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Lipids are a class of heterogenous compounds which are
  relatively insoluble in water and soluble in nonpolar
  solvents.




   Chemically: either esters of fatty acids
                or substances capable of forming such
                esters
BIOMEDICAL IMPORTANCE

1. Stored as a source of energy in the body.




                                           Lipid (TGL)
                                           Droplets In
                                           Adipose tissue
2. Structural components of biomembranes.
3. Thermal Insulator :
   Provides insulation against changes in external
   temperature.
4. Lipids act as electric insulators in neurons.
5. Act as metabolic regulators (steroid hormones and
    prostaglandins).
6. Act as surfactants and prevents collapse of lungs during
   expiration.

7. Lipids are used as detergents.

8. Lipids used in emulsification and intestinal absorption of
   non polar nutrients like fatty acids and fat soluble
   vitamins.
9. Associated with diseases such as atherosclerosis,
   diabetes mellitus and obesity.

10. Gives shape and contour to the body.
LIPIDS




1. Simple   2. Compound Lipids   3. Derived Lipids
Lipids
1. Simple Lipids
Esters of fatty acids with various alcohols.
     a. Fats :esters of fatty acids with glycerol.
      eg: triglycerides.
     b. Waxes: esters of fatty acids with higher
        molecular weight monohydric alcohols.
      eg: beeswax




  Glycerol
2. Compound
                      Lipids
Esters of fatty acids with various alcohols along
with an additional group.
  Simple lipid + Additional group = Compound Lipids



 a. Phospholipids:
 b. Glycolipids:
 c. Other Complex Lipids:
COMPOUND LIPIDS
Esters of fatty acids with various alcohols along
With an additional group.




   Phospholipids                     Glycolipids    Others
Glycerphospholipids
     -Phosphatidyl choline           Cerebrosides   Lipoproteins
       - Phosphatidyl ethanolamine
                                     Gangliosides   Aminolipids
       - Phosphatidyl serine
       - Phosphatidyl inositol       Globosides
       - Cardiolipin
       - Plasmalogens
Sphingophospholipids
3. Derived Lipids
Lipid molecules derived from simple/compound lipids
on their hydrolysis
       Fatty acids
      Eicosanoides
      Steroids
      Sterols
      Cholesterol
      Bile acids
      Vitamins (A,D,E,K)
      Ketone Bodies
SIMPLE LIPIDS


NAME    ALCOHOL       ACID         EXAMPLE

Fats    Glycerol      Fatty acid   Triglycerides


Waxes   Aliphatic /   Fatty acid   Bees wax
        Aromatic
        alcohol
Phospho lipids
NAME           ALCOHOL    ACID                Po4   ADDITIONAL
                                                    GROUP
GLYCERO PHOSPHO LIPIDS
Phosphatidyl   Glycerol   Fatty acid          Po4   Choline
choline
(lecithin)
Phosphatidyl   Glycerol   Fatty acid          PO4   Ethanolamine
ethanolamine
(cephalin)
Phosphatidyl   Glycerol   Fatty acid          PO4   Serine
serine
Phosphatidyl   Glycerol   Fatty acid          PO4   Myoinositol
inositol
Cardiolipin    Glycerol   Fatty acid          PO4   Phosphatidyl
                                                    glycerol
Plasmologens   Glycerol   Fatty acid (ether   PO4   Ethanolamine
                          link at C1)
SPHINGO PHOSPHO LIPIDS
Glycolipids
 NAME           ALCOHOL       ACID          GLYCOSYL       ADDITIONAL
                                            RESIDUE        GROUP
 Cerebrosides   Sphingosine   Fatty acid    Galactose/
                              (cerebronic   Glucose
                              acid)
 Gangliosides   Sphingosine   Fatty acid    Glucose        Sialic acid

 Globosides     Sphingosine   Fatty acid    Glucose +
                                            Galactose
 Sulphatides    Sphingosine   Fatty acid    Galactose      SO3


Note:
Ceramide: Sphingosine + Fatty acid                       Slide 51
CLASSIFICATION OF FATTY ACIDS

Based on ‘R’ group
     1. Small / Medium / Long Chain Fatty Acids

     2. Odd / Even Chain Fatty Acids
      3. Saturated / Unsaturated Fatty Acids

Nutritionally
      Essential / Non-Essential Fatty Acids
1. Small / Medium / Long Chain Fatty Acids


Small chain Fatty acids        : 2 – 4 carbons
  Medium chain Fatty acids   : 6 – 14 carbons
  Long chain Fatty acids     : more than 16 carbons
2. Odd / Even Chain Fatty Acids


 12    11    10    9       8       7       6       5       4       3       2       1




