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CHEMISTRY OF LIPID-I
(Introduction, fatty acids)
Naval Kishor Yadav
Asst. professor
Department of biochemistry
MCOMS, Pokhara
Lipids
• Heterogenous group of organic molecules including
fats, oils, steroids and related compounds which are
relatively insoluble in water and soluble in organic
solvents such as ether, chloroform, benzene, acetone
etc.
Bloor’s Criteria
Lipids are compounds having the following
characteristics:
 Insoluble in water
 Solubility in one or more organic solvents, such as
ether, chloroform, benzene, acetone etc.
 Some relationship to the fatty acids as esters either
actual or potential
 Possibility of utilization by living organisms
Classification
Simple lipids Compound lipids Derived lipids
Miscellaneous
Waxes Fat & Oils
(Triacyglycerols)
Phospholipids
Glycolipids
Lipoproteins
Other complex lipids
Fatty acids
Alcohols
Mono &
Diacylglycerols
Carotenoids
Squalene
Hydrocarbons
Lipids
Simple lipids
Esters of fatty acids with various alcohols
• Fats and oils : Esters of fatty acids with glycerol
Oil is a liquid while fat is a solid at room temp
Waxes:
• Esters of fatty acids (usually long chain) with alcohols
other than glycerol.
• Example: Cetyl alcohol : is a fatty alcohol with the
formula CH3(CH2)15OH
Complex lipids
Esters of fatty acids with alcohols containing additional
groups such as phosphate, nitrogenous base
carbohydrate, protein
i. Phospholipids : Lipids containing, in addition to fatty
acids and an alcohol, a phosphoric acid residue. Usually
have nitrogen containing bases and other substituents,
Examples:
a. glycerophospholipids : the alcohol is glycerol eg;
lecithin, cephalin and
b. sphingophospholipids: the alcohol is sphingosine eg;
sphingomyelin
II) Glycolipids (glycosphingolipids) : Lipids containing a
fatty acid, sphingosine, and carbohydrate
Example: Cerebrosides, Gangliosides
III) Other complex lipids: Lipids such as sulfolipids ,
lipopolysaccharides , aminolipids, Lipoproteins
Precursor and derived lipids:
• Include - fatty acids, glycerol, steroids, other alcohols,
fatty aldehydes, and ketone bodies, hydrocarbons,
lipid-soluble vitamins, and hormones
• Acylglycerols (glycerides), cholesterol, and cholesteryl
esters are uncharged, so they are termed as neutral
lipids
Function of lipids
 Storage form of energy (Triacylglycerol)
 Constituents of membrane structure and regulate
the membrane permeability (phospholipids and
cholesterol)
 Are important as cellular metabolic regulators
(steroid hormones and prostaglandins)
 Act as surfactants, detergents & emulsifying agents
• Provide insulation against changes in external
temperature
• Protect the internal organs, serve as insulating
materials and give shape and smooth appearance to
the body
• Help in absorption of fat soluble vitamins.
