LIPID CHEMISTRY & BIOLOGICAL MEMBRANES

Dolores V. Viliran, M.D. Dept of Biochemistry

Introduction
LIPIDS A diverse group of compounds that are related by A diverse group of compounds that are related by their insolubility in water their insolubility in water Soluble in non polar solvents such as ether, Soluble in non polar solvents such as ether, acetone, benzene and chloroform acetone, benzene and chloroform The bulk of lipid molecule is non polar The bulk of lipid molecule is non polar There is no common subunit in their structure There is no common subunit in their structure The primary building blocks in human lipids are fatty The primary building blocks in human lipids are fatty acids, glycerol, sphingosine and sterols acids, glycerol, sphingosine and sterols

 Energy source
9 calories per gram

Adipose Fatty acids CO2 + H2O + ATP

Major component of cell membrane Phosphoglycerides Sphingolipids Cholesterol

Specific functions of Lipids

LIPID FUNCTIONS

1. Fatty Acids
2. Triglycerides 3. Phospholipids

Metabolic fuel building blocks for other lipids

Main storage form of fatty acids and chemical energy Component of membranes; source of arachidonic acid, Inositol triphosphate and diglyceride for signal transduction Component of membranes Component of membranes, precursor of bile salts and steroid hormones

4. Sphingolipids 5. Cholesterol

Specific Functions of Lipids

LIPID 6. Bile salts FUNCTION Lipid digestion and absorption; main product of cholesterol metabolism Intracellular signals that regulate gene expression in target cells Regulators of physiological functions

7. Steroid hormones 8. Eicosanoids

9. Vitamins

Vision; calcium metabolism; antioxidants; blood coagulation

10. Ketone bodies

Metabolic fuel

Emulsification of Fats by Bile

Bile that is produced in the liver and stored in the gallbladder is released into the Intestines for fat emulsification

VVV

ENZYME
BILE

EMULSIFIED FAT

BILE

EMULSIFIED FAT EMULSIFIED FAT

LIPID CLASSES
FATTY ACID DERIVATIVES TRIACYLGLYCEROLS (TAG)

WAX ESTERS
PHOSPHOLIPDS

SPHINGOLIPIDS
ISOPRENOIDS o terpenes o steroids LIPOPROTEINS

FATTY ACIDS AND THEIR DERIVATIVES

Fatty acids and their derivatives

Chemical formula

R-COOH
= represents the alkyl chain composed of carbon and hydrogen atoms
Fatty acids are divided into: Short -2 to 4 arbon atoms Medium -6 to 10 arbon atoms Long -12 to 26 or more arbon atoms

Human cells = long-chain variety In nature fatty acids = even number of carbon atoms

R-COOH

RCOO- + H+

Fatty acids and their derivatives

Detergent properties The alkyl side chain seeks a nonpolar environment carboxylate seeks an aqueous environment The concentration of fatty acid in the circulation is 0.5 to 0.7 mM., and most of this fatty acid is bound to albumin Free fatty acids are not found as structural constituents of membranes

Saponification

WATER

DIRT

Saponification

SURF DETERGENT
WATER

DETERGENT MOLECULES

DIRT

Saponification
WATER

Saponification

WATER

MICELLE

FATTY ACIDS

Names and Chemical Descriptions of some common Fatty acids

Saturated Fatty Acids

The fatty acids can be divided into two groups: saturated and unsaturated. Saturated fatty acids have only single bonds in hydrocarbon chain.
Saturated fatty acids are solids at room temperature because the regular nature of their aliphatic chains allows the molecules to be packed in close, parallel alignment:
The Interaction between neighboring chains are weak ,but the regular packing allows these forces to operate over a large portion of the chain so that considerable amount of energy is needed in order to melt them

Unsaturated Fatty Acids

Unsaturated fatty acids have at least one C = C double bond in the chains.
In contrast, unsaturated fatty acids are all liquid at room temperature because the cis double bonds interrupt the packing of the chains. Thus less energy is required to melt them. The greater the degree of unsaturation, the lower the melting point.

