8.

1 Monosaccharides Monosaccharides are the simplest carbohydrates that compound with a single aldehyde and ketone unit and multiple hydroxyl group which havethe empirical formula (CH2O)n. The smallest compounds usually considered to be important natural carbohydrates are the thriose (n=3), glyceraldehydes (aldose) and dihydroxycetone (ketose). The draw of carbohydrate structure in Fischer projection is that the tetrahedral carbon atom is representated by two crossed lines. The carbon atomis assumed to be at the intersection of the lines. A horizontal bond to an asymmetric carbon designates bonds in the f ront plane of the page and verticalbonds behinds the plane of the page.

Fischer projection The monosacarides with n=5,6, 7 are called pentoses, hexosee and heptoses. Like th smallet monoshacaride, there are also aldoses ad ketoses among th larger carbohydrates. Several important monosaccharidesare are in the D-aldoses series. Dglucose, D-manose, D-galactose arethe most abundant of the aldohexoses.

Family of D-aldose and D-ketose

8.2 Carbohidrates in Cyclic Structures The monosaccharideswith five or more carbon atoms spend most of their time in solution as cyclic structures.the ring is formed by reaction of thealdehyde or ketone on one end of the molecule. The form of hemiacetal:

The five membrane ring is called a furanose because I is similar to the hetrocyclic ring, furan .The same reaction applied to D-glucose results in a six-membered ring called apyranosebecause I is similar to pyran. The form of hemiacetal in ketose:

The and formsof sugars are called anomers because they differ only by he stereochemistry at the anomeric carbon. The full names of three cyclic sugars above are - or D-ribofuranose, are - or fructofuranose, an are - or dglucopyranose. The cyclic structure for ribose, glucose, and fructose are drawn in the hHawort projection. This representation shows all hydroxyl groups and hydrogen atoms bu does not show carbon atoms in the ring.

8.3 Reaction of Glucose and other Monosaccharides Oxidation Reduction The complete metabolic breakdown of glucose to CO2 andH2O is a process involving several oxidation steps the details of which are covered. Oxidation reactions of carbohydrates can be illustrated with either the open chain or the cyclic form, which are in equilibrium.

Many oxidizing agents, including Tollens reagent or cupric are used to identify the presence of reducing sugars. Reducing sugars are those that contain a free aldehyde group and are capable of reducing metal ions in solution. Reduction of the aldehyde or ketone group of a carbohydrate is also of biological importance. The reduction of the aldehyde group in glucose yields sorbitol, a sweetening agent. Enzymes that catalyze oxidation reduction reactions in the cell use the coenzymes NADH or NADPH to carry out carbohydrates

Esterification Esters are compounds formed by reaction of hydroxyl group (alcohols) with acids.The hydroxyl groups of the carbohydrates react to alcohols to produces esters. The most important biological esters of carbohydrates are the phosphate esters made using phosphoric acid.In the cell,phosphate esters are produced not using the very acidic but,most often by transfer of a phosphoryl group from adenosine

triphosphate (ATP) to a carbohydrate hydroxyl group, a reaction catalyzed by enzymes called kinase: D-glucose + ATP D-glucose 6 phosphate + ADP.

Amino Derivatives of Sugars The replacement of a hydroxyl group on a carbohydrate by an amino group results in an unusual class of compounds, the amino sugars. Glucosaamine and its acetylated derivates, N acetylglucosaamine and N acetylmuramic acid, are found as structural components of bacterial cell walls.The acidic amino sugar N acetylneuraminic acid derived from the carbohydrate rhamnose, is a component of glycoproteins and glycolipids.

Glycoside Formation When carbohydrates are reacted with hydroxyl group under anhydrous, mildly acidic condition, a new linkage, and O-glycosidic bond, is formed. In the glycoside product, one glucose is linked via its anomeric hydroxyl group to the hydroxyl group on C4 of the second glucose unit. O glycosidic bonds are the basis for linking together carbohydrates (monossacharides) into the larger carbohydrates, discharrides and polysaccharides.

The dissacharides maltose can be easily digested by humans because of the presence of enzyme that can catalyze the hydrolysis of (1- 4 ) glycosidic bonds.The dissacharides lactose also called milk sugar is found only in diary

products.Sucroese,common table sugar is a disssacharide of glucose and fructose linked via an , (1 2) glycosidic bond. Both terms are necessary to define glycosidic bond because the anomeric carbon in configuration is linked to the anomeric carbon of fructose in configuration. Fructose is sweeter than sucrose, so less is required for the same level of sweetens.

8.5 Glycoprotein Protein that carry covalently bonded carbohydrate units are called glycoproteins. These protein are involved many biological functions, including immonulogical protection, cell-cell recognition events, blood clotting, and host-patogen interaction. Glycoprotein Structure There are two important types of linkages involved the attachment of sugars to protein: O-glicosidic bonds using the hydroxyl groups of serine and threonine residues in the protein o react with carbohydrates and N-glicosididc bondsusing the side chain amide nitrogen of the amino acid residue asparagines to link carbohydrate.