13    12    11    10   9       8       7       6       5       4       3       2       1
Saturated Fatty Acids
 a)    Even chain fatty acid
          eg.,   Palmitic acid
                 Stearic acid
 a)    Odd chain fatty acid
       eg., Propionic acid
Unsaturated Fatty Acids
a)    Mono unsaturated fatty acid (MUFA)
      eg., Oleic acid
b)    Poly unsaturated fatty acid (PUFA)
      eg., Linoleic acid, Linoleinic acid, Arachidonic acid
a)    Eicosanoids
USES / FUNCTIONS OF PUFA

 Major components of membrane lipids
 Contributes to the fluidity of membranes
 Used for Prostaglandin synthesis
 Decreases the incidence of Atherosclerosis,
Coronary Artery Diseases
Saturated fatty acids: rich in storage lipids (adipose tissue)




Unsaturated fatty acids: rich in membrane lipids
(to increase fluidity)
Based on Nutrition

      Essential
     Non essential
Essential Fatty Acids

Fatty acids that can not be synthesized by body & has to
be supplied by diet

Ex:   Linoleic acid
      Linolenic acid
      Arachidonic acid

Functions:
      Structural composition of Brain & Nervous system
      Precursor for Eicosanoid synthesis
      Prevents atherosclerosis
      Prevents skin lesions
12   11   10   9   8     7   6   5   4   3   2   1


ω                            ε   δ   γ   β   α

     Two types
           1. ω – type
           2. N - type
Indicating Number & Position of Double Bond




        18:1,9

        Δ9 18:1
                              ω3, ω6, ω9
                              Fatty Acids
       ω9,C18:1
Melting Point :
• Temperature at which fats are converted from solid
   state to liquid state.
• Saturated acids have high melting point than
   unsaturated acids
• Increases with increase in hydrocarbon chain length

Solubility:
     Decreases with increasing chain length
     Increases with temperature.
Unsaturated fatty acids exhibit cis-trans isomerism
GEOMETRIC ISOMERISM OF OLEIC AND ELAIDIC ACIDS




                       Natural Fatty acids – ‘cis’ form
1.   Salt Formation
2.   Esterification
3.   Hydrogenation
4.   Halogenation
5.   Hydrolysis
6.   Oxidation
1. SALT FORMATION


R – COOH + NaCl                  R – COONa + HCl


Fatty acids react with alkalies to form Salts of fatty acids
Na+ or K+ salts of fatty acids : Soaps
2. ESTERIFICATION



         +                                         +




Most of the fatty acids of body are in esterified form
3. HYDROGENATION
                  (hardening)
        CH3 – CH2 – CH – CH – CH2 – COOH
                       –
                               H2

        CH3 – CH2 – CH2 – CH2 – CH2 – COOH


Unsaturated FA converted to Saturated FA
Used to synthesize Vanaspathi & Margaraine
Trans Fatty acids are formed
4. HALOGENATION

         CH3 – CH2 – CH – CH – CH2 – COOH
                        –

                           I2

         CH3 – CH2 – CH – CH – CH2 – COOH
                     I     I

The amount of halogen taken by a fatty acid depends on
                         No of double bonds
                         Degree of unsaturation
TAG undergoes stepwise hydrolysis of its ester bonds to
form Glycerol & Free Fatty acids



                       Lipases




Digestion of Fats in GIT
Mobilisation of TGL from Adipose tissue
GLYCERO PHOSPHOLIPIDS




            Phosphatidic Acid
Choline
    Phosphatidyl
Phosphatidic acid
                    Ethanolamine


                       Serine


                      Inositol


                    Phosphatidyl
                    Glycerol
Plasmalogens
Phosphatidyl Choline (LECITHIN)



                                   Choline




Phosphatidic acid + Choline
Lecithin acts as lung surfactant
Most abundant phospholipid of biomembranes
Phosphatidyl Choline (LECITHIN)


 Dipalmitoyl Lecithin – Lung surfactant.

Synthesized by Alveolar type - II cells.

 Rich in alveolar fluid lining the alveoli

Reduces surface tension of alveolar fluid & prevents collapse
during expiration

Deficiency in premature infants leads to collapse
                             – Respiratory Distress syndrome
SITE OF ACTION OF PHOSPHOLIPASES

                   Phospholipase A1

Phospholipase A2

                                      Phospholipase D




               Phospholipase C
SPHINGO PHOSPHOLIPIDS


   Sphingosine – alcohol moiety
   Commonly found in nerve tissues
SPHINGOPHOSPHOLIPIDS Sphingomyelin




                      Sphingomyelin
SPHINGOPHOSPHOLIPIDS
1.   Structural components of cell membrane.
2.   Enable enzyme action.(mitochondrial enzyme
     system).
3.   Required for blood coagulation (prothrombin to
     thrombin, activation of factor 8 by factor 9).
4.   Transports lipids from intestine and liver.
5.   Choline acts as a lipotropic agent since it prevents
     the formation of fatty liver.
6.   Phospholipids of myelin sheath provides insulation
     around nerve fibers.
COMPOUND LIPIDS
Esters of fatty acids with various alcohols along
With an additional group.




