Carbohydrate Chemistry

CARBOHYDRATE CHEMISTRY
DEFINITION: Carbohydrates are organic substances composed of carbon, hydrogen and oxygen. CLASSIFICATION: Carbohydrates are classified into three main groups: 1. Monosaccharides (simple sugars): They consist of a single polyhydroxyaldehyde (glucose) or ketone units (fructose). They can not be hydrolysed into simpler units. The sugar unit is sometimes referred to as glycan. 2. Oligosaccharides (oligo = few): contain from two to ten monosaccharide units joined in glycosidic bonds. e.g. disaccharides (2 units) e.g. maltose and sucrose, trisaccharides (3 units).....etc. 3. Polysaccharides (poly = many): Also known as glycans. They are composed of more than ten mon-osaccharide units e.g. starch, glycogen, cellulose.....etc.

Monosaccharides
They have the common formula (CH2O)n, where n = 3 or some larger number. CLASSIFICATION OF MONOSACCHARIDES: Can be carried out by one of two methods: 1. According to the number of carbon atoms: Trioses, tetroses, pentoses,

hexoses, heptoses, octoses. 2. According to the characteristic carbonyl group (aldehyde or ketone

group): Aldo sugars: aldoses: monosaccharides containing aldehyde group

e.g. glucose, ribose, erythrose and glyceraldehyde. Keto sugars: ketoses: monosaccharides containing ketone group e.g.

fructose, ribulose and dihydroxy acetone.

Carbohydrate Chemistry
hexose i.e. containing ketone group and six carbon atoms.

N. B.: Monosaccharides can be classified according to both methods e.g. fructose is a keto-

Forms of Monosaccharides: Trioses:

D- glyceraldehyde Tetroses:

Dihydroxyacetone

Ketose
CH 2 OH C = O HC OH CH 2 OH

D - erythrulose

D - erythrose Pentoses:

Carbohydrate Chemistry Hexoses:

Heptoses:

D - sedoheptulose N. B.:
Derivatives of trioses, tetroses and heptoses are intermediates in carbohydrate metabolism. Aldopentoses enter in structure of nucleic acids, coenzymes and certain vitamins. All simple monosaccharides are white, crystalline, solids, freely soluble in water and have a sweet taste.

Ring structure of Monosaccharides and Haworth Configuration of Cyclic Sugars: Monosaccharides of five or more carbon atoms are present in ring forms. Ring formation involves condensation of the carbonyl group (C-1 in aldoses, and C-2 in ketoses) of the sugar with one of the alcohol groups of the same sugar forming a closed ring structure.

Carbohydrate Chemistry

The carbonyl carbon atom in the cyclic form will be called the anomeric carbon and it can exist in two different forms called (with the hydroxyl group to the right) or (with the hydroxyl group to the left). Haworth suggested that monosaccharides are existing in biological systems, not as a rectangle, but in a ring structure either pyran (a ring having 5 carbons and an oxygen) or furan (a ring having 4 carbons and an oxygen).

Aldohexoses exist mainly in the pyran form (link between C-1 and C-5) while fructose, if phosphorylated or linked to other sugars, will assume the furan form (link between C-2 and C-5).

In Haworth configuration, all groups to the right of carbons are oriented down while all groups to the left of carbons are oriented up except those around carbon
5, the reverse orientation occurs.

Aldohexoses can exist either in the pyran form as glucopyranose( between the
aldehyde group at C1 and the alcohol group (C5) or the furan form as glucofuranose ( between C1 and C4).

They exist mainly in the six membered pyranose ring . Fructose can potentially form either a 5 membered furan ring (linkage between C2
and OH group of C5) or a 6-membered pyran ring (between C2 & OH group of C6).

Carbohydrate Chemistry

When fructose is linked to other sugars or when it is phosphorylated it assumes

the furanose form.

CH 2OH C

OH CH2OH O O H OH Fructofuranose H OH CH2OH

HO - C - H H - C - OH H-C CH 20H

D- Glucose

Ring form

Carbohydrate Chemistry

Carbohydrate Chemistry ASYMMETRIC CARBON ATOM:

It is a carbon atom attached to four different atoms or groups of atom e.g. the middle carbon of glyceraldehyde. Any compound having asymmetric carbon(s) possess the following properties: 1. Formation of isomers. 2. Shows optical activity. Isomers are compounds which have the same molecular weight, same percentage composition, and differ in their physical and chemical properties. IMPORTANT TYPES OF ISOMERISM:

