CARBOHYDRATES

BY: GROUP IV

This are polyhydroxycarbonyl compounds (aldehydes or ketones) or subsatnces that yield these compound upon hydrolysis.

ISOMERISM - Is the existence of two or more compounds with the same composition but different constitution.

A. STRUCTURAL ISOMERS - It have the same molecular formula, but different attachments.
1. Skeletal or Chain Isomers, e.g. N-butane and Isobutane CH -CH-CH I CH 2. Position isomers, e.g., 1-chloropropane and 2chloropropane CH -CH -CH Cl CH -CH -CH I Cl CH -CH -CH -CH

3.Functional isomers, e.g. Ethyl alcohol and dimethyl ether CH -CH -OH CH -O-CH

B.STEREOISOMERS
1.Geometric or cis-trans isomerism e.g. Fumaric acid and maleic acid H-C-COOH lI HOOC-CH H-C-COOH ll H-C-COOH

2. Optical isomers a. Enantiomers or optical antipodes are mirror images of each other(chiral) and non-superimposable. They have the same melting point(MP),boiling point(bp) and solubility,but they rotate plane polarized light in different directions.Hence,enantiomers are either dextro-rotary( ) and rotates plane polarized light to the right;or levorotatory and rotates plane polarized light to left. b.Diastereomers are not mirror images of each other. They have different MP, BP and solubilities, e.g. erythrose

RACEMIC MIXTURES are equimolar amounts of dextorotatory and levorotatory isomers, and therefore do not exhibit optical activity. On the other hand, 2, 3, dichlorobutane has two chiral centers but do not exhibit optical activity. These are called MESO compound (molecules with chiral centers which are not optically actice) due to the presence of planes and symmetry

STRUCTURES OF GLUCOSE AND OTHER HEXOSES

D(+) GLUCOSE

D(+) MANNOSE

D(+) GALACTOSE

D(-) FRUCTOSE

NOTES: 1.All 4 sugars are D- sugars because they have the same configuration as D- glyceraldehydes on the penultimate carbon, C-5. 2.D- fructose is a keto hexose and is a structural isomer of the other 3. 3.The 3 aldohexoses are not mirror images of each other, hence they are diastereomers. 4.There are 4 chiral carbons, hence there are 16 expected optical isomers,i.e. eight pairs of enantiomers. 5.D(+) glucose and D(+) mannose are epimers at C-2 6.D(+) glucose and D(+) galactose are epimers at C-4 Apparently, a special type of diastereomerism exists in Epimers diastereomers that differ in a single carbon atom Anomers diastereomers that differ in a single atom, and the single atom is carbon-1.

FUNCTIONS OF CARBOHYDRATES Skeletal or Structural functions,e.g.,cellulose, the major structural component of plant cell walls; and peptidoglycans of bacterial cell walls Storage, nutrient and reservoir of chemical energy, to be enlarged or depleted as the organism needs e.g., glycogen and starch, which are produced or consumed in line with the energy needs of the cell. CLASSIFICATION According to the number of sugar units a.Monosaccharides simple sugars that could not be hydrolyzed further into smaller units under reasonably mild conditions. They are generally crystalline compounds which are soluble in water and has a sweet taste. E.g., glucose b.Oligosaccharides hydrolyzable polymers of monosaccharides containing 2-6 molecules of simple sugar, e.g., sucrose c.Polysaccharides very long chains or polymers of monosaccharides which may be linear or branched in structure; usually tasteless and water insoluble. c.1. Homopolysaccharides made up of only one kind of monosaccharides,e.g., starch and glycogen c.2. Heteropolysaccharides made up of 2 or more different kinds of monosaccharides,e.g., hyalurnic acid

2. According to functional groups a. Aldoses contain the aldehyde group,e.g., glucose, mannose, galactose b. Ketoses contain the ketone group,e.g., fructose 3. According to the number of carbon atoms

# Carbons
3 4 5 6

Category Name
Triose Tetrose Pentose Hexose

Relevant examples
Glyceraldehyde, Dihydroxyacetone Erythrose Ribose, Ribulose, Xylulose Glucose, Galactose, Mannose, Fructose

Alpha anomer Anomeric OH is in the same side as OH of C-5, the reference carbon. All bulky groups except anomeric OH are equatorial, and are written above the plane of the ring Less stable form

Beta anomer Anomeric OH is trans to the OH of the reference carbon All bulky groups are equatorial, and are written below the plane of the ring More stable form

NOTES: 1.An equilibrium exists between the alpha form (36%), the beta form (67%), and the open chain form of glcose(1%). 2.The alpha and beta differs only in position of H and OH at C-1 and are called anomers

The structure of glucose may be shown using: Puckered chair and boat forms

Fischer projection formula

-D-Glucose

-D-Glucose

Haworth formulas

-D-Glucose

REACTIONS OF MONOSACCHARIDES 1.Monosaccharides exhibit mutarotation (form and anomers) 2.When these sugars act as reducing agent, they are in turn oxidized. 3.The aldehyde and ketone functions may be reduced to sugar alcohols. 4.They form glycosides.

