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11/6/2014
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“You are what you eat !”
Thursday, November 06, 2014
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Rajesh Chaudhary
LIPIDS
Department of Biochemistry, KMC, Duwakot Thursday, November
06, 2014
Rajesh Chaudhary 2
Biomedical importance and function
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Phospholipids and Sterols are major structural elements of cell membrane.
Role as enzyme cofactor.
Electron carrier.
Light-absorbing pigment.
Hydrophobic-anchor for proteins.
Emulsifying agent in digestive tract.
Categories of biological lipids
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Eight major categories of Biological lipids
Lipids Vs. Fatty acids Vs.
Triacylglycerol
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Simplest lipid constructed from Fatty
acids are Triacylglycerol, also
referred to as TG, Fat or Neutral
fat.
How are ester link formed?
Triacylglycerol (TG)
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Examples of simple TG: Tripalmitin,
Tristearin, Triolein.
Types of Triacylglycerols
Simple Complex
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Triacylglycerol (TG)
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1. Triglycerides as storage
form of energy in
Eukaryotes and higher
vertebrates
2. Role of Lipases
Triacylglycerol (TG)
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What is the advantage of having TG as a stored
fuel rather than polysaccharide such as Glycogen and Starch?
1. The carbon atom of fatty acid are more reduced than glycogen and starch, thus, gives more energy.
(A gram for gram)
2. TG are hydrophobic thus unhydrated. Therefore, organisms don’t have to carry extra weight of water.
Classification of Lipids
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1. Simple lipids Examples: Fats and Waxes.
2. Complex lipids Examples: Phospholipids (glycerophospholipids, sphingophospholipids)
Glycolipids: glycosphingolipids
3. Precursor and derived lipids Examples: fatty acid, glycerol, steroids, fatty aldehydes, ketone
bodies.
Simple lipids Complex lipids
Classification of Lipids
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Fatty acids are aliphatic carboxylic acid.
Are either: 1. Saturated and 2. Unsaturated
1. Saturated: doesn’t contain double bond
2. Unsaturated: contains double bond
2. Unsaturated 2.1. Monounsaturated (E.g.: Oleic acid)
2.2. Polyunsaturated (E.g.: polyethenoid, polyenoic acids)
2.3. Eicosanoids (E.g.: Prostanoids, Lipoxin and Leukotrienes)
Nomenclature
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Saturated acids ends in “-anoic” acid.
Example: Octanoic acid
Unsaturated acids with double bonds end in
“-enoic” acid.
Example: Octadecenoic acid
Examples of saturated, monounsaturated
and polyunsaturated fatty acids
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Basic rules of nomenclature in Lipids
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1. Carbon atoms are named from the carboxyl carbon. (Carbon No. 1)
2. The rest of the carbon following are named as: 2,3,4… and so on
– also known as “a”, “b”, “g” and so on….
3. For polyunsaturated fatty acids: The no. of carbon is named from the opposite side of the carboxyl carbon and given the no.
(Carbon No. 1) – and called “omega (w)”.
Delta (D) is used for indicating the position and number of
double bonds.
Nomenclature
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Fatty acids are hydrocarbon derivatives (Length: C4 to C36).
Monounsaturated fatty acids
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… acids containing one double bond.
Figure. Oleic acid. n-9 is equivalent to w9.
Examples
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Palmitic acid: abbreviated form 16:0
Oleic acid: 18:1
Most commonly occurring fatty acids have even
no. of carbon chain 12 – 24.
Common pattern of location of
double bonds in Fatty acids
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In most monounsaturated fatty acids, double bond is between
C9 and C10. (D9)
Other double bonds of polyunsaturated fatty acids (PUFA)
are at D12 and D15.
Exception: Arachidonic acid
In most naturally occurring PUFA have cis-configuration.
Trans-FA are produced by fermentation in rumen of ruminants.
