Biochemistry I (SGS 236)

Lecture 5: Lipids Chemistry

Dr. Mohamed Farouk

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 Learning Outcomes
By the end of this lecture the students will be able to:
• State the functions of phospholipids.
• Enumerate different phospholipids.
• List enzymes of phospholipids degradation.
• Describe other conjugated lipids.
• Describe the functions of different derived lipids.
• Demonstrate the differences between eicosanoids and
hormones.
• Define and state the functions of lipoprotiens.
• Enumerate the steps of lipids digestion.
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Triacylglycerols
Neutral fats are classified to:
• Oils: contain high content unsaturated fatty
acids (USFA).
• Solid Fats: contain high content saturated
fatty acids (SFA).
Chemical Properties of fats and oils: Hydrolysis

• They are hydrolyzed into their constituents (fatty

acids and glycerol) by the action of super heated
steam, acid or enzyme (e.g.: lipases of pancreas).

O O
CH2 O C R1 H2C OH R1 C OH
O Lipase or Acid O
R2 C O C H HO C H + R C OH
2
O
O
CH2 O C R3 3 H2O H2C OH
R3 C OH
Triacylglycerol Glycerol Free fatty acids
Chemical Properties of fats and oils: Saponification

• Alkaline hydrolysis produces glycerol and salts of

fatty acids (soaps).
• Soaps cause emulsification of oily material this help
easy washing of the fatty materials

O O
CH2 O C R1 H2C OH R1 C ONa
O O
R2 C O C H HO C H + R C ONa
2
O
O
CH2 O C R3 3 NaOH H2C OH
R3 C ONa
Triacylglycerol Glycerol Sodium salts of
fatty acids (soap)
 Chemical Properties of fats and oils:
Hydrogenation or hardening
• It is an addition reaction where hydrogens are added
at the double bonds of unsaturated fatty acids.
• Example: change of oleic acid of fats (liquid) into
stearic acid (solid).
 Chemical Properties of fats and oils:
Oxidation (Rancidity)
• This toxic reaction of triglycerides leads to
unpleasant odour or taste of oils and fats
developing after oxidation by oxygen of air,
bacteria, or moisture.
• Process of the drying oils after exposure to
atmospheric oxygen.
• Example: linseed oil is used in paints and
varnishes manufacturing.
 Conjugated Lipids: Phospholipids
Functions:
1. Phospholipids are the predominant lipids of cell
membranes. The hydrophillic head of the phospholipid
extends outward facing the intracellular or extracellular
aqueous environment.
2. Membrane phospholipids also function as a reservoir
for intracellular messengers.
3. Membrane phospholipids serve as anchors to some
proteins.
4. Non-membrane phospholipids serve as components of
lung surfactant & essential components of bile
(emulsifying agent). 8
 Conjugated Lipids: Phospholipids
Classes:
1. Glycerophospholipids (phosphoglycerides):
alcohol is glycerol.
2. Sphingolipids: alcohol is sphingosine.

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 Conjugated Lipids: Phospholipids
1- Phosphoglycerides:
Types:
a) Phosphatidic acid:
• This is the simplest
phosphogyceride, and is the
precursor of the other
members of this group.
b) Lecithin (Phosphatidyl
• The phosphate group on the
choline)
phosphatidic acid (PA) can be
esterified by another
c) Cephalin (phosphatidyl
compound containing an ethanolamine)
alcohol group. d) Phosphatidyl serine
e) Phosphatidyl inositol
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 Conjugated Lipids: Phospholipids
Degradation of Phospholipids:
• Phospholipases hydrolyze the ester bonds of a
phosphoglycerides.
• Each enzyme is responsible for cleaving the
phospholipid at a specific site.
• The major enzymes are:
1. Phospholipase A1 & A2 cleave fatty acid from
C1 and C2 respectively, producing
lysophospholipid.
2. Phospholipase C cleaves the phosphate group
producing diacylglycerol.
3. Phospholipase D cleaves the alcohol attached
to phosphate group producing phosphatidic
acid.
• Removal of fatty acids from C1 or C2 of a
phosphoglyceride produces a
lysophosphoglyceride. 11
 Conjugated Lipids: Phospholipids
2- Sphingolipids: sphingomyelin
• The backbone of shingomyelin is the amino alcohol
sphingosine, rather than glycerol.
• It is an important constituent of the myelin sheath
that insulates & protects neuronal fibers of CNS.