5.Monosaccharides give characteristic color reactions in several qualitative test. This reaction is the basis for Molisch test for carbohydrates
Tests Molisch test Reagents & Procedures naphthol,then heat with concertrated H SO4 general test for carbohydrates orcinol,30% HCl FeCl solution. Presence of pentoses & nucleotides with pentoses Product Responsible for Color Furfural and hydroxyl furfural Positive Result Violet ring

Bial s Orcinol test

Seliwanoff s test

HCl + resorcinol differentiates aldohexoses from ketohexoses

Formation of furfural (pentoses) & hydroxyfurfural (hexoses)which yields blue green compound in the presence of Fe ions Dehydrated ketoses react faster to give colored condensation product

Trioses, uronic, heptoses give blue or green products, hexoses give yellow brown products

Bright cherry red with ketohexose, aldohexose give pale pink color

6. Based on their ability to reduce other substances, monosaccharides give the following results:
Tests Reagents & Procedure CuSO , Na CO , sodium citrate CuSO and sodium tartate Product Responsible for color Cu O Postive Result

Benedict s test

Brick red precipitate Brick red precipitate Brick red precipitate

Fehling s test

Cu O

Barfoed s test

Cu (Ac) in dilute Cu O HCl, can distinguish between reducing mono- and disaccharides AgNO , NH Ag mirror phenyllosazone

Tollen s test

Phenylhydrazine test Phenylhydrazine + heat

Deposition of Ag mirror Yellow precipitate

LINKAGES IN DISACCHARIDES 1.Maltose is the major degradation product of starch, is composed of 2 glucose monomers in an (1,4) glycosidic bond. It has free anomeric carbon, and can exist in a and b forms (can mutarotate), its a reducing sugar. 2. Cellobiose has 2 glucose units linked 1,4. It is formed by the hydrolysis of cellulose, can mutarotate and is reducing sugar. Methylation produces an octamethyl derivative and subsequent hydrolysis yields the same products as those of octamethyl maltose. 3. Isomaltose has 2 glucose units linked 1,6. Methylation gives an octamethyl derivative which hydrolyzes to 2,3,4,6 tetra-O-methyl D glucose and 2,3,4 tri-O-methyl D glucose.

4. Lactose has 1 glucose and 1 galactose unit linked -1,4. It is the disaccharide in milk. It can mutarotate and is reducing. 5. Sucrose is one glucose+ one fructose linked -1,2. Its sources are sugar cane and sugar beets. It is NOT a reducing sugar because both reducing groups of the two monosaccharides are involved in the formation of the glycosidic bond.

LINKAGES IN POLYSACCHARIDES Storage Polysaccharides A.Starch the storage polysaccharide of higher plants; consist of 2 fractions. 1.Amylose contains D glucose units linked -1,4 with reducing and non reducing end. Molecular weight varies from a few thousand to about 150000. It gives the characteristics blue color with iodine due to the ability of the halogen to occupy a position in the interior of the helical coil of glucose units when amylase is suspended in water.

Amylopectin a branched polysaccharide;short chains (about 30 units) of glucose linked -1,4 and -1,6. Molecular weight is 500,000 or higher; gives purple to red color with iodine.

Starch is susceptible to the action of the following hydrolytic enzymes: -amylase found in the digestive tract of animals(saliva and pancreatic juice) -amylase found in plants Debranching enzyme or -1,6 glucosidae hydrolyzes bonds at branch points yielding a mixture of glucose and maltose Glycogen is a structure similar to amylopectin but more highly branched and when acted upon by and amylase give glucose + maltose + limit dextrin

NUTRIENT POLYSACCHARIDES e.g, inulin, found in bulbs of many plants, consist fructofuranose units joined together by b-2,1 glycosidic linkage. STRUCTURAL POLYSACCHARIDES Cellulose consists of D glucose units linked -1,4. Its is found in cell walls of plants. Strong mineral acids cause partial hydrolysis to cellobiose and glucose. Pectins contains arabinose, galactose and galacturonic acid. Hemicelluloses are not cellulose derivatives; a homopolymer of D-xylose linked -1,4. Chitin a homoplymer of N-acetyl D glucosamine; found in the shell of crustaceans and scales of insects.

OTHER HETEROPOLYSACCHARIDES Cell coats of animal cells contain glycopids, glycoproteins and mucoploysaccharides which serve both as lubricant and as sticky cement. Hyaluronic acid a heteropolysaccharides composed of alternating units of D-glucuronic acid and N-acetyl O glucosamine with -1,3 linking the two monosaccharides, which in turn is linked -1,4 to the next repeating unit. Hyaluronic acid is found in the vitreous humor of the eye and in the umbilical cord, and is water soluble, forming viscous solutions. Chondroitin similar to hyaluronic acid except that the amino sugar is N-acetyl D galactosamine. It is also a component of cell coats. Sulfate esters of chondroitin at C-4 and C-6 of the amino sugar are major components of cartilage tendons, and bones.

Peptidoglycans a combination of polysaccharides with amino acids. The dissacharide consists of Nacetyl D glucose (NAG) and N-acetylmuramic acid (NAMA) joined by a -1,4 glycosidic bond. Peptidoglycans are found in bacterial cell walls which determine many of the physiological characteristics of the organism they enclose. Heparin this acidic polysaccharide is synthesized and stored in the mast cells of most tissue(lungs, liver, gutt). It has anticoagulant activity- binds to antithrombin III, a plasma protein involved in terminating the clotting process.