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Classification of Lipids
Classification of Lipids
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
1-Phospholipids (phosphatides):
As their name implies, phospholipids contain
phosphorus in the form of phosphoric acid groups
which contain substituted fats, composed of glycerol,
fatty acids, and phosphoric acid bound in ester
linkage to a nitrogen bases. Their molecular structure
is polar, consisting of one hydrophilic head group
because of the oxygen with all of their pairs of
unshared electrons and two hydrocarbon tails of the
fatty acids are still hydrophobic. Found chiefly in
animal tissues.
This means that phospholipids are soluble in both water and oil. lipid with phosphate head
group main membrane component, emulsifying agent & surface active agent.
The fatty acids present are mostly saturated at R1 unsaturated at R2 .ex. Phosohatidic acid :
simplest form and precursor for others with no base, Phosphatydyl choline : most abundant present
in cell membrane with choline base 4
Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Importance of Phospholipids
1. They are present in large amounts in the liver and brain as well as blood.
2. The membranes bounding cells and subcellular organelles are composed mainly of
phospholipids.
3. They are important components of the lipoprotein coat essential for secretion and transport
of plasma lipoprotein complexes. Thus, they are lipotropic agents that prevent fatty liver.
4. Myelin sheath of nerves is rich with phospholipids
5. Important in digestion and absorption of neutral lipids and excretion of cholesterol in the
bile.
6. Important function in blood clotting and platelet aggregation.
7. They provide lung alveoli with surfactants that prevent its irreversible collapse.
8. An important role in signal transduction across the cell membrane.
9. They are a source of polyunsaturated fatty acids for the synthesis of eicosanoids.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Sources
They are found in all cells (plant and animal),
milk and egg-yolk in the form of lecithin.
• Structure: phospholipids are composed of:
1. Fatty acids (a saturated and an unsaturated
fatty acid).
2. Nitrogenous base (choline, serine,
threonine, or ethanolamine).
3. Phosphoric acid.
4.Fatty alcohols (glycerol, inositol or
sphingosine).
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Classification of Phospholipids
• Classified into 2 groups according to the type of the alcohol present they may
be glycerophospholipids or sphingophospholipid depending upon the alcohol group present
(glycerol or sphingosine).
A-Glycerophospholipids: Phospholipids that contain glycerol are called glycerophospholipids
(or phosphoglycerides).
1. Phosphatidic acids[Phosphatidic acid is the simplest phosphoglyceride, and is the precursor
of the other members of this group.
2. Lecithins
3.Cephalins.
4.Plasmalogens.
5.Inositides.
6.Cardiolipin.
B-Sphingophospholipids: They contain sphingosine as an alcohol and are named
Sphingomyelins.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
A-Glycerophospholipids
1-Phosphatidic acids: They are metabolic intermediates in synthesis of triglycerides and
glycerophospholipids in the body and may have function as a second messenger. They exist in
two forms according to the position of the phosphate.
B-Sphingophospholipids
Sphingolipids: contain the alcohol sphingosine
which are structural components of membranes
and surface antigens
Sphingosine:
It is the alcohol present in sphingolipids. It is synthesized OH
in the body from serine and palmitic acids. CH3 (CH2)12 CH CH CH CH NH 2
1-Sphingomyelins Sphingosine CH2OH
• Definition: Sphingomyelins are found in large amounts in brain and nerves and in smaller
amounts in lung, spleen, kidney, liver and blood.
• Structure: Sphingomyelins differ from lecithins and cephalins in that they contain sphingosine as
the alcohol instead of glycerol, They contain two nitrogenous bases: sphingosine itself and
choline. Thus, sphingomyelins contain sphingosine base, one long chain fatty acid, choline and
phosphoric acid.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
2-Ceramide
This part of sphingomyelin in which the amino group of sphingosine is attached to the
fatty acid by an amide linkage.