Unsaturated Fatty Acids

Double bonds in the cis form 1 double bond= monounsaturated

2 double bonds= polyunsaturated Fish and plant fats have more polyunsaturated fatty acids than that of mammals or fowl
2 systems in designating location of double bonds; Based on lettering system,: (delta) system (omega) system 1 = carboxylate

2 = -carbon
3 = -carbon methyl group = -carbon

 Two systems are used to designate the position of double bonds

In the ( delta ) system, The carboxylate is considered as C1 The position of the double bond is denoted by the carbon atom of the double bond closest to the carboxylate In the n or -system, the methyl group is considered as C1.

PALMITATE 16:0

PALMITOLEATE 16:1; -7

LINOLEATE 16:1; -6

COOH

Fatty Acid Nomenclature

Descriptive Name Numeric n

PALMITATE PALMITOLEATE LINOLEATE

16:0 9-16:1 9,12-18:2 16:19 18:2 9,12 1 16:1n-7 8:2n-6 16:1-7 8:2 -6

LINOLENATE

9,12,15-18:3

18:3 9,12,15

18:3n-3

18:3-3

CIS and TRANS ISOMERISM

Occurrence Cis double bonds
in humans, other animals, plants and bacteria

Trans double bonds

- Catalytic hydrogenation of vegetable oils - Margarine, cookies, candies, fried foods

double bonds= melting point

-Liquid at room temperature

double bonds= melting point

-Solid at room temperature
Trans fatty acids do not accumulate in human tissues, and cells contain enzyme activities required to completely oxidize such nutrients.

ESSENTAL FATTY ACIDS

- body can synthesize needed fat except:
- linoleic and alpha-linolenic acid

- body cannot add double bonds 9 carbons from delta end

- not form w-3 and w-6 - form w-9 only

ESSENTAIL FATTY ACIDS

OMEGA 3 FAMILY

OMEGA 6 FAMILY

OMEGA 6 FAMILY

ESSENTIAL FATTY ACIDS

w-3 & w-6 family are produced from essential fatty acids w-3 family from alpha-linolenic acid

- w-6 family from linoleic acid

by ELONGASE add C atoms in pairs at delta end

by DESATURASE form double bond

Production of Essential fatty acid derivatives

ESSENTIAL FATTY ACIDS

Polyunsaturated, or polyenoic fatty acids linoleic acid (C18) having two double bond linolenic acid (C18) having three arachidonic acid (C20) having four double bonds

ESSENTAIL FATTY ACIDS

REMEMBER:

Linoleic acid (-6 class) and linolenic acid (-3 class) are termed essential fatty acids because they cannot be synthesized in mammals Linoleic acid can be converted to -linolenic acid and Arachidonic acid can be formed from linoleic in most mammals The true essential fatty acid is Linoleic acid.

ESSENTIAL FATTY ACIDS

ARACHIDONIC ACID

A 20 carbon Omega 6 Fatty acid with 4 double bonds

Give rise to Eicosanoids

prostaglandins, thromboxanes,

lipoxins and
leukotrienes

Biological Actions of Selected Eicosanoid Molecules

ARACHIDONIC ACID
LIPOOXYGENASE CYCLOOXYGENASE

Leukotrienes
Vasodilatation

PGI

PGH2

TxA2
Platelet aggregation Vasoconstriction

Anti-platelet aggregation

PGE2
Smooth muscle contraction Vasodilatation

PGF2
Smooth muscle contraction Vasoconstriction

Inflammations

Bronchoconstrictions Vasoconstriction Capillary Permeability

ESSENTIAL FATTY ACIDS

EICOSANOIDS

- 20 carbon substances

- prostaglandins in prostate gland - thromboxane in thrombocytes - leucotrienes in leucocytes

- like hormones - in inflammation, clotting, and immune response

EICOSANOIDS

TRIACYLGLYCEROLS (TAG)
The main storage forms of fatty acids The acylglycerols are esters of fatty acids bound to the sugar alcohol glycerol O CH2 O C-(CH2)12 CH3 O C-(CH2)7
MYRISTIC ACID

CH

CH=CH- (CH2)7-CH3

OLEIC ACID

CH2

C-(CH2)16 CH3 O

STEARIC ACID

TAG
Such Compounds are called Triglycerides or Triacyglycerides: All three OH groups of Glycerol are Esterified They Are the most common Lipid Material, although Mono- and Diglycerides are not infrequent; in the latter two types, only one or two OH groups of Glycerol are esterified by Fatty Acids They are Complex Mixtures; although some molecules have 3 identical fatty acids, in most cases 2 or 3 different FA are present.