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 Conjugated Lipids: Glycolipids
• Formed of ceramide (sphingosine + Fatty acids)
attached to CHO radical, they include:
• Cerebrosides
• Sulfolipids
• Gangliosides
Importance:
1. Cell membrane receptors are mainly glycolipids.
2. Glycolipids are important constituents of nervous
tissue.
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 Derived Lipids
• They are substances produced from hydrolysis of
simple and compound lipids.
• They include:
Alcohols
Fatty acids
Eicosanoids
Steroids
Carotenoids

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 Derived Lipids: Eicosanoids
• Synthesized from C20-PUFA (arachidonic acid), hence their
name eicosanoids.
• Powerful hormone-like molecules that are produced by
most mammalian tissues.
Difference between eicosanoids and true hormones:
1. Eicosanoids are produced in very small amounts in almost
all tissues rather in specialized glands.
2. Eicosanoids act locally rather than after transport in the
blood to distant sites as occurs with true hormones.
3. Eicosanoids are not stored, and they have an extremely
short half-life.
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 Derived Lipids: Eicosanoids
Eicosanoids include:
Prostaglandins:
1.Promote inflammation (production of pain and fever).
2.Involved in uterine contraction during labor.
Prostacyclins:
Produce vasodilatation and inhibit platelet aggregation.
Thromboxanes:
They produce vasoconstriction and promote platelet
aggregation, which helps thrombus formation.
Leukotrienes:
They are released during anaphylaxis (severe allergic
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reaction).
 Derived Lipids: Steroids
Steroids

Steroid Bile acids

Sterols
hormones & Salts
Cholesterol in animals Sex hormones Primary bile acids
Phytosterol in plants Glucocorticoids Secondary bile acids
Minarolocorticoids

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 Derived Lipids: Steroids
Cholesterol
• Cholesterol is the characteristic steroid alcohol of animal
tissues.
Functions:
1. It is a structural component of all cell membranes.
2. It is the precursor of bile acids, steroid hormones and
vitamin D.
3. Component of plasma lipoprotein.

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 Derived Lipids: Steroids
Cholesterol
Sources of cholesterol:
1. Dietary cholesterol.
2. De novo synthesis of cholesterol in all mammalian cells.
Elimination of cholesterol:
1. Excreted in bile.
2. Converted to bile salts.
• Liver regulates cholesterol homeostasis.
• Normal plasma cholesterol level is < 200 mg/dl.
• Imbalance between cholesterol influx and efflux result in gradual
deposition of cholesterol in the tissues leading to atherosclerosis
and increased risk of CAD
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 Derived Lipids: Steroids
Steroidal Hormones
Male Sex Hormone(Testosterone)
• It is produced by the testicles.
Function:
• Controls the development of secondary sex characteristics such as
facial hair and increased muscle mass.
What are anabolic steroids?
• They are man-made derivatives of testosterone used by athletes and
body builders, who use it to stimulate the body to build muscle tissue
and strengthen bones and speed muscle recovery following exercise
or injury.
• Their use is extremely harmful as they can cause reduced sperm count
and infertility.
• Anabolic steroids mimic testosterone. When routinely injected, the
body “thinks” it has too much testosterone and shuts down the
hormones from the pituitary that stimulate the cells in the gonads. 20
 Derived Lipids: Steroids
Steroidal Hormones
Female Sex Hormones
1- Estrogens:
• They are produced by the ovaries.
Function:
• Control the development of secondary sex characteristics.
2- Progesterone:
• They are produced by the ovaries.
Function:
• Thickening the lining of the uterus each month to be prepared
to receive and nourish a fertilized egg.

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 Derived Lipids: Steroids
Steroidal Hormones
Glucocorticoids: Mineralocorticoids:
• They are secreted from the • They are secreted from the
adrenal cortex.
adrenal cortex.
• The main hormone is cortisol.
• The main hormone is
Functions:
aldosterone.
• They are involved in:
1. Regulation of Functions:
carbohydrates, proteins • Conservation of sodium and
and lipids metabolism. water.
2. Stress and inflammatory
• Excretion of potassium.
responses.
3. Water and sodium
balance.
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 Derived Lipids: Steroids
Function:
Bile acids and Salts
• Emulsification necessary
for digestion and
absorption of fats
Primary bile acids:
• Synthesized in the liver
from cholesterol.
• Cholic acid
• Chenodeoxycholic acid
Secondary bile acids:
• Synthesized by the action
of intestinal bacteria act on
primary bile acids.
• Deoxycholic acid
• Lithocholic acid 23
 Derived Lipids: Steroids
Bile acids and Salts
• In bile glycine (or taurine) are added to bile acids
which are then secreted in bile in the form of their
sodium salt (bile salts).
Cholic acid + Glycine + Na+ Sodium Glycocholate
(Bile Acid) (or Taurine) Sodium Taurocholate
(Bile Salt)