• Ceramides have been found in the free state in the spleen, liver and red cells.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
2-Glycolipids
• Definition: They are fatty acids with carbohydrates and nitrogen but
without phosphoric acid. Glycolipids also include some compounds
like sulfolipids, gangliosides, and sulfatids which are structurally-
related. lipids that contain carbohydrate residues with sphingosine as
the alcohol and a very long-chain fatty acid (24 carbon series).They are
present in cerebral tissue, therefore are called cerebrosides also Present
in cell membrane and nervous tissues.
Classification: According to the number and nature of the
carbohydrate residue(s) present in the glycolipids the following are
1.Cerebrosides. simplest form of glycolipids contains ceramides.
They have one galactose molecule (galactosides).
2.Sulfatides. They are cerebrosides with sulfate on the sugar
(sulfated cerebrosides).
3. Gangliosides. They have several sugar and sugaramine residues
,predominantly found in ganglions.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
1-Cerebrosides:
Occurrence: They occur in myelin sheath of nerves and white matter of the brain
tissues and cellular membranes. They are important for nerve conductance.
Structure: They contain sugar, usually β-galactose and may be glucose or lactose,
sphingosine and fatty acid, but no phosphoric acid.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
2-Sulfatides:
• They are sulfated cerebroside, in which the sulfate
group is usually attached to the –OH group of C3
or C6 of galactose.
• Sulfatides are usually present in the brain, liver
3-Gangliosides:
• They are more complex glycolipids that occur in the
gray matter of the brain, ganglion cells, and RBCs.
• They transfer biogenic amines across the cell
membrane and act as a cell membrane receptor.
• The most simple type of it the
monosialoganglioside,. It works as a receptor for
cholera toxin in the human intestine.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
3-Lipoproteins
Lipoproteins are the macromolecular complex of lipids
and proteins. Transportation of lipids in the blood.
Structure of lipoproteins;-
Hydrophobic lipids (TG, CE) in core;
Hydrophilic lipids (UC, PL) on surface
Definition:
Lipoproteins are lipids combined with proteins in the tissues. They are non-covalent
assemblies. The protein part of lipoprotein is called as apolipoprotein or apoprotein.
The lipid constituents of lipoproteins are mostly triglycerides, free and esterified
cholesterol and phospholipids. The non-polar triglycerides and cholesterol esters are
usually present in the core of lipoproteins where as polar phospholipids along with
apoproteins forms outer coat. However, the proportion of triglycerides, cholesterol and
phospholipids differs in various lipoproteins
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Structural lipoproteins:
Lipoprotein structure consist of non-polar lipid core surrounded by apoproteins and more
polar lipids. The outer apoprotein and polar lipid coat of lipoprotein solubilizes these lipid rich
particles in aqueous plasma. These are widely distributed in tissues being present in cellular
and subcellular membranes. In lung tissues acting as a surfactant in a complex of a protein and
lecithin. In the eye, rhodopsin of rods is a lipoprotein complex.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Transport lipoproteins:
These are the forms present in blood
plasma. They are composed of a protein
called apolipoprotein and different
types of lipids. (Cholesterol, cholesterol
esters, phospholipids and triglycerides).
As the lipid content increases, the
density of plasma lipoproteins
decreases
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Classification of Lipoproteins
Lipoproteins differ in the ratio of protein to lipids, and in the particular apoproteins and lipids
that they contain. They are differ in lipid and protein in:
1. Composition 2. size 3. density 4. site of origin.
1. Based on their density, the liporoteins of blood plasma are classified into 4 classes. The four
classes of liporoteins can be separated by ultra-centrifugation. Density of a lipoprotein is
inversely related to the lipid content. The greater the lipid content, lower is the density.
Different classes of lipoproteins based on the density are:
1. Chylomicrons, 2. very low density lipoproteins(VLDL) , 3. low density lipoproteins
(LDL) and 4. high density lipoproteins.(HDL)
2. Different classes of plasma lipoproteins can be separated by electrophoresis. Based on
differences in electrophoretic mobilities the plasma lipoproteins are classified into 4 classes.