TAG
They are also called neutral fats, because the carboxyl groups of the fatty acids are bound in ester linkage and can no longer function as acids. The fatty acid moiety in lipid esters is known as an acyl group.
TAG mixtures are referred to as fats or oils
Fats= which are solid at room temperature, contain a large proportion of saturated fatty acids Oils = are liquid at room temperature because of their relatively high unsaturated fatty acid content

AGENERAL TYPES of TAG

O CH2 O C R1 HC - OH CH2OH MAG O CH2 O C R1 O HC O C R2 CH2OH DAG O CH2 O C R1 O HC O C R2 O CH2O O C R3 TAG

MAG

DAG

TAG

TRIACYLGLYCEROL

TAG
In humans Hydrolyzed by lipase to glycerol + FFA In industry Hydrolyzed by NaOH to create glycerol + watersoluble soaps In animals Major storage and transport form of FA Insulation in low temperatures Makes fur and feathers water-repellent In plants Energy reserve in fruits and seeds

WAX ESTERS
Waxes are complex mixtures of nonpolar lipids They are protective coatings on leaves, stems, and fruit of plants and the skin and fur of animals Esters composed of long-chain fatty acids and longchain alcohols are prominent constituents of most waxes Well-known examples of waxes include carnauba wax, produced by the leaves of the Brazilian wax palm, and beeswax
The predominant constituent of carnauba wax is the wax ester melissyl cerotate. Triacontyl hexadecanoate is one of several important wax esters in beeswax

Waxes also contain hydrocarbons, alcohols, fatty acids, aldehydes and sterols ( steroid alcohols).

COMPLEX LIPDS

SCEMATIC DIAGRAM OF SIMPLE AND COMPLEX LIPDS

SIMPLE AND COMPLEX LIPIDS

SIMPLE

COMPLEX

PHOSPHOLIPIDS

GLYCOLIPIDS

PHOSPHOGLYCERIDES
FA GLYCEROL FA ALCOHOL

SPHINGOLIPIDS
SPHINGOSINE FA

PO4

PO4

ALCOHOL

 Phosphoglyceride molecules are classified according to which alcohol becomes esterified to the phosphate group
Phosphatidylcholine (PC or Lecithin) =
the alcohol is choline

phosphatidylethanoalmine (PE) =
ethanolamime

Phosphatidylserine (PS) =
serine

diphosphatidylglycerol (dPG) =
phosphatidylyglycerol

phosphatidylinositol (PI) =
Inositol

A derivative of phosphatidylinositol, namely phosphatidyl-4,5-bisphosphate (PIP2), is found in only small amounts in plasma membranes. PIP2 is now recognized as an important component of a second messenger system

The most common fatty acids in the phosphoglycerides have between 16 and 20 carbons Saturated fatty acids usually occur at C-1 of glycerol The fatty acid substituent at C-2 is usually unsaturated

Phospholipids
Contains an alcohol, Fatty acid and a phosphate group. There are two types: Glycerophospholipids ( phosphoglycerides) Sphingolipids( sphingomyelins) In glycerophospholipids, the alcohol is glycerol In Sphingolipds, the alcohol is sphingosine

Phospholipids

PHOSPATIDYLSERINE PHOSPHATIDYLETHANOLAMINE PHOSPHATIDYLCHOLINE

Biological importance of Phospholipids

Lecithin or phosphatidylcholines or surfactants or surface-acting agents play an essential role in reducing surface tension in lung alveoli; they are Increase Pulmonary Compliance is usually seen in this disease where alveoli (in the Lungs) are collapse due to strong surface Tension secondary to reduced or absence of surfactants- usually fatal. Respiratory distress syndrome (RDS) of the newborn, which is common in premature infants, results from a lack of this surfactant in the lung