• Improve taste & palatability of food
• Lipoproteins, which are complexes of lipids and
proteins are involved in the transport of lipids in the
blood and are also components of cell membrane
• Lipids present in myelinated nerves act as insulators
for propagation of depolarization wave
• A knowledge of lipid biochemistry is important in
understanding many current biomedical areas of
interest, eg;
– obesity
– Atherosclerosis
– Myocardial infarction (heart attack)
– role of various polyunsaturated fatty
acids in nutrition and health
Fatty Acids
 Aliphatic carboxylic acids,
 General formula, R-CO-OH
 Depending on the R group (hydrocarbon chain), the
physical properties of fatty acid may vary
 Occurrence: esterified & free (unesterified) form
 Animal origin are much simpler in structure in
contrast of plant origin which often contain groups
like keto, hydroxy, cyclopentane rings
Classification of fatty acids
I. Depending on total number of carbon atoms
1. Even chain fatty acids:
 having carbon atoms 2,4,6 & series
Example: Acetic acid (CH3COOH)
Butyric acid (C3H7COOH)
Caproic acid (C5H11COOH)
Palmitic acid (C15H31COOH)
2. Odd chain fatty acids:
 having carbon atoms 3,5,7 etc
 Seen in microbial cell walls & also present in milk
Example: Propanoic (C2H5COOH)
II. Depending on the length of hydrocarbon chain
• Short chain = 2-6 carbons
• Medium chain = 8-14 carbons
• Long chain = 16-22 carbons,
• Very long chain fatty acids: 24 & above carbons
 Saturated fatty acids
 Unsaturated fatty acids
 Branched chain fatty acids (e.g. isovaleric acid)
 Hydroxy fatty acids (e.g. cerebronic acid)
III. Depending on the nature of hydrocarbon
chain
• Contain single bond, no double bond
• General formula: CH3-(CH2)n-COOH
Example: acetic acid : CH3-COOH
butyric acid: CH3-(CH2)2-COOH
palmitic acid: CH3-(CH2)14-COOH
stearic acid: CH3-(CH2)16-COOH
Saturated Fatty Acid
 Important metabolic intermediates: Acetic acid & butyric
acid
 Most abundant in body fat: palmitic acid & stearic acid
 Human body fat contains 50% oleic acid, 25% palmitic
acid, 10% linoleic acid & 5% stearic acid
 Carbon atoms of fatty acids are numbered as
C1,C2,….starting from the COOH group
 Starting from the methyl end, the carbon atoms may be
numbered as omega-1,2,3….
Unsaturated Fatty Acid
• contains one or more double bonds
• One double bond = monounsaturated fatty acid
• Two or more double bonds = poly- unsaturated
fatty acid
• Monounsaturated and polyunsaturated fatty
acids don’t stack compactly and are liquid at
room temperature
Example: Oleic acid (C17H33OOH)
Example: Linoleic acid (18:2;9,12)
Linolenic acid (18:3;9,12,15)
Arachidonic acid (20:4;5,8,11,14)
• Omega 3
• Omega 6
• Omega 9
Nomenclature of Unsaturated Fatty Acids
COOH
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Number of Double Bonds
Position of Double Bonds
Carbon Chain Length
18:3 ( 9, 12, 15)
The most commonly occurring fatty acids have even number
of carbon atoms in an un-branched chain of12-24 carbons
General Patterns of Double Bonds
• The most common positions for double bonds are
Δ9, Δ12, and Δ15.
• The double bonds of polyunsaturated fatty acids are
separated by methyl group:
-CH=CH-CH2-CH=CH-
• In almost all the naturally occurring unsaturated
fatty acids, the double bonds are in Cis- configuration
• CIS: hydrogens on the carbons joined by a double
bond are on the same side = the carbon chain is bent
• TRANS: hydrogens on the carbons joined by a
double bond are on the opposite side = the carbon
chain is straighter
Two types of bond formation
Isomerism
Two types of isomers can occur in an unsaturated fatty acid
1. Geometrical isomers: cis and trans
 Cis isomers have a curved configuration.
 Trans isomers have a linear configuration.
 Due to curve configuration cis unsaturated fatty acids have
a lower melting point as compared to there trans
counterpart.
 Most of the natural unsaturated fatty acids have cis double
bonds
Example: Oleic acid & Elaidic acid [ C17H33COOH]
2. Positional isomers:
• variation in the location of the double bond
along the unsaturated fatty acids chain produces
isomer of that compound
• Oleic acid have 15 different positional isomers
The Packing of Fatty Acids
Essential fatty acids
 The fatty acids that can not be synthesized by the
body, & therefore, should be supplied in the diet
is known as essential fatty acids
 Chemically, they are polyunsaturated
 Example:
- Linoleic acid (18:2,9,12)
- Linolenic acid (18:3,9,12,15)
- Arachidonic acid (20:4,5,8,11,14)
Function of EFA
 Structural elements of tissue and gonads
 Synthesis of prostaglandins and other compounds
 Structural components of mitochondrial membrane
 Effect on clotting time
 Effect on fibrinolytic activity
 Role of EFA in fatty liver
 Role in vision
Properties of fatty acids
1. Hydrogenation
2. Halogenation
3. Melting point
4. Salt formation
5. Ester formation
6. Oxidation of fatty acids
Hydrogenation
• Unsaturated fatty acids may be converted to the
corresponding saturated fatty acids by
hydrogenation of double bonds
• Eg:
Linolenic Lenoleic Oleic stearic
• Hydrogenation of oils can lead to solidification and
saturation eg: Vanaspathi
+2H +2H +2H
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
• Eg:
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.
