HC N C R2 HC N C R2
O

H2C O P OR1 CH2

CH2OH

O- O O
H
Phosphodiester group H
OH H CHO

OH H

H OH
 SphingoLipids:
These are

NonPhosphate
Containing
101
1 - Glycolipids: Contain

Sphingosine, Fatty acid & Sugars

( Glucose or Galactose ) e.g.
Cerebron, Nervon, Oxynervon, Kerasin,
Mainly in White Matter of Brain & Myelin Sheaths.

Include
- Cerebrosides - Sulpholipids
- Gangliosides - Ceramide oligosaccharides 102
 Glycolipids
Formed of : Ceramide ( Sphingosine + F.A. ) + Carbohydrate
Types of Glycolipids:
Sphingosine FA
 Cerebrosides:
Ceramide + Single Galactose or Glucose Glucose
or Galactose
 Sulfatides:
CerebroSides
Ceramide + Single Galactose + Sulfate
 Globosides:
Ceramide + 2 or More Sugars.
 Gangliosides:
Ceramide + oligosaccharide containing 1 or more sialic acid
Simplest Ganglioside is Formed of:
Ceramide + 1 Glucose + 1 Galactose + 1 Sialic acid
Sphingosine F.A

GanglioSides Glucose Galactose Sialic acid

 Cerebrosides
( Simple Glycolipids ):
Contain

Sphingosine, Fatty acid &

Sugar ( Glucose or Galactose )
Present in White Matter of Brain &
Myelin Sheath of Nerve Fibers
act as Insulators of Nerve Impluse 104
 According to Type of FA,
Cerebrosides can be
Classified into Many Subtypes e.g.

Kerasin; FA is Lignoceric acid ( C24 Saturated )

Cerebron; FA is Cerebronic acid ( C24 Hydroxy Sat. )

Nervon; FA is Nervonic acid ( C24 Unsaturated ώ9 )

Oxynervon; FA is Oxynervonic acid ( hydroxy Nervonic )

105
2- Sulfolipids (Sulphatides)
Are Cerebrosides
Containing Sulphate group ( attached to Sugar )

Composed of
Sphingosine, Fatty acid, Galactose
& Sulfate group,
Present Mainly in White Matter of Brain 106
3 - Gangliosides
Complex Glycolipids because contain
One or More Sialic acid Molecules in addition to hexose

- Sphingosine,
- Fatty acid,
- 3 Molecules of Hexoses ( Glucose & Galactose ),
- HexosAmine ( N-acetylHexosAmine ) &
- Sialic acid ( One or More NANA ). 107
 4 - Ceramide
Oligosaccharides
Contain
- Sphingosine Base,
- Fatty acid ( C24 ),
- Many Glucose & Galactose units

Present in Heart & Kidney 108

 MucoLipids
Resemble Gangliosides
e.g.

Globasides,
Hematosides,
Strandin. 109
Total Plasma Lipids
( 360 - 820 mg/dl ), Include;
Triacylglycerol ( 80-180 mg/dl ),
Phospholipids,
Cholesterol ( Less than 220 mg/dl ),
- Free Cholesterol ( 26-126 mg/dl )
- Esterified Cholesterol
Free FA ( 6-16 mg/dl ),
LipoProteins
 Lipid part & Protein part.

 Found in Cell Membrane,

Mitochondria & Plasma

 Transport Insoluble Lipids

between Blood & Different Tissues
 Separated
By
Electrophoresis,
Ultracentrifugation,
Gas Liquid Chromatography
&
Thin Layer Chromatography
By Electrophoresis: Separated into
 Chylomicrons
 Β-lipoproteins
 Pre Β-lipoproteins
 -lipoproteins

By Ultracentrifugation: Separated into

 Chylomicrons
 Very low density lipoproteins ( VLDLs )
 Low density lipoproteins ( LDLs )
 High density lipoproteins ( HDLs )
 Main Amount Amount of Types of
Fraction Source Lipids of Lipids Apolipoprotein Apolipoprotein

A, B48, C & E
CM Intestine TG 98 % 2%

VLDL Liver TG 90 % 10 % B100, C & E

LDL From CholesterolCh 78 % 22 % B100

olesterol
VLDL
Ester &
in blood phospholipids

HDL Liver CholesterolCh 50 % 50 % A, C, D & E

olesterol
&
Ester &
intestine phospholipids

FFA- Adipose FFA 1% 99 % Albumin

Albumin tissue
 Types, Source, Density, Size
and Functions of Lipoproteins
Fraction Source Density Size Function

Chylo Transport of dietary TAG (mainly),

Micron Intestine Lowest Largest cholesterol & cholesterol esters from
the intestine to the tissues.