   Phospholipids       Glycolipids     Others

Glycerphospholipids    Cerebrosides    Aminolipids
Sphingophospholipids   Gangliosides    Lipoproteins
                       Sulfatides
                       Globosides
o   Lipids containing carbohydrate moiety - Glycolipids
o   Alcoholic component – Sphingosine
o   Ceramide – Common group of all Glycolipids
o   Occur in brain, spinal cords and other tissues.
o   Predominant in outer leaflet of biomembranes
GANGLIOSIDES        (Ceramide + Oligosaccharide + Sialic acid)



   GM1 = Ganglioside with monosialic acid

   GD2 = Ganglioside with two sialic acid residues


   GT3 = Ganglioside with three sialic acid residues



Sialic acid = N-Acetyl Neuraminic acid (NANA)
1. Cerebrosides




              2. Sulfatides

 Types of
Glycolipids
              3. Globosides




              4. Gangliosides
STEROIDS
Lipids containing Cyclo Pentano Perhydro Phenanthrene
(CPPP) ring
                                      18
                                12         17

                          11                    16
                                     13

                                C          D
             1    19

                            9         14        15
       2
                 10              8

             A             B
       3                         7
                      5

             4             6
STEROLS

Steroids containing alcoholic group - Sterols
Plant Sterols : Ergosterol, Stigmasterol, Sitosterol
Animal Sterols : Cholesterol
CHOLESTEROL
Chemistry:
 Has Steroid Nucleus

 OH group at 3rd position

 Double bond between 5th & 6th carbons

 8-Carbon containing side chain at 17th position.




                                    17




                  3    5

                           6
CHOLESTEROL
Chemical Properties
  1. Undergoes rapid oxidation to form cholestenones.
  2. Hydroxyl group forms esters with acids to form
     Cholesterol Esters (cholesterol acetate,palmitate
     and propionates)
  3. Presence of double bond gives hydrogenation
     reactions (similar to unsaturated fatty acids).
  4. Colour reactions:
       LIEBERMANN BURCHARD,
       SALKOWSKY,
       ZAKS.
CHOLESTEROL

Biomedical Importance
Structural role – Biomembranes, Lipoproteins
Occur in large amounts in brain and nerve tissues.
Act as insulator against nerve impulses which discharge
 electric charges.
Biomolecules synthesized from cholesterol
            Bile acids
            Vitamin D
            Steroid hormones :
                  Androgens, Estrogens, Progesterone,
                  Aldosterone etc
BILE ACIDS


   Cholesterol is eliminated from the body as bile
    acids through bile.
   Help in digestion & absorption of fats and fat
    soluble vitamins
   Synthesised in liver, stored in gall bladder and act
    in intestine
BILE ACIDS



     Primary Bile Acids           Secondary Bile Acids

Synthesised from Cholesterol   Synthesised from primary
in Hepatocytes                 Bile acids in Intestine
Ex:                            Ex:
Cholic acid                    Deoxycholic acid
Chenodeoxycholic acid          Lithocholic acid
EICOSANOIDES

20 CARBON CONTAINING FATTY ACIDS GENERATED FROM
ARACHIDONIC ACID

    • Discovered in prostate gland secretions
    • Synthesized in all tissues
    • Acts as local hormones
    • Function in even low concentrations
EICOSANOIDES
         COX            LOX




Prostanoides     Leukotrienes   Lipoxins

Prostaglandins
Thromboxanes
Prostacyclins
Prostaglandin

           O




        OH

Protanoic acid – Precursor molecule
Cyclopentane ring substituted with hydroxyl / keto groups
Based on difference in these substituted groups, PGs classified as
      PG-A, PG-B, PG-C, PG-D, PG-E, PG-F, PG-H
Based on number of double bonds, PGs have three series
      PG1 – One double bond
      PG2 – 2 double bonds        PG2 - most common series
      PG3 – 3 double bonds
Functions of prostaglandin
   Smooth muscle contraction/relaxation
     Vaso constriction
     Broncho dilation (PGE2)

       Uterine contraction (PGF2)


   Capillary permeability
   Inflammation and pain
   Platelet aggregation
Thromboxanes




Unsaturated, substituted C-20 fatty acids with an oxane
ring.
Occur in the cells of many tissues like blood platelets,
lung, brain etc.
PGI2 Vs TXA2
Prostacyclin (PGI2)             Thromboxane (TXA2)

Produced mainly from            Produced mainly from
vascular endothelium            platelets

Smooth muscle relaxation        Smooth muscle contraction

Inhibits platelet aggregation   Stimulates platelet
                                aggregation
Leukotrienes, Lipoxins
Lipids having both hydrophobic and hydrophilic groups

Ex:

  Phospholipids
  Cholesterol
  Glycolipids
Lipid Aggregates in Aqueous
        Compartment
       Micelle Formation
Bilayer Formation
Liposome Formation




Prepared by sonication of amphipathic lipids
Liposomes
   Liposomes (microscopic spherical vesicles) when
    mixed with water under special condition, the
    phospholipids arrange themselves to form a bilayer
    membrane enclosing water-filled central core

   Impermeable to polar materials and helps maintain
    the composition of the enclosed aqueous fluid.
Uses of Liposomes

  To deliver
         drugs
         proteins
         enzymes
         genes
Drug release
Are spherical complexes made up of lipids and
proteins .
STRUCTURE



     Inner Core                   Outer Wall

  Nonpolar lipids         Amphipathic lipids & Proteins.



