CARBOHYDRATES Classification A. Monosaccharides consist of a single polyhydroxyaldehyde or ketone unit; may be aldoses or ketoses B.

. Oligosaccharides compounds formed when a few (2 to 10) monosaccharide units are linked together C. Polysaccharides formed when many monosaccharide units are bonded together in linear or branched chains A. Monosaccharides Structure Fischer projection structures Haworth projection formulas Stereochemistry All monosaccharides (except dihydroxyacetone) contain one or more chiral centers and therefore can exist in two different isomeric forms (stereoisomers) that have different configurations in space. Configuration denotes the spatial arrangement of an organic molecule that is conferred by the presence of either double bonds or a chiral center. A molecule with n chiral centers can have 2n stereoisomers. Enantiomers are stereoisomers that are nonsuperimposable mirror images of each other. Enantiomers differ in their ability to rotate the plane of polarized light (optical activity). Diastereomers are nonsuperimposable, non-mirror image stereoisomers. Diastereomers that differ from each other in the configuration at only one chiral carbon are called epimers. Most of the important sugars found in nature have the D configuration. Reactions 1. Oxidation-reduction (a) Oxidation

O C
aldose aldose aldose

O C
aldonic acid aldaric acid alduronic acid

OH
(mild oxidizing agent) (strong oxidizing agent)

Reducing sugars undergo oxidation reactions.

(b) Reduction
O C OH C H H

aldose

alditol

OH

aldose deoxysugar 2. Formation of glycosides Sugar OH + ROH Sugar O R + H2O Hemiacetal + alcohol acetal or glycoside + H2O (anomeric C) The newly formed bond is called a glycosidic bond. Examples: -D-glucopyranose + CH3OH methyl--D-glucopyranose + H2O -D-glucopyranose + -D-glucopyranose -D-glucopyranosyl-(14)--D-glucopyranose + H2O 3. Esterification Sugar OH + acid (or acid derivative) esters Example: -D-glucose + ATP -D-glucose phosphate + ADP

4. Other derivatives of sugars: amino sugars Example: N-acetyl--D-glucosamine

B. Oligosaccharides compounds formed by linking 2 to 10 monosaccharide units by glycosidic bonds

Examples: 1. sucrose -D-fructofuranosyl-(21)--D-glucopyranose or -D-glucopyranosyl-(12)--D-fructofuranose (12) linkage or (11) linkage table sugar non-reducing sugar

2. 3. 4.

lactose -D-galactopyranosyl-(14)--D-glucopyranose may be or form milk sugar reducing sugar maltose -D-glucopyranosyl-(14)--D-glucopyranose may be or form disaccharide obtained from hydrolysis of starch reducing sugar cellobiose -D-glucopyranosyl-(14)--D-glucopyranose may be or form disaccharide obtained from hydrolysis of cellulose reducing sugar

5. Others Trehalose: -D-glucopyranosyl-(11)--D-glucopyranose Raffinose: -D-galactopyranosyl-(16)- -D-glucopyranosyl-(12)--Dfructofuranose Melizitose: -D-glucopyranosyl-(13)--D-fructofuranosyl-(21)--Dglucopyranose

C. Polysaccharides formed when many monosaccharide units are bonded together by glycosidic linkages in long, linear or branched chains. a polymer that consists of one type of monosaccharide is a homopolysaccharide; one that consists of more than one type of monosaccharide is a heteropolysaccharide

some serve as structural materials; others as carbohydrate storage polymers

Examples: 1. Cellulose major structural component of plants homopolysaccharide of -D-glucose linkage (14) individual chains are hydrogen-bonded together giving plant fibers their mechanical strength

2.

Starch serve as vehicle for storage of glucose in plants homopolysaccharide of -D-glucose consists of 2 types: amylose is a linear polymer of glucose, with all residues linked together by -(14) bonds; its most usual conformation is a helix with 6 residues per turn amylopectin is a branched chain polymer, with the branches starting at -(16) linkages along the chain of -(14) linkages; branch points occur about every 25 residues

amylose

amylopectin

Enzymatic hydrolysis of starch (to glucose) -amylase is an endoglycosidase which can hydrolyze -(14) linkages anywhere along the chain to produce glucose and maltose -amylase is an exoglycosidase that cleaves -(14) linkages from the nonreducing end of the polymer. Debranching enzymes degrade the -(16) linkages Glycogen carbohydrate storage polymer in animals (found in liver and muscle cells) branched-chain polymer of -D-glucose like amylopectin, consists of -(14) linkages with -(16) linkages at the branch points branch points occur about every 10 residues (glycogen is more highly branched than amylopectin); average chain length is about 13 glucose residues and there are 12 layers of branching a more branched polysaccharide is more water-soluble and will have more potential targets for attack by hydrolytic enzymes

3.

4. Chitin structural component of exoskeletons of invertebrates (also in cell walls of algae, fungi and yeasts)

homopolysaccharide of N-acetyl--D-glucosamine residues are linked by -(14) glycosidic bonds

5. Glycosaminoglycans polysaccharides based on a repeating disaccharide in which one of the sugars is an amino sugar and at least one of them has a negative charge these molecules function as components in connective tissue (chondroitin and keratan sulfates), lubricating fluid of joints (hyaluronic acid) etc. Blood group antigenic determinants -N-acetylgalactosamine-(13)--galactose-(13)- -N-acetylgalactosamine 2 1 L-fucose A blood group antigen -galactose-(13)--galactose-(13)- -N-acetylgalactosamine 2 1 L-fucose

B blood group antigen

Glycosaminoglycan Chondroitin-4-sulfate

Monsaccharide components (linkage) D-glucuronic acid N-acetyl-D-galactosamine-4sulfate -(13) D-glucuronic acid-2-sulfate N-acetyl-D-galactosamine-4sulfate -(13) D-glucuronic acid-2-sulfate N-sulfo-D-glucosamine-6sulfate -(14) D-glucuronic acid N-acetyl-D-glucosamine -(13) D-galactose N-acetyl-D-glucosamine-6sulfate -(14)

Function Connective tissue component Sold as over-the-counter drug to help replace damaged cartilage (esp. in knees) Component of extracellular matrix of skin

Dermatan sulfate

Heparin

anticoagulant

Hyaluronic acid

Keratan sulfate

Component of vitreous humor of the eye and of lubricating fluid of joints Component of connective tissue