VLDL Liver Transport of endogenous TAG from

the liver to the peripheral tissues
From Transport of cholesterol from the
LDL VLDL liver to the peripheral tissues
in blood
Liver Transport of cholesterol from
HDL & Highest Smallest peripheral tissues to the liver for
intestine elimination
FFA- Adipose Very Very
Albumin tissue high small
I. Based on Density:
i. High Density Lipoproteins-- HDL
ii. Low Density Lipoporteins--- LDL
iii. Very Low Density Lipoproteins --- VLDL
iv. Chylomicrons - lighter than water

II. Based on Electrophoresis:

i. Alpha - Lipoproteins--- ( HDL )
ii. Beta - Lipoproteins---- ( LDL )
iii. Prebeta - Lipoproteins -- ( VLDL )
iv. Chylomicrons - Stationary ( does not move )

III. Clinical Classification:

i. Atherogenic : LDL, VLDL, Chylomicrons
ii. Atheroprotective
117 : High density lipoproteins
Derived
Lipids
 Derived Lipids
Substances derived from
Simple & Conjugated lipids By hydrolysis
Include:
1 - Fatty acids ( Saturated & Unsaturated )
2 - Glycerol
3 - Polycyclic Compounds as steroids.
4 - Carotenoids
5 - Ketone bodies
6 - Cholantherene
Derived Lipids
Hydrolytic Products:
Monoglycerides, Glycerol,
Fatty acids, Prostaglandins.

Miscellaneous lipids
Sterols, Cholesterol, Vitamins D,E,K & Steroids
120
 Sterols & Steroids;
Group of Compounds Contain Ring
called

Cyclopentano-
Perhydro-
Phenantherene Ring 121
• Three six-membered & one five-membered
rings
Ring C
• Includes cholesterol, adrenocortical sexD
Ring
and
hormones, and bile salts

Ring A Ring B
Cyclopentano-Perhydro-Phenantherene Ring
Is

Three Six-Membered
&
One Five-Membered Rings

123
 Steroids
have Steroid Nucleus
Composed of 17 carbon atoms
( 4 Rings A, B, C, D )
& 2 Methyl Groups
at C10 & C13
Making C18 & C19
Cyclopentano Perhydro Phenantherine Nucleus
18
18

19
19

Steroid Nucleus ( Ring )

Types of Sterols & Steroids
- Cholesterol (Animal sterol)
- Ergosterol (Plant sterol)
- Vitamin D group (D2 & D3)
- Bile Salts
- Steroid Hormones
( Male & Female Sex hormones )
( Adrenocortical Hormones )
- Digtalis Glycosides
- Some Carcinogenic Substances 126
 Steroids include:
 Sterols: Steroid alcohol for Example Cholesterol
 Bile acids:
Primary bile acids & Secondary bile acids.

 Steroid hormones:
Sex Hormones:
Male sex hormones: e.g., Testosterone
Female sex hormones: Estrogens & Progesterone
Adrenocortical Hormones:
Glucocorticoides as Cortisol, Cortisone & Corticosterone
Mineralocorticoids as aldosterone

 Vitamins D
Cholesterol
( 27C )
 Cholesterol ( 27C )
is Formed of

Steroid Nucleus,
- OH group at C3 ( only polar group ),

- 2 Methyl groups at C10 & C13

- One Double bond between C5 & C6
- 8 Hydrocarbon Side Chain at C17
Cyclopentano Perhydro Phenantherine Nucleus
18

19

Steroid Nucleus ( Ring )

 Cholesterol is
Present in Every Body Cell
( Cell Membranes )
Especially in;
- Adrenal Cortex
- Liver
- Kidney
- Brain & Nervous System
- Skin
 Occurs in Blood Either Esterified or Free
Esterified with Long Chain FA to OH group at C3

 Cholesterol may be of Exogenous ( Dietary )

or Endogenous ( formed Inside the Body )

 Normal Plasma Level is

Less than 220 mg/dl ( 5.3 mmol/ml )

 High Cholesterol Levels Predispose to

Atherosclerosis or Gall Bladder Stones
 Steroid Nucleus, OH group at C3,
One Double Bond between C5 & C6 & Long Side Chain at C17
- It is an Alchohol