TAG, Cholesterol esters    Phospholipids, Cholesterol
Lipoproteins = lipids + proteins


                    Apoproteins

                          Al All Alll
                          B48 B100
                          Cl Cll
                          D
                          E
Functions of Apoproteins:
 1. Act as structural components of lipoproteins.
 2. Recognize the cell membrane surface receptors,.
 3. Activate enzymes involved in lipoprotein
    metabolism .
TYPES OF LIPOPROTEINS

         Based on density (lipid:protein ratio)


1. Chylomicrons

2 . Very Low Density Lipoproteins (VLDL)

3 . Low Density Lipoproteins (LDL)

4 . High Density Lipoproteins (HDL)
Ultracentrifugation   Electrophoresis
Ultracentrifugation




                      Chylomicrons
                      VLDL
                      IDL
                      LDL
                      HDL
Electrophoresis
     +ve          +ve

                        α -lipoprotein
                        HDL
                        VLDL Pre β
                        IDL

                        LDL     β Lp

                        Chylomicron


     -ve          -ve
Lipoprotein   Apo lipoprotein                       Functions
                                                    (trnspt Chol.,)
Chylomicron   Apo AI, AI, B48, CI, CII, CIII, E     Intestine to
                                                    tissue
VLDL                       B100, CI, CII, CIII, E   Liver to tissue
LDL                        B100                     Liver to tissue
IDL                        B100                     Liver to tissue


HDL           Apo AI, AII, AIV, CI, CII, CIII, E    Tissue to liver
RANCIDITY OF FATS

Formation of unpleasant odour and taste in stored lipids is
called as Rancidity.

• Denotes the deterioration of lipids & becomes unsuitable
  for consumption
• Occurs when exposed to air, moisture or bacteria

• TGL with unsaturated fatty acids more susceptible for
  rancidity
Types of Rancidity

1. Hydrolytic Rancidity:
   Partial hydrolysis of TGL by the bacterial enzymes

  2. Oxidative Rancidity:
     Partial oxidation of fats leading to formation of peroxides &
     their corresponding aldehydes


    Prevented by adding Anti-oxidants
LIPID PEROXIDATION

          Free Radicals
 Lipids                   Lipid peroxides + Free Radicals
                O2


Lipid peroxidation - generates of free radicals
                     (ROO*,RO*,OH*)
Free radicals : Have unpaired electrons in their outer orbits
                They oxidize & damage any biomolecules

Peroxidation : damages tissues in vivo,
(free radicals) causes of cancer, Inflammatory diseases,
                atherosclerosis, and aging etc.
Three Stages of Peroxidation
 1. Initiation


2. Propagation




3. Termination
   Substances which control and prevent free radicals.
Types
1. Preventive Antioxidants:
      Decrease the rate of chain initiation step.
      Ex: Catalase, Metal ion chelators such as EDTA
2. Chain Breaking Antioxidants:
     Interfere with chain propagation step.
     Ex : Superoxide dismutase(SOD), Vitamin E
Uses
     Protects biomembrane from the effect of free radicals
     Added in fats for storage purpose
     Protects the body from multiple diseases
Tests to check the purity of Simple Lipids

1.   Iodine Number
2.   Saponification Number
3.   Reichert Miesel Number
4.   Acid Number
5.   Acetyl number
Defined as the number of grams of iodine taken up
by 100gms of fat.


Index of degree of unsaturation
Iodine Number        degree of unsaturation
                ‫ﻌ‬


Uses:
        To detect the degree of unsaturation
        To detect adulteration
IODINE NUMBER


   Fats / Oils    Iodine No
Coconut oil         7-10
Butter              25-28
Groundnut oil      85-100
Sunflower oil      125-135
SAPONIFICATION NUMBER

Defined as the number of milligrams (mgs) of potassium
Hydroxide (KOH) required to saponify one gram of fat.


Index of molecular weight / chain length fatty acids
                                        1
Saponification Number  ‫ﻌ‬
                           molecular weight (or) chain length


Uses:
        To detect molecular weight / chain length fatty acids
        To detect adulteration
ACETYL NUMBER

Defined as the Milligrams of KOH required to combine
with the acetic acid liberated by the saponification of
1 gm of acetylated fat.