1. D and L isomers :
They are pairs of compounds that have the same structural formulas but differ in spatial configuration; one of them is the mirror image of the other and they rotate the plane of polarised light equally but in opposite directions. LOOK AT THE PRE-LAST CARBON: If the OH is on the right: D-sugar If the OH is on the left: L-sugar Most of the monosaccharides occurring in mammals are of the D configuration. The monosaccharides with asymmetric carbon atoms are also optically active, i.e when a beam of polarized light (light vibrating in one plane) is allowed to pass through a solution of them, it will be rotated either to the: 1. right (dextrorotatory), or to the 2. left (levorotatory)

CHO HC OH CH2OH D-Glyceraldehyde

CHO HO-C- H CH2OH L-Glyceraldehyde

Carbohydrate Chemistry

Naturally occurring L sugars are not so abundant e.g. L-fucose and Lrhamnose. In humans the vast majority of the sugars are D. Two exceptions are Lfucose found in glycoproteins and L- iduronic acid found in GAG. 2. Epimers: Two monosaccharides differ only in the configuration around one specific carbon atom (not the anomeric or subterminal ones). D-glucose and D-mannose are epimers with respect to carbon atom 2, D-glucose and D-galactose are epimers with respect to carbon atom 4. 3. Aldose-Ketose isomerism: Two monosaccharides have the same molecular formulae and similar R groups but differ in their functional groups, One has an aldehyde group (aldose e.g. glucose) and the other has a ketone group (Ketose e.g. fructose). Other examples of aldose-ketose isomers include: D-glyceraldehyde and dihydroxyacetone, D-ribose and D-ribulose, D-mannose and D-fructose. They have similar R group. HC=O H - C OH R CH2 OH C=O R

Carbohydrate Chemistry 4. and anomers:

The asymmetric carbon atom obtained from the carbonyl carbon atom in the ring forms of monosaccharides is called the anomeric carbon. In cyclic forms the new asymmetric carbon (anomeric carbon) can exist as two different isomers called: - anomer (with the hydroxyl group to the right) and - anomer (with the hydroxyl group to the left). - and - anomers are isomers of monosaccharides that differ from each other only in configuration about the anomeric carbon. - anomer has the OH to the right (below the plane in the Haworth configuration). anomer has the OH group to the left (above the plane in Haworth configuration).

Carbohydrate Chemistry Monosaccharides of physiologic importance 1-Pentoses: -D-ribose is a structural element of ribonucleic acid (RNA)and coenzymes e.g. ATP, NAD, NADP and others. D-ribose-phosphate and D-ribulose-5-phosphate are formed from glucose in the body (HMS). 2-deoxy D-ribose enters in the structure of DNA. 2-Hexoses:

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a) D-glucose (grape sugar, Dextrose as D-glucose is dextrorotatory ). It is the sugar carried by the blood (normal plasma level 70-100 mg/dL) and the principal one used by the tissues. It is found in fruit juices and obtained by hydrolysis of starch, cane sugar, maltose and lactose. b) D-Fructose (honey sugar = levulose as D-fructose is levorotatory). It is found in fruit juices (fruit sugar ) and obtained from sucrose and inulin by hydrolysis. Free fructose in solution is in pyranose form, while in the combined state in sucrose or inulin, it is in furanose form. It is present in the semen in pyranose form c) D-galactose: It is obtained from hydrolysis of lactose. It is a constituent of galactolipids, glycoprotein and GAGs. It is epimer of glucose DERIVATIVES OF MONOSACCHARIDES 1. Sugar acids: oxidation products of monosaccharides Uronic acids oxidation of the last carbon By specific enzymes only the primary alcohol group is oxidized to a carboxyl group e.g. D-glucose yields D- glucuronic acid D- glucuronic acid is important as a component of many polysaccharides and also in detoxication processes). L-ascorbic acid (vitamin C) is another important naturally occurring sugar acid.

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2. Sugar alcohols: reduction products of mono-saccharides. e.g. ribose gives ribitol, glucose gives sorbitol mannose gives mannitol galactose gives galactitol ribose gives ribitol fructose gives sorbitol or mannitol The aldehyde and ketone groups of monosaccharides can be reduced, by addition of H2 non enzymatically (in the presence of metal catalyst) or by enzymes to yield the corresponding alcohol (pentitols and hexitols and So on ).

CH2 OH H- C- OH HO-C- H HO-C- H H- C-OH CH2OH

D-Sorbitol D-Mannitol D-Galactitol D-Ribitol

Carbohydrate Chemistry important in formation of phosphatidyl inositol.