Melting point
• The short and medium chain fatty acids are liquids
where as long chain fatty acids are solids at 25oC
• The solubility in water decreases, while melting and
boiling points increase, with increase in chain
length
• The unsaturtaed fatty acids have lower melting
point compared with saturated fatty acids with the
same chain length
• Eg: stearic acid (C18, no double bond) has the
melting pont 69oC
- Oleic acid (c18, 1 double bond) has 13oC
- Lenoleic (C18, 2 double bond) has -5oC
- Lenolenic (C18, 3 double bond) has -10oC
Salt formation
• Saturated and unsaturated fatty acids form salts
with alkali
• Sodium and potassium salts of long chain fatty acids
are called soaps
• Calcium and magnesium soaps are insoluble and
Calcium soaps are used in grease
• Akyl sulfonate and akyl sulfate are used as
detergents
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
Oxidation of fatty acids
• All the 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
Composition of oils & fats
Name Saturated fatty acids (%) MUFA (%) PUFA (%)
Coconut oil 86 12 2
Groundnut oil 18 46 36
Sunflower oil 12 24 64
Safflower oil 9 12 79
Butter 75 20 5
Mustard oil 34 48 18
Cotton seed oil 26 19 55
Fish oil 30 13 57
Pig 42 46 12
Chemistry of lipid-I.ppt

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Chemistry of lipid-I.ppt

  • 1. CHEMISTRY OF LIPID-I (Introduction, fatty acids) Naval Kishor Yadav Asst. professor Department of biochemistry MCOMS, Pokhara
  • 2. Lipids • Heterogenous group of organic molecules including fats, oils, steroids and related compounds which are relatively insoluble in water and soluble in organic solvents such as ether, chloroform, benzene, acetone etc.
  • 3. Bloor’s Criteria Lipids are compounds having the following characteristics:  Insoluble in water  Solubility in one or more organic solvents, such as ether, chloroform, benzene, acetone etc.  Some relationship to the fatty acids as esters either actual or potential  Possibility of utilization by living organisms
  • 4. Classification Simple lipids Compound lipids Derived lipids Miscellaneous Waxes Fat & Oils (Triacyglycerols) Phospholipids Glycolipids Lipoproteins Other complex lipids Fatty acids Alcohols Mono & Diacylglycerols Carotenoids Squalene Hydrocarbons Lipids
  • 5. Simple lipids Esters of fatty acids with various alcohols • Fats and oils : Esters of fatty acids with glycerol Oil is a liquid while fat is a solid at room temp
  • 6. Waxes: • Esters of fatty acids (usually long chain) with alcohols other than glycerol. • Example: Cetyl alcohol : is a fatty alcohol with the formula CH3(CH2)15OH
  • 7. Complex lipids Esters of fatty acids with alcohols containing additional groups such as phosphate, nitrogenous base carbohydrate, protein i. Phospholipids : Lipids containing, in addition to fatty acids and an alcohol, a phosphoric acid residue. Usually have nitrogen containing bases and other substituents, Examples: a. glycerophospholipids : the alcohol is glycerol eg; lecithin, cephalin and b. sphingophospholipids: the alcohol is sphingosine eg; sphingomyelin
  • 8. II) Glycolipids (glycosphingolipids) : Lipids containing a fatty acid, sphingosine, and carbohydrate Example: Cerebrosides, Gangliosides III) Other complex lipids: Lipids such as sulfolipids , lipopolysaccharides , aminolipids, Lipoproteins
  • 9. Precursor and derived lipids: • Include - fatty acids, glycerol, steroids, other alcohols, fatty aldehydes, and ketone bodies, hydrocarbons, lipid-soluble vitamins, and hormones • Acylglycerols (glycerides), cholesterol, and cholesteryl esters are uncharged, so they are termed as neutral lipids
  • 10. Function of lipids  Storage form of energy (Triacylglycerol)  Constituents of membrane structure and regulate the membrane permeability (phospholipids and cholesterol)  Are important as cellular metabolic regulators (steroid hormones and prostaglandins)  Act as surfactants, detergents & emulsifying agents
  • 11. • Provide insulation against changes in external temperature • Protect the internal organs, serve as insulating materials and give shape and smooth appearance to the body • Help in absorption of fat soluble vitamins.