Biological importance of Phospholipids

To predict the likelihood of RDS in high-risk pregnancies, obstetricians commonly perform amniocentesis for laboratory determination of the ratio of phosphatidylcholine (lecithin) to sphingomyelin in the amniotic fluid (L/S ratio)

The higher the L/S ratio, the more surfactant is present to allow the lung to expand normally

The major features of the lungs include the bronchi, the bronchioles and the alveoli. The alveoli are the microscopic blood vessel-lined sacks in which oxygen and carbon dioxide gas are exchanged.

Hyaline membrane disease (Neonatal Respiratory Distress Syndrome - NRDS) is characterized by collapsed alveoli alternating with hyperaerated alveoli, vascular congestion and hyaline membranes (resulted from fibrin, cellular debris, red blood cells, neutrophils and macrophages). Hyaline membranes appear like an eosinophilic, amorphous material, lining or filling the alveolar spaces and blocking the gases exchange.

Biological importance of Phospholipids

Serologic test for syphilis, the Venereal Disease Research Laboratory (VDRL) test, utilizes cardiolipin, a diphosphatidyl glycerol as the antigen

The highly polar phosphate, choline, and serine groups of the phosphoglycerides make these compounds water-soluble, while their fatty acyl groups confer solubility in nonpolar agents
Hence, they can serve to cement lipids to membranes and lipoproteins to the polar proteins and carbohydrates.

SPHINGOLIPIDS
The Sphingolipids contain sphingosine as their amino alcohol There are three general classes of Sphingolipids: a) Sphingomyelin b) Cerebrosides c) gangliosides substituent attached to the C1-hydroxyl group of sphingosine separates these three classes:
Sphingomyelin contains phosphocholine Cerebrosides contain a monosaccharide Gangliosides contain an oligosaccharide CERAMIDE- Plays an important role in the formation of these 3 classes .

SPHINGOLIPIDS
CERAMIDES consist of a fatty acid bound to sphingosine In humans, ceramides function principally as intermediates in the synthesis of other sphingolipids SPHINGOMYELIN By joining choline phosphate or ethanolamine phosphate to ceramides, one generates the sphingomyelin. . important components of the myelin sheath surrounding the fastest conducting fiber. CEREBROSIDES They consist of a hexose sugar, such as glucose or galactose, bound to a ceramide. These ceramide-monosaccharides are also part of the myelin sheath.

SPHINGOLIPIDS
GANGLIOSIDES
Consist of ceramide bound to an oligosaccharide that contains an acidic sugar such as Nacetylneuraminic acid

SULFATIDES Are sulfated cerebrosides, or cerebroside-sulfate esters.

The coating of nerve axons (myelin) contains a different kind of complex lipid called sphingolipids. In sphingolipids the alcohol portion is sphingosine: NONE CONTAINS GLYCEROL

ISOPRENOIDS
With repeating 5-carbon units (isoprene) Types: terpenes and steroids TERPENES
Monoterpenes
Geraniol in oil of geranium

2 isoprene units 3 isoprene units

Sesquiterpenes
Farnesene in oil of citronella

Diterpenes
Phytol, a plant alcohol Squalene, in shark liver oil

4 isoprene units

Triterpenes
Olive oil and yeast

6 isoprene units 8 isoprene units bet. 3,000 and 6,000 units

Tetraterpenes
Carotenoids

Polyterpenes
Natural rubber

 Mixed Terpenoids Several important biomolecules are composed of nonterpene components attached to isoprenoid groups (often referred to as prenyl or isoprenyl groups) Examples of these biomolecules, referred to as mixed terpenoids, include vitamin E ( -tocopherol), ubiquinone, vitamin K and some cytokinins ( plant hormones)

STEROIDS
The third major class of lipids is the steroids, which are compounds containing this ring system
There are three cyclohexane rings (A,B, C) connected in the same way as in phenanthrene and a fused cyclopentane ring (D). Steroids are thus completely different in structure from the lipids.