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 Derived Lipids: Carotenoids
• They are a class of more than 600 naturally occurring pigments
synthesized by plants.
• They are the sources of the yellow, orange, and red colors of many
plants.
• Fruit and vegetables provide most of the carotenoids in the human
diet.
• Carotenoids are precursors of vitamin A.
• Liver is the organ responsible for the conversion of carotenoids to
vitamin A.

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 Lipids Digestion
1-Digestion:
• An adult ingests about 60 to 150 gm
of lipids per day, 90% of them is
triacylglycerol (TAG). The remainder
of dietary lipids consist of cholesterol
(C), cholesterol ester (CE),
phospholipids (PL) and unesterified
fatty acids (FFA).
• Digestion begins in the stomach.
• There are two types of enzymes
called lipases stable at this pH:
a- acid lipase (lingual lipase).
b- gastric lipase.
• TAG is the primary target of these
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enzymes.
 Lipids Digestion
2- Emulsification:
It takes place in the duodenum and is done by:
• bile salts acting as surface active agents, secreted from liver
& stored in gall bladder.
• peristalsis, mechanical mixing by intestine.
Importance of emulsification:
• It increases the surface area of the hydrophobic lipid
droplets so that the digestive enzymes, which work at the
interface of the droplet and the surrounding aqueous
solution can act effectively.
• It stabilizes the particles preventing them from coalescing.
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 Lipids Digestion
3- Degradation of dietary lipids in the intestine by pancreatic
enzymes:
a- Triacylglycerol degradation:
• TG are acted upon by the pancreatic lipase, it removes the FA at carbon 1 & 3
to produce 2-Monoacylglycerol.
• Orlistate is an antiobesity drug which inhibits gastric and pancreatic lipases,
thereby decreasing fat absorption.
b- Cholesteryl ester(CE) degradation:
• CE is hydrolysed by pancreatic cholesterol ester hydrolase (cholesterol
esterase).
C- Phospholipid (PL) degradation:
• Phospholipase A2 is present as pro-enzyme in the pancreatic juice and is
activated by both trypsin and bile salts.
• It removes one fatty acid from carbon -2 of a phospholipid leaving a
lysophospholipid. 28
 Lipids Digestion
d- Hormonal control of dietary lipids degradation:
The pancreatic secretion of the hydrolytic enzymes is hormonally controlled.
Cholecystokinin (CCK) (also called before pancreozymin):
• Produced by jejunum and lower duodenum
• Acts on the gallbladder, causing it to contract to release bile.
• Acts on the exocrine cells of the pancreas causing them to release
digestive enzymes.
• Decreases gastric motility resulting in a slower release of gastric contents
into the small intestine, to keep the pH of the intestine.
Secretin:
• Produced from intestinal cells.
• Helps the liver and pancreas to produce watery solution rich in HCO3-.
• HCO3- neutralize the pH of the intestinal contents, to be appropriate for
the action of the pancreatic digestive enzymes.
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 Lipid Absorption and Transport
The mixture of lipids absorbed by enterocytes where:
• Fatty acids are activated into acyl CoA.
• Free cholesterol are esterified to cholesterol ester.
• Lysophospholipids are again converted to phospholipids(PL).
• 2-Monoacylglycerol is converted back to triacylglycerol (TAG).
• TAG, PL and CE are assembled to form chylomicrons (lipoprotein).

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 Lipoproteins
• Complexes of lipids and proteins. What is the difference between
Function: proteolipids and lipoproteins?
• Proteolipids: formed of lipids
• Transport of fat soluble surrounding proteins thus
substances. reendering them insoluble in water
but soluble in lipids.
• Lipoproteins: formed of proteins
that surround lipids to render them
water-soluble. Lipids

Proteins
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Proteolipid Lipoprotein
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