  • 12. • Improve taste & palatability of food • Lipoproteins, which are complexes of lipids and proteins are involved in the transport of lipids in the blood and are also components of cell membrane • Lipids present in myelinated nerves act as insulators for propagation of depolarization wave
  • 13. • A knowledge of lipid biochemistry is important in understanding many current biomedical areas of interest, eg; – obesity – Atherosclerosis – Myocardial infarction (heart attack) – role of various polyunsaturated fatty acids in nutrition and health
  • 14. Fatty Acids  Aliphatic carboxylic acids,  General formula, R-CO-OH  Depending on the R group (hydrocarbon chain), the physical properties of fatty acid may vary  Occurrence: esterified & free (unesterified) form  Animal origin are much simpler in structure in contrast of plant origin which often contain groups like keto, hydroxy, cyclopentane rings
  • 15. Classification of fatty acids I. Depending on total number of carbon atoms 1. Even chain fatty acids:  having carbon atoms 2,4,6 & series Example: Acetic acid (CH3COOH) Butyric acid (C3H7COOH) Caproic acid (C5H11COOH) Palmitic acid (C15H31COOH) 2. Odd chain fatty acids:  having carbon atoms 3,5,7 etc  Seen in microbial cell walls & also present in milk Example: Propanoic (C2H5COOH)
  • 16. II. Depending on the length of hydrocarbon chain • Short chain = 2-6 carbons • Medium chain = 8-14 carbons • Long chain = 16-22 carbons, • Very long chain fatty acids: 24 & above carbons
  • 17.  Saturated fatty acids  Unsaturated fatty acids  Branched chain fatty acids (e.g. isovaleric acid)  Hydroxy fatty acids (e.g. cerebronic acid) III. Depending on the nature of hydrocarbon chain
  • 18. • Contain single bond, no double bond • General formula: CH3-(CH2)n-COOH Example: acetic acid : CH3-COOH butyric acid: CH3-(CH2)2-COOH palmitic acid: CH3-(CH2)14-COOH stearic acid: CH3-(CH2)16-COOH Saturated Fatty Acid
  • 19.  Important metabolic intermediates: Acetic acid & butyric acid  Most abundant in body fat: palmitic acid & stearic acid  Human body fat contains 50% oleic acid, 25% palmitic acid, 10% linoleic acid & 5% stearic acid  Carbon atoms of fatty acids are numbered as C1,C2,….starting from the COOH group  Starting from the methyl end, the carbon atoms may be numbered as omega-1,2,3….