STEROIDS
Complex derivatives of triterpenes All with 4 fused rings Distinguished by placement of C-C double bonds and other substituents (hydroxyl, carboxyl, alkyl) The essential structural nucleus of the steroids consists of three fused cyclohexane rings (A-C) joined to a cyclopentene ring (D)
They are found in all eukaryotes and a small number of bacteria Cholesterol, an important molecule in animals, is an example of the steroids. In addition to being an essential component in animal cell membranes, cholesterol is a precursor in the biosynthesis of all steroid hormones, vitamin D, and bile salts

Animal Steroids

cholesteroL

Free cholesterol

testosterone

estradiol (estrogen)

Progesterone

CHOLESTEROL

CH3 CH3 HO

CHOLESTEROL

Cholesterol in Selected Foods

STEROIDS
Estrogens= OVARIAN STEROID
Contain 18 carbon atoms (Carbon 18 is found in a methyl

group)
Unlike other steroids, the A ring of the steroid nucleus of estrogen is aromatic. Estradiol has OH groups attached to carbons 3 and.17.

 Androgens, This Steroid is produced in the adrenal cortex and the testes Having19 carbon atoms (Carbons 18 and 19 are in methyl groups) Testosterone is one of the more potent androgen Dehydroepiandrosterone (DHA), unlike testosterone, is a 17-ketosteroid

Animal Steroids
CH3 CH3 A B HO C D

CHOLESTEROL
OH CH3 CH3 CH3 OH CH3

FREE CHOLESTEROL
OH CH3 CH3 O

HO

TESTOSTERONE

ESTROGEN

PROGESTERONE

STEROIDS
Progesterone= synthesized in the corpus luteum, has 21 carbons, as do the adrenocortical steroids such as corticosterone and cortisol Progesterone has an acetyl group joined at carbon 17 The bile acids are 24-carbon steroids secreted into the bile to emulsify dietary fats They have a five-carbon side chain at position 17 that contains a carboxyl group, making them acidic Cholic acid is a major human bile acid

STEROIDS
The adrenal cortex produces glucocorticoids, which Cortisol is a potent glucocorticoid with weak
raise the serum glucose level, and mineralocorticoids, which promote renal sodium retention
mineralocorticoid activity, whereas aldosterone is a potent mineralocorticoid (presumably due to its aldehyde group at carbon 18) but a weak glucocorticoid A hydroxyl or keto group at carbon 11 is found to correlate with glucocorticoid activity The urinary 17-hydroxycorticosteroid assay detects all 21-carbon steroids with a 17-OH group, such as cortisol

LIPOPROTEINS
Lipids must bind to proteins to make them watersoluble for transport in the blood Free fatty acids, for example, avidly bind to serum albumin and will displace albumin-bound drugs from their binding sites. Two laboratory techniques are used to separate lipoproteins from one another:
ultracentrifugation separates them according to their
differing densities

electrophoresis separates them on a basis of their varying

net charges

LIPOPROTEINS

Each type of lipoprotein contains a neutral lipid core composed of Cholesterol esters and TAG The core is sorrounded by a layer of Phospholipid, free cholesterol and protein Charged and polar residues on the surface of a lipoprotein enable it to dissolve in blood

LIPOPROTEINS

Chylomicrons
Chylomicrons are the least dense lipoproteins, because consist mainly of triglycerides with small amounts of cholesterol, phospholipids, and proteins They do not migrate when subjected to electrophoresis, because their high triglyceride content (triacylglycerols have no charge) After a fatty meal, the blood appears milky due to the high concentration of chylomicrons Lipoprotein lipase hydrolyzes triglycerides bound in lipoproteins such as chylomicrons and VLDL, yielding monoglycerides and free fatty acids

CHYLOMICRONS
Heparin, an anticoagulant, also helps to clear chylomicrons from the blood, perhaps by stimulating lipoprotein lipase The inherited absence of lipoprotein lipase causes hyperchylomicronemia, termed Fredericksons type 1 hyperlipoproteinemia.