- Insoluble in Water ( Soluble in Fat Solvents )

- Form Characteristic Crystals with Broken

Corner

- Give Positive Lieberman Test ( Bluish Green

Color )

- Present Only in Animals, Not in Plants

 CopraStanol
( CoproSterol ) :
Cholesterol in Intestine is Reduced
( Reduction of Double Bond Between C5 & C6 )
By Bacteria Flora
Into Coprastanol
Before its Excretion
 FORMS OF CHOLESTEROL
 Free Cholesterol: 30 %

 Esterified Cholesterol: 70 %

TRANSPORTATION BY:

 LDL - Bad Cholesterol

 HDL - Good Cholesterol

Cholesterol
• Important in cardio-
vascular disease → lower intake of cholesterol
• Critical to many physiological functions
• A component of membranes
• Precursor to all other animal steroids including adrenocortical
& sex hormones, and bile salts

• Body synthesize cholesterol if it’s excluded from diet

 Exogenous
 Butter, Cream & Milk & Milk Products
 Eggs, Especially Egg Yolk
 Beef, Meat ( Brain, Liver & Kidney )

Endogenous
 Synthesized in Tissues & Liver: I gm/day
140
 Importance of Cholesterol
 Structure of cell membrane, brain, liver and
other organs.
 Formation of Vitamin D.
 Precursor of steroid hormones.
 Gives bile salts by oxidation.
 Biomedical Importance of Cholesterol

Formation of:
Bile acids
Steroid Hormones
Vit. D3 in Skin
Lipoproteins
Cell Membranes
- Transport of Long chain FA

- Has Insulating Effect in CNS

- Makes Skin Highly Resistant to Absorb

Water Soluble Substances

- Prevents Water Evaporation from Skin

Cholesterol
• Important in cardio-
vascular disease → lower intake of cholesterol
• Critical to many physiological functions
• A component of membranes
• Precursor to all other animal steroids including adrenocortical
& sex hormones, and bile salts

• Body synthesize cholesterol if it’s excluded from diet

 Ergosterol
 Plant Sterol ( absorbed from Small Intestine )
 Give Vitamin D2 by Ultraviolet Rays
 Similar to Cholesterol but
 Differ in
- Extra Double Bond between C7 & C8
- Side Chain is Unsaturated & Has Extra Methyl group
 Vitamin D Group
Vitamin D2
Derived From Ergosterol By
Rupture of Second Ring by Ultraviolet Rays

Vitamin D3
Derived from 7-dehydrocholesterol By
Rupture of Second Ring by Ultraviolet Rays
 Bile Acids
Are
Hydroxy Derivatives of Cholanic acid
( C24 Steroid )

Two Types :
1 - Primary Bile Acids
2 - Secondary Bile Acids
( Not Containing OH at C7 )
 1 - Primary Bile Acids
- Cholic acid = 3, 7, 12 TriHydroxy Cholanic acid &
- ChenodeoxyCholic acid = 3,7 Dihydroxy Cholanic acid
formed in Liver during Cholesterol Catabolism

2 - Secondary Bile Acids

( Not Containing OH at C7 )
- DeoxyCholic acid = 3, 12 Dihydroxy Cholanic acid &
- LithoCholic acid = 3 Monohydroxy Cholanic acid
Formed By Action of
Intestinal Bacterial 7 -dehydroxylase enzyme
 Bile Salts:
are
Bile acids ( Cholic acids ) Conjugated with
Glycine ( 80% ) & Taurine ( 20% )
Excreted in Bile from Liver in Form of:
Na Salts of Glycocholate & Taurocholate
Bile Salts in the Intestine Undergo
Enterohepatic Circulation
( Reabsorbed from Intestine to Blood then Returned Back to
the Liver to be Excreted Again in Bile )
 Function of Bile Salts:
Essential for
- Digestion: Needed for Emulsification of Fat
- Absorption: Participate in Micelle ( form of
lipid during its absorption ) formation
- Good way for Excretion of Cholesterol
- Choleretic Effect: Enhance Liver to Excrete
More Bile
- Prevent Cholesterol Precipitation
 Hormones of
Steroid Nature
“ Derived from Cholesterol ”
 Female Sex Hormones
Esrtogen:
Three types:
Estrone ( E1 ), Estradiol ( E2, most active ) & Estriol ( E3 )

