Fatty acids & Lipid

Structure & Function

Lipids are another type of ORGANIC molecule (contains carbon). When you think of fats you should know that they are lipids. Lipids are also used to make STEROIDS and WAXES. So if you pick out some ear wax and smell it... That's a lipid too!

Waxes

Waxes are used to coat and protect things in nature. Bees make wax. Your ears make wax. Plant leaves even have wax on the outside. It can be used for structures as the bees make honeycombs. Waxes can also be used for protection. Plants use wax to stop evaporation of water from their leaves.

LIPIDS
Biomolecules with low solubility in water (polar) and high solubility in nonpolar solvents. Lipids are less oxidized. Lesser oxygen atoms in lipid. Highly reduced. Metabolic oxidation yield large amounts of energy. Excellent for storing energy in living organisms. We will be looking at the structure, chemistry and biological functions of fatty acids and lipids in this lecture.

Biological functions of lipids

1. As structural components of cell membrane (phospholipids) 2. As energy storage compounds in the form of triacylglycerols (better than carbohydrates; WHY?) 3. As inter and intracellular signal molecules (steroids) 4. As absorbents of lipids from the small intestine (bile acids)

Forms of lipids

Triglycerides

LIPIDS

Phospholipids

Steroids
The lipids found in organisms are either hydrophobic (containing only nonpolar groups) or amphipathic (possessing both polar and nonpolar groups)

Lipid (triglyceride) component

+ 3 fatty acid molecules

What is the type of reaction involved? GLYCEROL is a very simple molecule with just three carbons and three OH-groups. It is a colourless, viscous liquid sometimes called 'glycerine'

Structure of fatty acid

General formula: RCOOH
R represents an H atom or an alkyl group (-CH3, -C2H5, ..) Hydrocarbon chain (hydrophobic)

The functional group in a fatty acid molecule is the carboxyl group Would you be able to recognize this structure?

Three fatty acids bond to the glycerol in a TRIPLE CONDENSATION REACTION to form a standard TRIGLYCERIDE LIPID held together by three ESTER BONDS Three molecules of water are released in the process. There are many different types of fatty acids: differing in their number of carbons; and it is the different types of fatty acids which make the different types of lipids. The types of fatty acids in a lipid (triglyceride) can be all different; two the same and one different; or all three the same type

Triglyceride

3 fatty acid molecules

1 glycerol molecule

Structure of triglyceride

Diglyceride

Monoglyceride

Saturated/unsaturated fatty acids

Animal fats

Vegetable oils The 'kink' in unsaturated lipids due to the double bond makes the molecules lie against one-another less easily and so these molecules tend to be liquid rather than solid.

Nomenclature
Fatty acids are long-chain hydrocarbon molecules containing a carboxylic acid moiety at one end The numbering of carbons in fatty acids begins with the carbon of the carboxyl group At physiological pH, the carboxyl group is readily ionized, rendering a negative charge onto fatty acids in bodily fluids

Nomenclature (contd)
Fatty acids that contain no carbon-carbon double bonds are termed saturated fatty acids; those that contain double bonds are unsaturated fatty acids The numeric designations used for fatty acids come from the number of carbon atoms, followed by the number of sites of unsaturation (eg, palmitic acid is a 16-carbon fatty acid with no unsaturation and is designated by 16:0) The site of unsaturation in a fatty acid is indicated by the symbol and the number of the first carbon of the double bond (e.g. palmitoleic acid is a 16-carbon fatty acid with one site of unsaturation between carbons 9 and 10, and is designated by 16:19)

Fatty acids with physiological relevance

Symbol/Chemical Name
14:0 n-tetradecanoate 16:0 n-hexadecanoate 18:29,12 cis,cis-Delta-9,12octadecadienoate 18:39,12,15 all-cis-Delta-9,12,15octadecatrienoate

Common Name
Myristic acid

Chemical Structure
CH3(CH2)12COOH

Palmitic acid

CH3(CH2)14COOH

Linoleic acid (essential)

CH3(CH2)4C=CCH2C=C(C H2) 7COOH

Linolenic acid (essential)

CH3CH2C=CCH2C=CCH2 C=C(CH2)7COOH

Melting temperature of fatty acids

Effect of unsaturated bonds on the melting temperature of fatty acids

Oleic acid

The effect of double bond on the melting point of fatty acids

Tm is dependent on the length of the hydrocarbon chain because of van der Waals interaction

van der Waals interaction is weaker in fatty acids with cis double bonds. So, theTm will be lower