Very low-density lipoproteins (VLDL)

Very low-density lipoproteins (VLDL) also contain principally triglycerides, but have a greater protein, phospholipid, and cholesterol content than chylomicrons Their protein and phospholipid content makes them charged so that they migrate just before the Bglobulins in electrophoresis; hence, they are termed pre-B Lipoproteins VLDL is synthesized in the liver This VLDL fraction is markedly elevated in type IV hyperlipoproteinemia.

Low-density lipoproteins (LDL)

Low-density lipoproteins (LDL) contain mainly cholesterol, in contrast to the content of chylomicrons and VLDL, which is mainly triglyceride LDL also contains appreciable amounts of proteins, phospholipids, and triglycerides. Because they migrate together with the -globulins, they are termed -lipoproteins The LDL fraction is markedly elevated in type II hyperlipoproteinemia and is associated with a high incidence of atherosclerosis.

High-density lipoproteins (HDL)

High-density lipoproteins (HDL) contain mainly protein and phospholipid They contain significant amounts of cholesterol, but have little triglyceride

The high protein, low triglyceride content makes them very dense They are termed alpha-Lipoproteins and are separated from other lipoproteins by electrophoresis.

BIOLOGICAL MEMBRANE
Biological membranes are thin sheet-like structures composed mainly of lipid and protein Membrane lipids create the permeability barrier, while membrane proteins serve as pumps, enzymes, receptors, and energy transducers Membranes create compartments ranging from mitochondria and nuclei to cells. Three main classes of lipids are found in biological membranes:
Phospholipids glycolipids Cholesterol

Biological Membrane
The phospholipids are based on either glycerol or sphingosine Glycerol-based phospholipids include phosphatidyl choline, phosphatidyl inositol, and phosphatidyl ethanolamine Sphimgomyelin is one of the sphingosinebased phospholipids Membrane glycolipids include cerebrosides and Gangliosides

Biological Membrane
Non-polar Polar A PHOSPHOLIPID BILAYER
EXTRACELLULAR MEMBRANE PROTEIN

TRANS-MEMBRANE PROTEIN

INTRACELLULAR MEMBRANE PROTEIN

MEMBRANE PROTEINS EMBEDDED IN PHOSPHOLIPID BILAYER

Biolological Membrane

BIOLOGICAL MEMBRANE
The purpose of the membrane is to separate cells from the external environment and to provide selective transport for nutrients and waste products. That is, membranes allow the selective passage of substances into and out of the cells. The cell membrane is made up of lipid bilayers. In a lipid bilayer there are two layers of lipid molecules arranged tail to tail. The hydrophobic tails point toward each other because that enables them to get as far away from the water as possible. This leaves the hydrophilic heads projecting to the inner and outer surfaces of the membrane.

BIOLOGICAL MEMBRANES
Membrane Lipid
Phosphoglycerides

Hydrophobic Unit Hydrophilic Unit

Fatty acid side chains Phosphorylated alcohol

Sphingomyelin

Fatty acid chain & hydrocarbon chain of sphingosine

Phosphoryl choline

Glycolipid

Fatty acid chain & hydrocarbon chain of sphingosine

One or more sugar residue

Cholesterol

Entire molecule except OH group

OH group of C-3

Lipid Bilayer

Amphipathic
Hydrophilic: water-loving polar head group Hydrophobic: waterhating non-polar tails

The Lipid Bilayer Forms the Membrane Structure

Before there was the Fluid Mosaic Model...

1895: Charles Overton
membranes are made of lipids

1917: Irving Langmuir

model looks like a half of the lipid bilayer

1925: Gorter and Grendel

cell membranes must actually be phospholipid bilayers, two molecules thick

1935: Davson and Danielli

sandwich model (Campbell, 2002)

Fluid Mosaic Model (Singer and Nicolson, 1972)

The cell membrane is a mosaic of protein molecules bobbing in a fluid bilayer of phospholipids.

What makes up the cell membrane?