 Indicator of number of hydroxyl groups

 Castor oil has acetyl value of 146 to 150 indicating the
 presence of sufficient hydroxylated acids.

 Butter has an acetyl value of 1.9 to 8.6 ,indicating the
 presence of very small amounts of hydroxylated acids.
REICHERT-MEISSL NUMBER

Defined as the millimeters of 0.1N alkali required to
neutralize the volatile acids obtained from 5 gm of fat .


  Butter fat has a Reichert-Meissl number of 26-33
  whereas the number for lard is 0.6.
ACID NUMBER

Defined as the Milligrams of KOH required to neutralize
the free fatty acids present in 1gm of fat.


 It is of value in determining rancidity due to
 free fatty acids.
Lipids chemistry reference

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Lipids chemistry reference

  • 1.
  • 2. Lipids are a class of heterogenous compounds which are relatively insoluble in water and soluble in nonpolar solvents.  Chemically: either esters of fatty acids or substances capable of forming such esters
  • 3. BIOMEDICAL IMPORTANCE 1. Stored as a source of energy in the body. Lipid (TGL) Droplets In Adipose tissue
  • 4. 2. Structural components of biomembranes.
  • 5. 3. Thermal Insulator : Provides insulation against changes in external temperature.
  • 6. 4. Lipids act as electric insulators in neurons.
  • 7. 5. Act as metabolic regulators (steroid hormones and prostaglandins). 6. Act as surfactants and prevents collapse of lungs during expiration. 7. Lipids are used as detergents. 8. Lipids used in emulsification and intestinal absorption of non polar nutrients like fatty acids and fat soluble vitamins. 9. Associated with diseases such as atherosclerosis, diabetes mellitus and obesity. 10. Gives shape and contour to the body.
  • 8.
  • 9. LIPIDS 1. Simple 2. Compound Lipids 3. Derived Lipids Lipids
  • 10. 1. Simple Lipids Esters of fatty acids with various alcohols. a. Fats :esters of fatty acids with glycerol. eg: triglycerides. b. Waxes: esters of fatty acids with higher molecular weight monohydric alcohols. eg: beeswax Glycerol
  • 11. 2. Compound Lipids Esters of fatty acids with various alcohols along with an additional group. Simple lipid + Additional group = Compound Lipids a. Phospholipids: b. Glycolipids: c. Other Complex Lipids:
  • 12. COMPOUND LIPIDS Esters of fatty acids with various alcohols along With an additional group. Phospholipids Glycolipids Others Glycerphospholipids -Phosphatidyl choline Cerebrosides Lipoproteins - Phosphatidyl ethanolamine Gangliosides Aminolipids - Phosphatidyl serine - Phosphatidyl inositol Globosides - Cardiolipin - Plasmalogens Sphingophospholipids
  • 13. 3. Derived Lipids Lipid molecules derived from simple/compound lipids on their hydrolysis Fatty acids Eicosanoides Steroids Sterols Cholesterol Bile acids Vitamins (A,D,E,K) Ketone Bodies
  • 14. SIMPLE LIPIDS NAME ALCOHOL ACID EXAMPLE Fats Glycerol Fatty acid Triglycerides Waxes Aliphatic / Fatty acid Bees wax Aromatic alcohol
  • 16. NAME ALCOHOL ACID Po4 ADDITIONAL GROUP GLYCERO PHOSPHO LIPIDS Phosphatidyl Glycerol Fatty acid Po4 Choline choline (lecithin) Phosphatidyl Glycerol Fatty acid PO4 Ethanolamine ethanolamine (cephalin) Phosphatidyl Glycerol Fatty acid PO4 Serine serine Phosphatidyl Glycerol Fatty acid PO4 Myoinositol inositol Cardiolipin Glycerol Fatty acid PO4 Phosphatidyl glycerol Plasmologens Glycerol Fatty acid (ether PO4 Ethanolamine link at C1) SPHINGO PHOSPHO LIPIDS
  • 17. Glycolipids NAME ALCOHOL ACID GLYCOSYL ADDITIONAL RESIDUE GROUP Cerebrosides Sphingosine Fatty acid Galactose/ (cerebronic Glucose acid) Gangliosides Sphingosine Fatty acid Glucose Sialic acid Globosides Sphingosine Fatty acid Glucose + Galactose Sulphatides Sphingosine Fatty acid Galactose SO3 Note: Ceramide: Sphingosine + Fatty acid Slide 51
  • 18.
  • 19. CLASSIFICATION OF FATTY ACIDS Based on ‘R’ group 1. Small / Medium / Long Chain Fatty Acids 2. Odd / Even Chain Fatty Acids 3. Saturated / Unsaturated Fatty Acids Nutritionally Essential / Non-Essential Fatty Acids
  • 20. 1. Small / Medium / Long Chain Fatty Acids Small chain Fatty acids : 2 – 4 carbons Medium chain Fatty acids : 6 – 14 carbons Long chain Fatty acids : more than 16 carbons