Key convention on Polyunsaturated
Fatty Acids (PUFA)
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Double bond between the 3rd. And 4th. Carbon atom from methyl end is of special importance in human nutrition.
Alternative nomenclature is used for PUFA rather than conventional one.
1. Carbon atom to the most distant site from the carboxylic
terminal gets the name “w” – the carbon no. 1.
Example: Omega-3 fatty acid.
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Key convention in PUFAS
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Example: Omega-3 PUFA (a-linolenic acid)
(ALA; 18:3(D9,12,15))
(EPA; 20:5(D5,8,11,14,17) (DHA; 22:6(D4,7,10,13,16,19)
An imbalance in 𝑂𝑚𝑒𝑔𝑎−6 𝑓𝑎𝑡𝑡𝑦 𝑎𝑐𝑖𝑑
𝑂𝑚𝑒𝑔𝑎−3 𝑓𝑎𝑡𝑡𝑦 𝑎𝑐𝑖𝑑 Cardiovascular diseases
Optimal ratio is 1:1 or 4:1, but North American diet contains
10:1 or 30:1.
Geometric isomerism of D9, 18:1 fatty
acids (Oleic and Elaidic acids)
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Effect of temperature on structure of lipids (Higher Vs. Lower)?
Presence of acyl chains on same side vs opposite side around carbon containing double bond
Arachidonic acid
Physical and Physiologic properties
of Fatty acids
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Melting point of even numbered carbon fatty acids
increase with chain length and decrease according
to unsaturation.
Triacylglycerol containing three saturated fatty acids
of 12 carbons or more Vs. if, fatty acid residues
are 18:2
Membrane lipids are liquid at room temperature.
Structural Lipids in Membranes
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What are the structural lipids in membrane? 1. Glycerophospholipids (2 fatty acids + glycerol) –
hydrophobic region
2. Galactolipids & Sulfolipids (2 fatty acids + 1 glycerol) but lacks Phosphate
3. Archael tetraether lipids (2 acyl long chain + ether-linked to glycerol)
4. Sphingolipids (1 fatty acids + fatty amine (Sphingosine))
5. Sterol
Phospholipids Vs. Glycolipids
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In Glycerophospolipids and some Sphingolipids, a
polar head group is joined to hydrophobic moiety
with phosphodiester linkage – these are called
“Phospholipids”.
But, some lacks “Phosphate” group an can be
simple or complex – known as “Glycolipids”.
Some common types of storage and
membrane lipids
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Glycerophospholipids
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… called “Phosphoglycerides”.
2 fatty acids + 1st. And 2nd. Carbon of glycerol.
Glycerol is Prochiral.
No asymmetric carbon atom.
Some glycerophospholipids have ether-linked fatty acids.
Glycerophospholipids
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1
2
… released from leukocyte called
“basophils” and stimulate platelet
aggregation and release of
serotonine (a vasoconstrictor)
Sphingolipids
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… 4th. Large class of membrane lipids.
… contains one polar head and two non-polar tail.
Doesn’t contain “glycerol”.
3 subclasses of Sphingolipids
1. sphingomyelins
2. neutral glycolipids
3. and, gangliosides
Sphingolipids
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Sphingolipids at cell surface are
sites of biological recognition.
Many of these are specially
prominent in the plasma
membranes of neurons.
Carbohydrate moieties of certain
sphingolipids define the human
blood groups.
NOTE: Phospholipids and Sphingolipids
are degraded in lysosomes.
Sterols
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… structural lipids present in the membrane of most eukaryotic cells.
Cholesterol is one major sterol.
Phospholipids are the main lipid
constituents of membranes
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… is derivative of Phosphatidic acid.
1. Phosphatidylcholines (Lecithins) in membranes.
2. Phosphatidylinositol Precursor of second messengers
3. Cardiolipin major lipid in mitochondrial membrane.
4. Lysophospholipids intermediate in metabolism of
phosphoglycerols.
5. Plasmalogens occur in brain & muscle.
6. Sphingomyelins in Nervous system