Saturated fatty acids of less than eight carbon atoms are liquid at physiological temperature, whereas those containing more than ten are solid The presence of double bonds in fatty acids significantly lowers the melting point relative to a saturated fatty acid

The majority of body fatty acids are acquired in the diet. However, the lipid biosynthetic capacity of the body (fatty acid synthase and other fatty acid modifying enzymes) can supply the body with all the various fatty acid structures needed. Two key exceptions to this are the highly unsaturated fatty acids know as linoleic acid and linolenic acid, containing unsaturation sites beyond carbons 9 and 10. These two fatty acids cannot be synthesized from precursors in the body, and are thus considered the essential fatty acids; essential in the sense that they must be provided in the diet. Since plants are capable of synthesizing linoleic and linolenic acid humans can acquire these fats by consuming a variety of plants or else by eating the meat of animals that have consumed these plant fats

Phospholipid

Phospholipid is a tryglyceride in which one of the fatty acid has been replaced with a phosphate group

Structure of phospholipids

The Phosphate group is referred to as being HYDROPHILIC (which means 'WATER SOLUBLE') and the Fatty Acids are referred to as being HYDROPHOBIC (which means 'WATER INSOLUBLE'). Clearly these two parts of the molecule do not like to be near one-another and so to 'escape' from oneanother they rotate through 180 degrees in space

Significance of phospholipid structure in biology

If you mix phospholipids and water and stir them up, they automatically assume the shape shown here (this is a two-dimensional section through a sphere-like structure called a Phospholipid

Micelle

Can this be the structure of cells millions of year ago?

The structure shown in the previous slide is probably very similar to the first cell, which evolved hundreds of millions of years ago Phospholipids would have formed through random combination of elements and would then have automatically formed into these cell-like micelles in rock-pool and other bits of water Inside the micelle chemical reactions could occur independently of the external environment - which is principally what is required for a cell to function

What do you think..?

Structure of cell membrane

The reason that the phospholipids line up like this is because there is both water outside and trapped inside and so the hydrophilic phosphate groups point out and in. The hydrophobic fatty acids have nowhere to go so they turn to face one-another to 'escape' from the water.

FLUID-MOSAIC model of membrane structure

The only molecules which the phospholipid bilayer will let through are as follows: a) Gases such as Oxygen and Carbon Dioxide (these are small enough simply to pass through the bilayer). b) Water itself (which is small enough to pass through the bilayer, even though anything dissolved in the water will not pass through). c) Any fat-soluble substance (which will simply dissolve through the hydrophobic fatty acid layer). Included in this category are steroid hormones such as Testosterone (which are lipid derivatives) and anything natural or synthetic which dissolves fats or dissolves in fats.

The phospholipid bilayer consists very largely of a central hydrophobic area due to the presence of the Fatty Acids. It is therefore completely impermeable to any large hydrophilic (water soluble) substance such as Salts, Sugars and Amino Acids. Clearly these substances need to get through the membrane at various times in the life of the cell. In order for them to do so, specific PROTEINS are required in the membrane - these can be carrier or channel proteins (which are passive) or active transport proteins. The combination of phospholipids, proteins and other ingredients which make up a membrane is referred to as the FLUID-MOSAIC model of membrane structure.

Hierarchy of lipids

FLUID-MOSAIC model of membrane structure

Steroids
Structurally different from other lipids! (Note: Unlike other biomolecules, lipids are classified based on their properties and NOT their structure) The basis of a steroid molecule is a four ring structure, one with five carbons and three with six carbons in the ring. Variable fatty 4 rings acid side chain

Steroids are used in animals to make HORMONES. You may have heard of steroids in the news. Many body builders and athletes use anabolic steroids to build muscle mass. The steroids make their body want to add more muscle than they normally would. The body builders wind up stronger and bulkier (but not faster). Never take drugs to enhance your body. Those body builders are actually hurting their bodies. They can't see it because it is slowly destroying their internal organs and not the muscles. When they get older they can have kidney and liver problems. Some even die because of the complications!.

Issues of interest
Is palm oil healthy? What is a trans fatty acid? Is palm oil plantation destroying our tropical forests and its biodiversity, including the survival of orangutans? Why is palm oil a threat to other vegetable oils?