They are: 1. -lipoproteins, 2. pre- β -lipoproteins, 3. β -lipoproteins and 4. chylomicrons
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Types of lipoproteins:
a)Chylomicrons: from the Greek chylø, meaning juice or milky fluid, and micron, meaning
small particle)are lipoprotein particles that consist of the largest diameter (size) and the
least density. They contain 1-2% protein only and 98-99% fat (contain highest percentage
of lipid and lowest percentage of protein).
Function:
Transport of lipid (comes from diet) to adipose tissues for storage and to muscles or
heart for energy needs. The main lipid fraction is triglycerides absorbed from the
intestine and they contain small amounts of the absorbed cholesterol and phospholipids.
b) Very low-density lipoproteins (VLDL) or pre-β-lipoproteins: Their diameter is smaller
than chylomicrons. They contain about 7-10% protein and 90-93% lipid. The lipid content
is mainly triglycerides about 60% formed in the liver and convert in to LDL in the
capillaries. They contain phospholipid and cholesterol more than chylomicrons.
Function:
Transport of TG synthesis in liver as VLDL to the peripheral tissues.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Functions of Lipoproteins
Lipoproteins are involved in the transportation of
lipids in the body.
1. Chylomicrons They transport dietary or
exogenous triglycerides from intestine to liver.
2. Very low density lipoproteins (VLDL) They
are involved in the transport of endogenous
triglycerides from liver to extra hepatic tissues.
3. Low density lipoproteins (LDL) is the major
vehicle for the transport of cholesterolfrom
liver to extra hepatic tissues.
4. High density lipoproteins (HDL) is the major
vehicle for the transport of cholesterol from
extra hepatic tissues to the liver.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
2. Electrophoresis:
• Is the migration of charged particles in an
electric field either to the anode or to the
cathode. It sequentially separates the
lipoproteins into chylomicrons, pre- β- , β -,
and -lipoprotein and albumin-free fatty
acids complex
• The mobility of lipids depend on protein
content.Particles with higher content of
protein move faster towards anode(+), HDL is
faster, then VLDL, LDL , chylomicron.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
C-Derived Lipids:
• They are the hydrolysis products of simple and compound lipids and/or their
derivatives that still possess the general characteristics of lipids and these include fatty
acids (saturated as well as unsaturated), glycerol, steroids, bile acids and substances
associated with lipids in nature such as carotenes, vitamin A, D, E and K.
1. Terpenes:-
They are linear or cyclic compounds formed by
condensation of two or more isoprene units. which are large
group of volatile unsaturated hydrocarbons found in the
essential oils of plants. Terpenoid compounds include,
tocopherol (vitamin E), Coenzyme Q(ubiquinone), Vitamin
K ( napthaquinon), carotenes, squalene etc. especially
conifers and citrus trees.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
2. Steroids
are the chemical messengers in our bodies are known as hormones which are organic
compounds synthesized in glands and delivered by the bloodstream to certain tissues in
order to stimulate or inhibit the desired process. Constitute an important class of
biological compounds are usually found in association with fat. They can be separated
from fats after saponification since they occur in the unsaponifiable residue. It is actually
metabolic derivatives of terpenes, but they are customarily treated as a separate group.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
A-Sterols
It has a hydroxyl group (OH) at C3 and an aliphatic side chain at C17 (Alcohol)
Types
1. Animal sterols :cholesterol and its derivatives (vit D3)
2. Plant sterols : ergosterol (pro vit D2) and its derivatives
General consideration about naturally occurring steroids:
A typical member of this group is cholesterol. Certain facts
have to be considered when drawing steroid formula:
1) There is always oxygen in the form of hydroxyl or ketone on C3.
2) Rings C and D are saturated (stable).