  • 21. 2. Odd / Even Chain Fatty Acids 12 11 10 9 8 7 6 5 4 3 2 1 13 12 11 10 9 8 7 6 5 4 3 2 1
  • 22. Saturated Fatty Acids a) Even chain fatty acid eg., Palmitic acid Stearic acid a) Odd chain fatty acid eg., Propionic acid Unsaturated Fatty Acids a) Mono unsaturated fatty acid (MUFA) eg., Oleic acid b) Poly unsaturated fatty acid (PUFA) eg., Linoleic acid, Linoleinic acid, Arachidonic acid a) Eicosanoids
  • 23. USES / FUNCTIONS OF PUFA Major components of membrane lipids Contributes to the fluidity of membranes Used for Prostaglandin synthesis Decreases the incidence of Atherosclerosis, Coronary Artery Diseases
  • 24. Saturated fatty acids: rich in storage lipids (adipose tissue) Unsaturated fatty acids: rich in membrane lipids (to increase fluidity)
  • 25. Based on Nutrition Essential Non essential
  • 26. Essential Fatty Acids Fatty acids that can not be synthesized by body & has to be supplied by diet Ex: Linoleic acid Linolenic acid Arachidonic acid Functions: Structural composition of Brain & Nervous system Precursor for Eicosanoid synthesis Prevents atherosclerosis Prevents skin lesions
  • 27.
  • 28. 12 11 10 9 8 7 6 5 4 3 2 1 ω ε δ γ β α Two types 1. ω – type 2. N - type
  • 29. Indicating Number & Position of Double Bond 18:1,9 Δ9 18:1 ω3, ω6, ω9 Fatty Acids ω9,C18:1
  • 30. Melting Point : • Temperature at which fats are converted from solid state to liquid state. • Saturated acids have high melting point than unsaturated acids • Increases with increase in hydrocarbon chain length Solubility: Decreases with increasing chain length Increases with temperature. Unsaturated fatty acids exhibit cis-trans isomerism
  • 31. GEOMETRIC ISOMERISM OF OLEIC AND ELAIDIC ACIDS Natural Fatty acids – ‘cis’ form
  • 32. 1. Salt Formation 2. Esterification 3. Hydrogenation 4. Halogenation 5. Hydrolysis 6. Oxidation
  • 33. 1. SALT FORMATION R – COOH + NaCl R – COONa + HCl Fatty acids react with alkalies to form Salts of fatty acids Na+ or K+ salts of fatty acids : Soaps
  • 34. 2. ESTERIFICATION + + Most of the fatty acids of body are in esterified form
  • 35. 3. HYDROGENATION (hardening) CH3 – CH2 – CH – CH – CH2 – COOH – H2 CH3 – CH2 – CH2 – CH2 – CH2 – COOH Unsaturated FA converted to Saturated FA Used to synthesize Vanaspathi & Margaraine Trans Fatty acids are formed
  • 36. 4. HALOGENATION CH3 – CH2 – CH – CH – CH2 – COOH – I2 CH3 – CH2 – CH – CH – CH2 – COOH I I The amount of halogen taken by a fatty acid depends on No of double bonds Degree of unsaturation
  • 37. TAG undergoes stepwise hydrolysis of its ester bonds to form Glycerol & Free Fatty acids Lipases Digestion of Fats in GIT Mobilisation of TGL from Adipose tissue
  • 38.
  • 39. GLYCERO PHOSPHOLIPIDS Phosphatidic Acid
  • 40. Choline Phosphatidyl Phosphatidic acid Ethanolamine Serine Inositol Phosphatidyl Glycerol
  • 42. Phosphatidyl Choline (LECITHIN) Choline Phosphatidic acid + Choline Lecithin acts as lung surfactant Most abundant phospholipid of biomembranes
  • 43. Phosphatidyl Choline (LECITHIN) Dipalmitoyl Lecithin – Lung surfactant. Synthesized by Alveolar type - II cells. Rich in alveolar fluid lining the alveoli Reduces surface tension of alveolar fluid & prevents collapse during expiration Deficiency in premature infants leads to collapse – Respiratory Distress syndrome
  • 44. SITE OF ACTION OF PHOSPHOLIPASES Phospholipase A1 Phospholipase A2 Phospholipase D Phospholipase C
  • 45. SPHINGO PHOSPHOLIPIDS  Sphingosine – alcohol moiety  Commonly found in nerve tissues
  • 48. 1. Structural components of cell membrane. 2. Enable enzyme action.(mitochondrial enzyme system). 3. Required for blood coagulation (prothrombin to thrombin, activation of factor 8 by factor 9). 4. Transports lipids from intestine and liver. 5. Choline acts as a lipotropic agent since it prevents the formation of fatty liver. 6. Phospholipids of myelin sheath provides insulation around nerve fibers.
  • 49. COMPOUND LIPIDS Esters of fatty acids with various alcohols along With an additional group. Phospholipids Glycolipids Others Glycerphospholipids Cerebrosides Aminolipids Sphingophospholipids Gangliosides Lipoproteins Sulfatides Globosides