Structure:
- Ring A is unsaturated
- OH at C3
- Methyl group at C13
* Ketone group at C17 (E1),
* OH at C17 (E2)
* 2 OH at C16, C17 (E2)
Synthesis:
From Cholesterol

Site of Production:
- Mainly: Ovary & Placenta in Female
- Minor amounts: Adrenal cortex in both Male & Female
Testis in Male

Fate:
E3 is the End product,
Produced in the Liver &
Conjugated with Sulphuric acid & Glucuronic acid
then Excreted in Urine
Biochemical Role of Estrogens
- Stimulate development of
Female Secondary Sex Characters e.g.
Voice, Hair & Fat Distribution
- Stimulate Development of
Female Sex Organs e.g. Uterus
- E2 has Anabolic Effects on Bone & Cartilages

- Synthetic Estrogen can be

Used for Contraception
 Progestrone:
Structure:
* Ketone group at C3
* Double bond between C4 & C5
* Methyl group at C10 & C13
* Ketone ketone at C17
Site of Production:
- Ovary & Placenta in female
- Adrenal Cortex in Both Male & Female
Fate:
Pregnadiol is the End Product, Produced in the Liver
& Conjugated with Sulphuric acid & Glucuronic acid
then Excreted in Urine
Biochemical Role of Progesterone:
- Prepare Uterus for
Implantation of the Ovum
- Stabilizes Pregnancy ( Prevent Abortion )
- Stimulate Breast Acini
during Puberty & Pregnancy
- Inhibit Milk Production in Late Pregnancy
After Delivery
( Progesterone Decreases Sharply & Cause Lactation )
- Adntagonizes Action of
Estrogens at Various Tissues
 Male Sex Hormones
Androgens:
Three Types:
Testosterone, Dihydrotestosterone ( DHT )
Structure:
- Ketone group at C3
- Double bond between C4 & C5
- 2 Methyl group at C10 & C13
- OH at C17

Dihydrotestosterone ( DHT ) ( active form in tissues )

has the Same Structure of Testosterone
Without Double Bond Between C4 & C5
 Androgens:
Site of Production:
- Interstitial cells of Leyding of the Testis in Male
- Adrenal Cortex in Both Male & Female

Fate:
17-Keto Steroids is the End Product
( Compounds having =O Instead of -OH at C17 e.g.
Dehydro-Epiandrosterone Acetate (DHEA), Androsterone & Epiandrosterone )
Which is Excreted in Urine
Biochemical role of Androgens:
- Stimulate Development of Male Secondary
Sex Characters e.g. Voice, Hair & Fat Distribution
- Stimulate Sperm Formation ( Spermatogenesis )
- has Anabolic Effects on Proteins

Variations in Urinary 17-keto Steroids

Increased in Testicular Tumors & HyperCortisism
( Cushing syndrome )
Decreased in Hypogonadism & HypoCortisism
( Addison Disease )
Adrenal Cortical Hormones
Three Types:
Glucocorticoids & Mineralocorticoids
Structure:
- All have a ketone group at C3
- All have double bond between C4 & C5
- All have 2 Methyl group at C10 & C13 (except aldosterone)
- All have a ketol group at C17
- Glucocorticoids have an - OH group or oxygen at C11
but Mineralocorticoids have No free OH group or
Oxygen at C11
 Adrenal Cortical Hormones:
Site of Production:
are Derived from Cholesterol in
Adrenal Cortex of Suprarenal Gland

Types:
* Gluco-Corticoids:
Corticosterone, Cortizol, Cortisone & 11-dehydrocorticosterone

* Mineralo-Corticoids:
Aldosterone, DeoxyCorticoSterone ( DOC )
Synthetic Derivative of DOC is called DeoxyCorticoSterone
acetate (DOCA) used in treatment of addison disease ( hypocortissism )
 Biochemical Role of
Adrenal Cortical Hormones
- GlucoCorticoids:
Control Metabolism of CHO, Lipids & Proteins
( Have Anabolic Effect on CHO i.e. Anti-Insulin Effect )
( have Catabolic Effect on Lipids & Proteins )

- MineralCorticoids:
Control Metabolism of Minerals,
Act Mainly on Kidneys where it promotes
Secretion of K+ & H+ & Reabsorbtion of Na+
Lipid Peroxidation,

Free Radicals,
Antioxidants,
 Free Radical is an Atom or Fragment of Molecule
having One or More Unpaired Electron
(it is Not Positively or Negatively Charged).
So it is Very Reactive & Unstable.