  • 20. Unsaturated Fatty Acid • contains one or more double bonds • One double bond = monounsaturated fatty acid • Two or more double bonds = poly- unsaturated fatty acid • Monounsaturated and polyunsaturated fatty acids don’t stack compactly and are liquid at room temperature
  • 21. Example: Oleic acid (C17H33OOH) Example: Linoleic acid (18:2;9,12) Linolenic acid (18:3;9,12,15) Arachidonic acid (20:4;5,8,11,14)
  • 22. • Omega 3 • Omega 6 • Omega 9
  • 23. Nomenclature of Unsaturated Fatty Acids COOH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Number of Double Bonds Position of Double Bonds Carbon Chain Length 18:3 ( 9, 12, 15) The most commonly occurring fatty acids have even number of carbon atoms in an un-branched chain of12-24 carbons
  • 24. General Patterns of Double Bonds • The most common positions for double bonds are Δ9, Δ12, and Δ15. • The double bonds of polyunsaturated fatty acids are separated by methyl group: -CH=CH-CH2-CH=CH- • In almost all the naturally occurring unsaturated fatty acids, the double bonds are in Cis- configuration
  • 25. • CIS: hydrogens on the carbons joined by a double bond are on the same side = the carbon chain is bent • TRANS: hydrogens on the carbons joined by a double bond are on the opposite side = the carbon chain is straighter Two types of bond formation
  • 26. Isomerism Two types of isomers can occur in an unsaturated fatty acid 1. Geometrical isomers: cis and trans  Cis isomers have a curved configuration.  Trans isomers have a linear configuration.  Due to curve configuration cis unsaturated fatty acids have a lower melting point as compared to there trans counterpart.  Most of the natural unsaturated fatty acids have cis double bonds Example: Oleic acid & Elaidic acid [ C17H33COOH]
  • 27. 2. Positional isomers: • variation in the location of the double bond along the unsaturated fatty acids chain produces isomer of that compound • Oleic acid have 15 different positional isomers
  • 28. The Packing of Fatty Acids
  • 29. Essential fatty acids  The fatty acids that can not be synthesized by the body, & therefore, should be supplied in the diet is known as essential fatty acids  Chemically, they are polyunsaturated  Example: - Linoleic acid (18:2,9,12) - Linolenic acid (18:3,9,12,15) - Arachidonic acid (20:4,5,8,11,14)
  • 30. Function of EFA  Structural elements of tissue and gonads  Synthesis of prostaglandins and other compounds  Structural components of mitochondrial membrane  Effect on clotting time  Effect on fibrinolytic activity  Role of EFA in fatty liver  Role in vision
  • 31. Properties of fatty acids 1. Hydrogenation 2. Halogenation 3. Melting point 4. Salt formation 5. Ester formation 6. Oxidation of fatty acids
  • 32. Hydrogenation • Unsaturated fatty acids may be converted to the corresponding saturated fatty acids by hydrogenation of double bonds • Eg: Linolenic Lenoleic Oleic stearic • Hydrogenation of oils can lead to solidification and saturation eg: Vanaspathi +2H +2H +2H
  • 33. 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 • Eg: 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.
  • 34. Melting point • The short and medium chain fatty acids are liquids where as long chain fatty acids are solids at 25oC • The solubility in water decreases, while melting and boiling points increase, with increase in chain length • The unsaturtaed fatty acids have lower melting point compared with saturated fatty acids with the same chain length • Eg: stearic acid (C18, no double bond) has the melting pont 69oC - Oleic acid (c18, 1 double bond) has 13oC - Lenoleic (C18, 2 double bond) has -5oC - Lenolenic (C18, 3 double bond) has -10oC
  • 35. Salt formation • Saturated and unsaturated fatty acids form salts with alkali • Sodium and potassium salts of long chain fatty acids are called soaps • Calcium and magnesium soaps are insoluble and Calcium soaps are used in grease • Akyl sulfonate and akyl sulfate are used as detergents
  • 36. 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
  • 37. Oxidation of fatty acids • All the 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
  • 38. Composition of oils & fats Name Saturated fatty acids (%) MUFA (%) PUFA (%) Coconut oil 86 12 2 Groundnut oil 18 46 36 Sunflower oil 12 24 64 Safflower oil 9 12 79 Butter 75 20 5 Mustard oil 34 48 18 Cotton seed oil 26 19 55 Fish oil 30 13 57 Pig 42 46 12

Editor's Notes

  1. Sphingosine (2-amino-4-trans-octadecene-1,3-diol) is an 18-carbon amino alcohol with an unsaturated hydrocarbon chain, which forms a primary part of sphingolipids, a class of cell membrane lipids that include sphingomyelin, an important phospholipid.