  • 50. o Lipids containing carbohydrate moiety - Glycolipids o Alcoholic component – Sphingosine o Ceramide – Common group of all Glycolipids o Occur in brain, spinal cords and other tissues. o Predominant in outer leaflet of biomembranes
  • 51. GANGLIOSIDES (Ceramide + Oligosaccharide + Sialic acid) GM1 = Ganglioside with monosialic acid GD2 = Ganglioside with two sialic acid residues GT3 = Ganglioside with three sialic acid residues Sialic acid = N-Acetyl Neuraminic acid (NANA)
  • 52. 1. Cerebrosides 2. Sulfatides Types of Glycolipids 3. Globosides 4. Gangliosides
  • 53. STEROIDS Lipids containing Cyclo Pentano Perhydro Phenanthrene (CPPP) ring 18 12 17 11 16 13 C D 1 19 9 14 15 2 10 8 A B 3 7 5 4 6
  • 54. STEROLS Steroids containing alcoholic group - Sterols Plant Sterols : Ergosterol, Stigmasterol, Sitosterol Animal Sterols : Cholesterol
  • 55. CHOLESTEROL Chemistry:  Has Steroid Nucleus  OH group at 3rd position  Double bond between 5th & 6th carbons  8-Carbon containing side chain at 17th position. 17 3 5 6
  • 56. CHOLESTEROL Chemical Properties 1. Undergoes rapid oxidation to form cholestenones. 2. Hydroxyl group forms esters with acids to form Cholesterol Esters (cholesterol acetate,palmitate and propionates) 3. Presence of double bond gives hydrogenation reactions (similar to unsaturated fatty acids). 4. Colour reactions: LIEBERMANN BURCHARD, SALKOWSKY, ZAKS.
  • 57. CHOLESTEROL Biomedical Importance Structural role – Biomembranes, Lipoproteins Occur in large amounts in brain and nerve tissues. Act as insulator against nerve impulses which discharge electric charges. Biomolecules synthesized from cholesterol Bile acids Vitamin D Steroid hormones : Androgens, Estrogens, Progesterone, Aldosterone etc
  • 58. BILE ACIDS  Cholesterol is eliminated from the body as bile acids through bile.  Help in digestion & absorption of fats and fat soluble vitamins  Synthesised in liver, stored in gall bladder and act in intestine
  • 59. BILE ACIDS Primary Bile Acids Secondary Bile Acids Synthesised from Cholesterol Synthesised from primary in Hepatocytes Bile acids in Intestine Ex: Ex: Cholic acid Deoxycholic acid Chenodeoxycholic acid Lithocholic acid
  • 60. EICOSANOIDES 20 CARBON CONTAINING FATTY ACIDS GENERATED FROM ARACHIDONIC ACID • Discovered in prostate gland secretions • Synthesized in all tissues • Acts as local hormones • Function in even low concentrations
  • 61. EICOSANOIDES COX LOX Prostanoides Leukotrienes Lipoxins Prostaglandins Thromboxanes Prostacyclins
  • 62. Prostaglandin O OH Protanoic acid – Precursor molecule Cyclopentane ring substituted with hydroxyl / keto groups Based on difference in these substituted groups, PGs classified as PG-A, PG-B, PG-C, PG-D, PG-E, PG-F, PG-H Based on number of double bonds, PGs have three series PG1 – One double bond PG2 – 2 double bonds PG2 - most common series PG3 – 3 double bonds
  • 63. Functions of prostaglandin  Smooth muscle contraction/relaxation  Vaso constriction  Broncho dilation (PGE2)  Uterine contraction (PGF2)  Capillary permeability  Inflammation and pain  Platelet aggregation
  • 64. Thromboxanes Unsaturated, substituted C-20 fatty acids with an oxane ring. Occur in the cells of many tissues like blood platelets, lung, brain etc.
  • 65. PGI2 Vs TXA2 Prostacyclin (PGI2) Thromboxane (TXA2) Produced mainly from Produced mainly from vascular endothelium platelets Smooth muscle relaxation Smooth muscle contraction Inhibits platelet aggregation Stimulates platelet aggregation
  • 67. Lipids having both hydrophobic and hydrophilic groups Ex: Phospholipids Cholesterol Glycolipids
  • 68. Lipid Aggregates in Aqueous Compartment Micelle Formation
  • 70. Liposome Formation Prepared by sonication of amphipathic lipids
  • 71. Liposomes  Liposomes (microscopic spherical vesicles) when mixed with water under special condition, the phospholipids arrange themselves to form a bilayer membrane enclosing water-filled central core  Impermeable to polar materials and helps maintain the composition of the enclosed aqueous fluid.
  • 72. Uses of Liposomes To deliver drugs proteins enzymes genes
  • 74. Are spherical complexes made up of lipids and proteins .