3) Methyl groups at C18 & C19. In case of vitamin D, the CH3
group at C19 becomes a methylene group (=CH2) and the ring B is
opened, whereas, this methyl group is absent in female sex
hormones (estrogens).
4) In estrogens (female sex hormones) ring A is aromatic and there
is no methyl group on C10.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
B .Cholesterol:
1. The word cholis derived from Greek words, Cho=bile,
steros= solid , ol= alcohol
2. All steroids have cyclopentanophenanethrene ring (A,
B,C and D) called steroid nucleus.Cholesterol is called
sterols because it has hydroxyl group, while steroids
contain ketone groups (C=O) or carboxyl group (COOH).
3. In 70 kg man a total of 140 gm of cholesterol is available, which is distributed in brain,
nerves ,muscles , adipose tissues, skin, blood, liver, spleen, bone marrow , alimentary tract ,
adrenal gland and present in all cell membranes .
4. In blood: - Cholesterol is present in two forms:-
A. Free cholesterol: which presents 1/3 rd of the total.
B. Cholesterol esters: which represents 2/3 rd of the total cholesterol.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Importance: -
1. It is the most important sterol in animal
tissues as free alcohol or in an esterified form
(with linoleic, oleic, palmitic acids or other
fatty acids).
2. Steroid hormones, bile salts and vitamin D
are derivatives from it.
3. Tissues contain different amounts of it that
serve a structural and metabolic role, e.g.,
adrenal cortex content is 10%, whereas, brain
is 2%, others 0.2-0.3%.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Sources of cholesterol:
Cholesterol originates both endogenously and exogenously.
Endogenously, It is synthesized in the body from acetyl-CoA (1gm/day, cholesterol does not
exist in plants).
Exogenously, It exists in the diet 0.3 ~ 0.5 gm/day (butter, milk, egg yolk, brain, liver, meat
and animal fat).
• Cholesterol is produced by the liver and also made by most cells in the body. It is carried
around in the blood by little carriers called lipoproteins. We need blood cholesterol because
the body uses it to:
A. Build the structure of cell membranes
B. Make hormones like estrogen, testosterone, cortisone, cortical and adrenaline
Elimination of cholesterol:
Cholesterol is eliminated from the liver by converted to:
1. bile acid and bile salts that are secreted into the intestinal lumen(duodenum).
2. Serve as a component of lipoproteins sent to the peripheral tissues. 35
Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Function of cholesterol
1. Regulated of body fluids
2. Cholesterol is widely distributed in all cells of the body but particularly in nervous tissue.
3. Cholesterol is esterified with essential fatty acids to form ester cholesterol, tend to lower
the plasma bad cholesterol level.
4. It is a major constituent of the plasma membrane and of plasma lipoproteins.
5. 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 which help the
body digest fat and absorb important nutrients , vitamin D and steroid hormones
(testosterone, estradiol, progesterone).
6.Cholesterol is a major constituent of gallstones.
7.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.
8.Neutralize the hemolytic action of number of agents like snake venoms and bacterial
toxins.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
3 CH3
of Rye).found in plant tissues, yeast, and fungi. Converted
HO
to Vitamin
HO
D2 on irradiation and it is less stable than cholesterol (because of
7-dehydrocholesterol Ergosterol
E-Other steroids-
Bile acids, adrenocortical hormones, gonadal hormones,
vitamins D and Cardiac glycosides
vitamin D2
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
F -Eicosanoids
These compounds are derived from long chain polyenoic fatty acids (20-carbon).
Examples of eicosanoids;-
Prostaglandins.