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myoinositol is a cyclic sugar alcohol occurs in nature and is

CH2 OH CH OH CH2 OH Glycerol

CH2 -OH H-C OH H-C-OH H-C- OH CH2 -OH D.Ribitol OH H

OH H OH H

OH H H OH

OH

Myoinositol

3. Deoxysugars: In deoxysugars a hydroxyl group has been replaced by a hydrogen atom. The most abundant naturally occurring deoxysugars are: 2-deoxy-D ribose in DNA. 4. Aminosugars: They are monosaccharides in which the hydroxyl group at carbon 2 is replaced by an amino group (NH2). The amino group of an aminosugar may be acetylated. Naturally occurring aminosugars include, D-glucosamine, D-galactosamine and D-mannosamine.
CH2OH H OH OH H O H OH NH2
CH2OH H O H H OH H NH2 OH

CH2OH OH O H H OH H H H OH NH2

OH H

D-Glucosamine

- D- galactosamine

- D -mannosamine

5. Amino sugar acids (e.g. Neuraminic acids): They are nine-carbon amino sugar derivatives consisting of 6-carbon aminosugar linked to 3-carbon acid; the amino group is usually acetylaletd.

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Neuraminic acid is an important building unit of the structural polysaccharides in the cell coats of higher animals. Sialic acids are N-acetyl derivatives of neuraminic acid which is present in glycolipids(Gangliosides).
COOH C=O CH2 H C OH H2 N C H HO C - H H - C OH HC

Neuraminic acid (D-Mannosamine-pyruvic acid)

N-acetylneuraminic acid (NANA)

6. Glycosides There are two types of glycosides : Glycosides are compounds formed from a condensation between: O- Glycosides: A sugar and another sugar e.g. disaccharides or oligo and polysaccharides. N-glycosides: A sugar & an aglycone (non sugar radical), e.g. Nucleosides = pentose + nitrogenous base. These are components of nucleotides and nucleic acids.
NH2 N N CH 2OH O H OH H OH N N
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N
O CH 2OH O H OH H OH

Adenosine

Uridine

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DISACCHARIDES
Disaccharides have two monosaccharides, either the same or different, linked by Oglycosidic linkage. Depending on their reactions with Fehling, s solution they are classified into a group (has free anomeric carbon) , and a non reducing group (both anomeric carbons are involved in the formation of the glycosidic bond). A . Reducing disaccharides : 1.MALTOSE( Malt sugar ): Chemistry: Contains two D-glucose residues, in pyranose form, linked by -1-4 glucosidic bond. It is a abbreviated as Glc (1
H CH2OH O H OH OH H OH H O H OH H H

4) Glc.
CH2OH H OH O H OH H

Maltose The second glucose residue has a free anomeric carbon atom and is capable of: Existing in and forms. Reducing alkaline metal salts. Forming osazone. Germinating cereals and malt. Intermediate product of the action of amylases on starch. Hydrolysis: By acid or by maltase enzyme into two D-glucose units. Fermentation: It is fermented by yeast enzymes.

Sources:

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2. LACTOSE (Milk sugar ): Chemistry: -D-galactopyranose and -D-glucopyranose linked by -1,44) Glc

galactosidic linkage. It is abbreviated as Gal (1

CH2OH OH O H OH H H H H OH O

CH2OH O H OH H H OH

OH

- Lactose Since it has a free anomeric carbon on the glucose residue, lactose is: Reducing disaccharide. Capable of forming osazone. Able to occur in and forms Sources: It is only found in milk. Hydrolysis: By acid or lactase enzyme in the intestine, it yields D-galactose and Dglucose. Fermentation: It is non fermentable. B. Non reducing disaccharides : SUCROSE ( Cane sugar = Table sugar = Beet sugar ) Chemistry: It is a disaccharide of -D fructofuranose and -D-glucopyranose linked by ( -2,-1)-fructosidic linkage or (-1, 2)-glucosidic linkage. It is abbreviated as Glc (1 2) Fru.
H CH2OH O H O H OH H HOCH2 O H H OH H O H CH2OH H H O O H

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The anomeric carbon atoms of the two hexoses are linked to each other, thus, sucrose contains no free anomeric carbon atom so: It does not act as a reducing sugar. Does not form osazone. Does not occur in and forms. Sources: Sugar Cane and sugar beet . Hydrolysis: By acids or by sucrase (invertase enzyme) to D-glucose and Dfructose. Inversion: It is hydrolysis of sucrose to D-glucose and D-fructose because it is accompanied by a net change in optical rotation from dextro (of sucrose), to levo (of invert sugar).

Invert sugar:

e.g. natural honey

It is an equimolar mixture of D- glucose and D- fructose produced by hydrolysis of sucrose and it is levorotatory since the strongly levorotatory fructose produced by hydrolysis, changes (inverts) the previous dextrorotatory action of sucrose. Fermentation: It is fermentable sugar.