Lipids

Proteins

Carbohydrates

LIPIDS
phospholipids, glycosphingolipids and sterols insoluble in water form the cell membrane lipid-soluble substances (i.e. O2, CO2, steroid hormones) readily cross the cell membrane

Phospholipids

Phosphoglycerides have glycerol backbone

Myelin, a type of sphingomyelin has a sphingosine backbone

Cholesterol
Most common sterol in membranes Generally more abundant toward the outside of the plasma membrane Intercalates among phospholipids (Murray et al., 1996)

Cholesterol and Membrane Fluidity

Temperature and Membrane Fluidity

..cell membrane\membrane_structure.mov ..active_transport_1.mov ..diffusion.mov ..Exocyt and Endo Anim.mov

COMPOSITION OF DIETARY FATS

Mixture or fatty acid derivatives Fats from animals have more saturated fats than from plants Saturated FA HDL, LDL Mono-UFA HDL, LDL PUFA maintains HDL, LDL Trans FA HDL, LDL

COMPOSITION OF DIETARY FATS

Treatment of hypercholesterolemia Diets that contain MUFA and PUFA Treatment of hypertriglyceridemia and protection against thrombosis -3 class of PUFA Produced by plants that grow in cold sea
water. Fish such as salmon feed on this vegetation

COMPOSITION OF DIETARY FATS

PALMITIC 0) (C-16STEARIC (C-18-0) OLEIC (C-18:1) LINOLEIC (C-18:2) -LINOLENIC (C-18:3)

Perilla oil Flaxseed oil Manhattan Herring oil Canola oil Walnut oil

6 3 19 5 7

2 7 4 2 2

17 21 13 53 50

15 16 1 22 16

61 53 1 10 10

Soybean oil
Butter/milkfat Beef fat Palm oil Olive oil Corn oil Sunflower seed oil Borage seed oil Evening primrose oil Safflower seed oil

11
25 29 45 14 11 6 11 6 7

4
11 20 5 3 2 4 4 1 3

23
26 42 38 71 25 24 16 11 15

51
2 2 10 10 55 65 39 72 75

7
2 0 0 0 0 0 0 1 0

LIPID PEROXIDATION
Peroxidation- exposure of lipids to O2
Causes deterioration of food (rancidity) May cause tissue damage leading to cancer, inflammatory diseases, atherosclerosis, aging, etc.

The deleterious effects are initiated by free radicals (Ko, KOo, KOOo, OHo) produced during peroxide formation from fatty acids containing methyleneinterrupted double bonds, such as those found in naturally-occuring PUFA Chain reaction producing continuous supply of free radicals that initiate peroxidation

LIPID PEROXIDATION
Initiation ROOH + metal (n+1) ROO0+ metal (n-1) RH + X R0 + XH Propagation R0 + O2 ROOH ROO0 + RH ROOH + R0, etc

Termination ROO0 + ROO0 ROOR + O2 ROO0 + R0 ROOR R0 + R0 RR

Classes Of Antioxidants
Preventive antioxidants Reduce the rate of chain initiation Examples Catalase Chelators of metal ions DTPA (diethylenetriaminepentaacetate) EDTA (ethylenediaminetetraacetate) Chain-breaking antioxidants Interfere with chain propagation Examples Phenols Aromatic amines In vivo, superoxide dismutase which acts on aqueous phase to trap superoxide free radicals (O-o) Peroxidation is also catalyzed by heme compounds and by lipooxygenases found in platelets and leukocytes

Separation & Analysis of Lipids

Thin layer chromatography Gas-liquid chromatography Saponification Salting out method

Amphipathic Lipids
Self-orient at oil-water interfaces Form membranes, micelles, liposomes, emulsions Amphipathic Hydrophobic- water-insoluble Hydrophilic water soluble

Amphipathic LIpids
Oriented at oil-water interface with polar at water phase, nonpolar at oil phase Biologic membrane lipid bilayer Micelles polar lipids in an aqueous solution or medium Liposomes lipid bilayer forming a vesicle by sonicating an amphipathic lipid serves as cancer drugs Receptors tissue-specific antibodies Emulsions larger particles, formed by non-polar lipids in an aqueous medium stabilized by emulsifying agents such as polar lipids (lecithin)