Free Radical will Steal Electron from another

Molecule (e.g. in a cell wall) Creating a New One &
a Chain reaction will Begins which leads to
Cell damage.
 Free Radicals can be Considered to be
Partially Reduced Metabolites of Oxygen
e.g.

Superoxide Anion ( O-.2 ),

Hydroxyl Radical ( OH-. ),
H2O2
Peroxidation of Unsaturated FA
Creates also Free Radicals.
Sources of Free Radicals:
A - Sources of Superoxide anion O-.2:
1 – Ischemia of Mitochondria
2 – Vascular Endothelium
3 – Circulating White Cells such as Neutrophils
4 – Conversion of Hypothanthin & Xanthin to Uric acid

by Xanthin Oxidase
 Sources of Free radicals:
B - Peroxidation of Unsaturated FA
Exposure of Lipids containing PUFA to Oxygen leads to
Auto-oxidation = Peroxidation i.e. free radical formation

Lipid Peroxidation is a Chain Reaction (i.e. Provide

Continous Supply of Free Radicals which in Turn
initiate Further Peroxidation & so on), initiation
begins by Light or Metal ions.
C- Other Sources of Free Radicals:
1 – Oxidation of Catecholamines
2 – Activated Neutrophils (produce free
radicals to act as defense mechanism against
bacteria)
3 – Reaction with Xenobiotic drugs through
cytochrome P450 system of liver microsome.
4 – Cell ischemia in Myocardial Infarction
5 – Exposure to Sun Light & Osazone
6 – X-rays & -rayes
Toxic effects of Free radicals:
1 – Cell damage due to rupture of cell membrane by
free radicals produced by lipid (of cell membrane)
Peroxidation

2 – AtheroScelerosis

3 – Malignancy (free radicals interact with DNA &

other macromolecule leading to mutation &
molecular damage)
 4 – Aging process (in form of weakened
immune system & some inflammatory diseases)

5 – Oxidation of - SH groups in protein

(leads to loss of biological activity of some
proteins & enzymes)

6 – Myocardial infarction (ischemic

myocardial cells may produce free radicals Such
as Superoxide O-.2, Hydroxyl Radicals OH-. &
H2O2 which cause myocardial cell damage)
Antioxidants & Prevention of
Toxic effects of Free radicals:
Antioxidants are substances (atoms) that can give up an
electron to free radicals. So prevent their toxic effects.
Through its conversion to normal atoms.

1- Artificial Antioxidants Types: Such as

Propyl-gallate e.g.
Butylated hydroxyanisol (BHA) &
Butylated hydroxytoluene (BHT)
Can be used as food additives
2- Natural Antioxidants: e.g.
- Vitamin E - Vitamin C - B-carotenes
- Some Enzymes (Peroxidase, Superoxide dismutase)

Natural Antioxidants
can be Classified into:
A- Preventive natural antioxidants;
reduce rate of chain initiation.
They include:
1- Catalase (convert toxic hydrogen peroxide into water)
2- Peroxidase (convert toxic hydrogen peroxide into water)
3- Metal Chelators: (remove metals which may initiate FA peroxidation)
A- Preventive natural antioxidants;
reduce rate of chain initiation. They include:
1 - Catalase
(Convert Toxic Hydrogen Peroxide into Water)
Catalase
2H2O2 2H2O + O2
2 - Peroxidase
(Convert Toxic Hydrogen Peroxide into Water) e.g.
Glutathione Peroxidase (Need Selineum as Trace Mineral)
glutathione peroxidase
H2O2 + 2 GSH 2H2O + GSSG
3 - Metal Chelators:
(Remove Metals which May initiate FA Peroxidation)
e.g. EDTA (ethylenediamine tetraacetate),
DTPA (diethylene triamine penta-acetate)
B- Chain breaking natural antioxidants;
interfere with chain propagation. They include:
1 - Superoxide Dismutase:
(convert Superoxide Free radicals into Hydrogen Peroxide )
Superoxide Dismutase
O-.2 H2O2
2- Vitamin E (Tochopherols): (break chain reaction through
transfer a hydrogen atom of its phenolic group to peroxyl
(ROO.) free radical of PUFA)
3 - Vitamin C : (It may react to regenerate Tochopherols.
Also it may react with 2 molecules of peroxyl (ROO.)
free radical converting them to non free radical products)

4 - Urate, Phenols & other amines

End Of The Show