Carbohydrates

The four major biomolecules are: (i) carbohydrates; (ii) lipids; (iii) nucleic acids and (iv) proteins.

Functional significance

Carbohydrates are both the energetic fuel (metabolic role) of the cell and the brick-and- mortar (structural role) of the cell parts.

Structure

Carbohydrates display two levels of structural organization:

1. monosaccharides are polymers of (CH2O)n;

2. polysaccharide are chains of monosaccharides i.e. they are polymer of polymers.

Monosaccharides

The number of CH2O units can vary.

sugarno. of CH2O
triose3
tetrose4
pentose5
hexose6
Most common monosaccharides are pentoses (ribose) and hexoses (glucose) but glycerol (triose) is also very important.

Hexoses are alcohols with additional aldehyde or keto group.

If they have a an aldehyde group they are called aldoses, if the keto group is present we refer to them as ketoses.

All hexoses undergo cyclization. Linear structure forms a ring structure bridged by an oxygen.

Hexose which is a ketose makes a 5-membered ring (fructose) while aldoses make a 6-membered ring: (glucose).

Sugar rings are predominantly planar with the hydrogen and hydroxide groups sticking below and above the plane of the ring

Depending whether OH group of the first carbon in the ring is below or above the ring we talk about a and b forms. In solution glucose undergoes rapid transformation between a and b forms via a straight chain conformation.

Di-saccharides

At the heart of polymerization of individual sugar units is the condensation reaction to form di-saccharides.

Condensation reaction

sucrose = glucose + fructose

Condensation of glucose and fructose is accomplished by extraction of water molecule from the two -OH to form oxygen bridge between the monosaccharide units. Such a bridge is called glycosidic bond.

Hydrolysis

The glycosidic bond can be split by the reversal of condensation reaction i.e. addition of water. The splitting reactions involving addition o water are called hydrolysis.

Condensation and hydrolysis reactions are make-and-brake reactions of the cellular metabolism.

Polysaccharides

Polysaccharides are long polymers of monosaccharides and are formed by condensation reactions.

The oxygen bridges can be formed between C1and C4 or C1 and C6 of neighboring sugars units. The accompanying numbers identify the bridged carbons and the placement of the O-bridge with respect to the ring plane

Starch

Starch is a energy storage polysaccharide common in plants.

It consists of two different polymers of glucose: amylose and amylopectin.

Amylose is made of a straight glucose chain with the glycosidic bonds between C1 and C4 of neighboring molecules. The glucose is in a form forming an O-bridge above the polysaccharide chain. Amylose curls up into a helix stabilized by hydrogen bonds.

Amylopectin is similar to amylose but in addition to a 1-4 links it contains branch points formed by a 1-6 links every 6 glucose residues.

Glycogen

Glycogen is a energy storage polysaccharide in animal cells.

Its structure is the same as for amylopectin but more branched.

Cellulose

Cellulose is part of the plant cell walls.

Cellulose is made of straight chains of b 1-4 linked glucose residues. The b linkage forces alternate placement of glucose rings.

Such an arrangement of glucose residues allows for hydrogen bonding between neighboring cellulose chains. This pattern of intermolecular H-bonds gives cellulose its structural rigidity.

Lipids

Function of lipids

structural: building blocks of cell membranes

information transfer: hormones

energy storage: fat

Structure of lipids

Fatty acids

The simplest of lipids is an amphipatic molecule, it consists of polar head (carboxyl) and a non-polar, alkyl (CH2)n tail.

Fatty acids make spherical micelles in water, tails forming the inside while polar heads stick out on the surface.

Tri-acylglycerols

Condensation of fatty acids and glycerol results in tri-acylglycerols..

Adipose tissue is made primarily of tri-acylglycerols (fat).

Phospholipids

A special class are phospho-ester of dia-acyl-glycerol, phospholipids.

Two fatty acid chains are joined to glycerol backbone, the third hydroxyl of glycerol has phospho- derivative of sugars, amines, a variety of groups often charged constituting polar head.

Heads are often zwitterions: they have both +ve and -ve charge.

Phospholipids make in water a bilayer sandwich: heads out - acyl chains in. Bilayer sandwich is a basic component of cell membranes.

Steroids

Steroids are honorary lipids, they are made of a fused ring system with small acyl tail.

Cholesterol: most common of the steroids, part of membranes, precursor of hormones.

Testosterone: male sex hormone

Progesterone: female sex hormone

P. Fajer Carbohydrates and Lipids 8/6 Chem-6 1/6/96 2:00 PM 8