  • 75. STRUCTURE Inner Core Outer Wall Nonpolar lipids Amphipathic lipids & Proteins. TAG, Cholesterol esters Phospholipids, Cholesterol
  • 76.
  • 77. Lipoproteins = lipids + proteins Apoproteins Al All Alll B48 B100 Cl Cll D E
  • 78. Functions of Apoproteins: 1. Act as structural components of lipoproteins. 2. Recognize the cell membrane surface receptors,. 3. Activate enzymes involved in lipoprotein metabolism .
  • 79. TYPES OF LIPOPROTEINS Based on density (lipid:protein ratio) 1. Chylomicrons 2 . Very Low Density Lipoproteins (VLDL) 3 . Low Density Lipoproteins (LDL) 4 . High Density Lipoproteins (HDL)
  • 80. Ultracentrifugation Electrophoresis
  • 81. Ultracentrifugation Chylomicrons VLDL IDL LDL HDL
  • 82. Electrophoresis +ve +ve α -lipoprotein HDL VLDL Pre β IDL LDL β Lp Chylomicron -ve -ve
  • 83.
  • 84. Lipoprotein Apo lipoprotein Functions (trnspt Chol.,) Chylomicron Apo AI, AI, B48, CI, CII, CIII, E Intestine to tissue VLDL B100, CI, CII, CIII, E Liver to tissue LDL B100 Liver to tissue IDL B100 Liver to tissue HDL Apo AI, AII, AIV, CI, CII, CIII, E Tissue to liver
  • 85. RANCIDITY OF FATS Formation of unpleasant odour and taste in stored lipids is called as Rancidity. • Denotes the deterioration of lipids & becomes unsuitable for consumption • Occurs when exposed to air, moisture or bacteria • TGL with unsaturated fatty acids more susceptible for rancidity
  • 86. Types of Rancidity 1. Hydrolytic Rancidity: Partial hydrolysis of TGL by the bacterial enzymes 2. Oxidative Rancidity: Partial oxidation of fats leading to formation of peroxides & their corresponding aldehydes Prevented by adding Anti-oxidants
  • 87. LIPID PEROXIDATION Free Radicals Lipids Lipid peroxides + Free Radicals O2 Lipid peroxidation - generates of free radicals (ROO*,RO*,OH*) Free radicals : Have unpaired electrons in their outer orbits They oxidize & damage any biomolecules Peroxidation : damages tissues in vivo, (free radicals) causes of cancer, Inflammatory diseases, atherosclerosis, and aging etc.
  • 88. Three Stages of Peroxidation 1. Initiation 2. Propagation 3. Termination
  • 89. Substances which control and prevent free radicals. Types 1. Preventive Antioxidants: Decrease the rate of chain initiation step. Ex: Catalase, Metal ion chelators such as EDTA 2. Chain Breaking Antioxidants: Interfere with chain propagation step. Ex : Superoxide dismutase(SOD), Vitamin E Uses  Protects biomembrane from the effect of free radicals  Added in fats for storage purpose  Protects the body from multiple diseases
  • 90. Tests to check the purity of Simple Lipids 1. Iodine Number 2. Saponification Number 3. Reichert Miesel Number 4. Acid Number 5. Acetyl number
  • 91. Defined as the number of grams of iodine taken up by 100gms of fat. Index of degree of unsaturation Iodine Number degree of unsaturation ‫ﻌ‬ Uses: To detect the degree of unsaturation To detect adulteration
  • 92. IODINE NUMBER Fats / Oils Iodine No Coconut oil 7-10 Butter 25-28 Groundnut oil 85-100 Sunflower oil 125-135
  • 93. SAPONIFICATION NUMBER Defined as the number of milligrams (mgs) of potassium Hydroxide (KOH) required to saponify one gram of fat. Index of molecular weight / chain length fatty acids 1 Saponification Number ‫ﻌ‬ molecular weight (or) chain length Uses: To detect molecular weight / chain length fatty acids To detect adulteration
  • 94. ACETYL NUMBER Defined as the Milligrams of KOH required to combine with the acetic acid liberated by the saponification of 1 gm of acetylated fat. Indicator of number of hydroxyl groups Castor oil has acetyl value of 146 to 150 indicating the presence of sufficient hydroxylated acids. Butter has an acetyl value of 1.9 to 8.6 ,indicating the presence of very small amounts of hydroxylated acids.
  • 95. REICHERT-MEISSL NUMBER Defined as the millimeters of 0.1N alkali required to neutralize the volatile acids obtained from 5 gm of fat . Butter fat has a Reichert-Meissl number of 26-33 whereas the number for lard is 0.6.
  • 96. ACID NUMBER Defined as the Milligrams of KOH required to neutralize the free fatty acids present in 1gm of fat. It is of value in determining rancidity due to free fatty acids.