Prostacyclines,
Thromboxanes
Leukotrienes
lipoxins
They have roles in:
1. Inflammation 2. Fever 3. Regulation of blood pressure 4. Blood viscosity
5. Male fertility 6. Female conception 7. Muscle contraction 8. Blood clotting
9. Tissue growth 10. Broncho constriction 11. Regulation of sleep/wake cycle 12. Asthma.
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
Prostaglandins
They are unsaturated carboxylic acids (fatty acid ) Synthesized from arachidonic acid consisting of a
twenty-carbon skeleton that contains a five-carbon ring produce in prostate and in small amounts in all
tissue All the PGs have an –OH group at C12 and trans double bond at C13. Prostaglandins are found in
seminal fluid, plasma and other tissues.They found as a regulator of metabolism. members of this group
of structurally related natural hormones have an extraordinary range of biological effects.
1. Stumulation of smooth muscle.
2. Regulation of steroid biosynthesis.
3. Inhibition of gastric secretions.
4. Inhibition of hormone sensitive lipases.
5. regulation of nerve transmission
6. Stimulate uterine contractions.
7. Lower blood pressure and influence blood clotting.
8. And induce asthma-like allergic responses. Because their genesis in
body tissues
Prostaglandins, leukotrienes and thromboxanes regulate, blood clotting, the inflammatory response,
the reproductive system, the gastrointestinal tract, the kidneys, and the respiratory tract. These have
pharmacological and biochemical actions and act on smooth muscle, blood vessels and adipose tissues. 41
Lect (2) Chemistry of prepared by Aseel Al-Hinde
Many lipids consist of a polar head group (P) and a nonpolar tail(U)
for unpolar .)The lipid shown is a phospholipid( which has two
tails.)The term" lipid "is really a catch-all phrase for a wide variety of
hydrocarbon-based molecules of biological origin .Lipids encompass a
huge range of structures ,which can be aromatic or aliphatic( with or
without a benzene ring ,)acyclic( open-chain )or cyclic( ringed ,)
straight or branched ,saturated or unsaturated ,flexible or rigid .This
diversity makes it impossible to define lipids on the basis of a single
core structural feature or biosynthetic origin.
However ,one shared property of many lipids is that they are
amphipathic( or amphiphilic )molecules ;that is ,contains both
hydrophobic and hydrophilic groups .Although lipids are predominantly
nonpolar or hydrophobic"( water-fearing ,)"meaning that they do not
interact well with polar solvents like water ,most lipids also have some
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Lect (2) Chemistry of prepared by Aseel Al-Hinde
• polar or hydrophilic ("water-loving") component. In the case of cholesterol, the polar group is a
mere -OH (hydroxyl or alcohol). For the membrane lipids called phospholipids, however, the polar
groups are considerably larger and more polar
Their amphipathic qualities allow lipids to form lipid bilayers
(left) and micelles (right). The amphipathic character of the
phospholipids ,in particular ,directly influences their biological
function ,causing them to spontaneously organize into cellular or
intracellular membranes in water .
Within the aqueous environment of the body ,the polar heads of lipids tend to orient
outward to interact with water molecules ,while the hydrophobic tails tend to minimize their
contact with water by clustering together internally .
Single-tailed amphipathic lipids form a small sphere called a micelle
(pictured at left ),while two-tailed phospholipids form lipid bilayers ,
which create a hollow sphere that encloses a separate aqueous
compartment .These lipid bilayers are the structural components of the
cellular membranes as well as intracellular compartments called
organelles. 44
Lect (2) Chemistry of prepared by Aseel Al-Hinde
Our cell membranes are made mostly of phospholipids arranged in a double layer with
the tails from both layers “inside” (facing toward each other) and the heads facing “out”
(toward the watery environment) on both surfaces
Membrane lipids are amphipathic (amphiphilic) - one end is hydrophobic and the other is
hydrophilic Directs packing into micelles, bilayers (membranes), liposomes
Membrane lipids:
* Phospholipids - (glycerophospholipids &
sphingolipids) hydrophobic region attached to
polar group by phosphate
* Glycolipids - (sphingolipids & galactolipids)
hydrophobic region attached to polar group
(sugar)
* Sterols - rigid system of four fused
hydrocarbon rings
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Lect (2) Chemistry of prepared by Aseel Al-Hinde