Carbohydrates

Definition:
Organic compounds composed of C, H and O with H and O present in the same ratio as in water.
E.g. Glucose C6H12O6.

Exceptions:
Deoxy sugars such as Rhamnose C6H12O5, digitoxose C6H12O4 Some non carbohydrates follow the definition:
Acetic acid C2H4O2 Formaldehyde HCHO Lactic acid C3H6O3

New definition: Optically active Polyhydroxy aldehydes or ketones, or substances that hydrolyze to yield polyhydroxy aldehydes or ketones.

Carbohydrates

Sugars (Saccharides)

Non-Sugars (Polysaccharides) More than 10 sugar unites

Monosaccharides
Trioses e.g. Glyceraldehyde Tetroses e.g. Erythose Pentoses e.g. Arabinose Hexoses

Disaccharides

Oligosaccharides (3- 10 unites)

Trisaccharides e.g. Raffinose

Reducing Lactose Maltose Cellibiose

Non-Reducing Sucrose

Tetrasaccharides

Pentasaccharides

Aldohexeoses Glucose

Ketohexeoses Fructose

Non-Sugars (Polysaccharides) More than 10 sugar unites

Homopolysaccharides Holosaccharides

Heteropolysaccharides Gums Mucilages Pectins Agar Heparin Alginate

Hexosanes

Pentosans Xylans

Glucosans Starch Glycogen Cellulose Dextrins

Fructosans Inulin

Physical Characters
Condition:
Sugars are white, crystalline in shape and with sharp melting points, while polysaccharides are white amorphous solids.

Taste:
Sugars have a sweet taste. Polysaccharides are tasteless.

Solubility:
Monosaccharides are soluble in cold water and hot alcohol. Polysaccharides are partially soluble in hot water.

 Optical activity:
A compound is optically active when, in solution, it is capable to rotate the plane of polarized light either to right (dextrorotatory, + or d) or to the left (levorotatory, - or l).

Nickel prism Plane polarized light Normal light

The optical activity of a compound is measured by determination of its specific optical rotation ([] Dt) using a polarimeter, and applying the following equation:

[]D25 = /LC
Where: = extension of rotation, L = length of tube (light path) in decimeter, C = concentration g /ml, 25 = operating temperature (t) in 0C, D = line spectrum of sodium light (589 nm).

Sugar isomers:
Hexoses like glucose have 4 asymmetric (chairal) carbons. Number of isomers can be calculated from the formula: Number of isomers = 2n = 24 = 16

CHO * CH OH * HO CH * CH OH * CH OH CH2OH

D and L in sugars:
A monosaccharide in which the OH group attached to the carbon atom next to the CH2OH (farthest asymmetric carbon atom from the carbonyl group) is always to the right is designated as a D-sugar and that with the same OH to the left as L -sugar. D and L designations are like (R) and (S) designations in that they are not necessarily related to the optical rotations of the sugars to which they are applied. Thus, one may encounter sugars that are D (+) or D (-) and others that are L (-) or L (+).

CHO H OH CH2OH
D-Glyceraldehyde

CHO HO H CH2OH
L-Glyceraldehyde

- and - anomers of glucose:

When sugars under go cyclization C-1 became a new chairal carbon and two isomers exist. They are called Anomers. In the -anomer the OH group is directed downside and in the -anomer is directed to the upper side. These two forms have different specific rotation, in solution an equlibrium exsit between the two forms (mutarotation phenomenon).
H OH HO HO H H O H OH OH H OH
6

1 H

HO HO H

H O H OH H

CH 2OH O H OH H H OH H
1

CH 2OH H OH H OH O H OH H H OH

1 OH
OH

OH

-glucopyranoside Chair forms

-glucopyranoside

-glucopyranoside

-glucopyranoside

Haworth formulations

Mutarotation
When a sugar is dissolved in water, the specific rotation of the solution gradually changes until it reaches to a constant value due to equilibrium between the and forms. e.g. freshly prepared solution of -glucose has a specific rotation +112o. When this solution is allowed to stand the rotation falls till reach + 52.7o. The equilibrium reached is: 36% D- glucose []D = + 18.7 0 64% D- glucose []D = + 112 0 The sum is + 52.7o

Terms used to describe isomerism:

Glucose and Galactose are different from each other in the stereochemistry of carbon 4. They are described as Epimers. Glucose and Mannose are different from each other in the stereochemistry of carbon 2. They are described as Epimers.
Epimers: CHO CH OH HO CH CH OH CH OH CH2OH D-Glucose CHO CH OH HO CH HO CH CH OH CH2OH D-Galactose CHO CH OH HO CH CH OH CH OH CH2OH D-Glucose CHO HO CH HO CH CH OH CH OH CH2OH D- Mannose

 Galactose and Mannose are different from each other in the stereochemistry of carbons 2 and 4. They are described as DiastereoisomersDiastereomers.
Diastereomers: CHO CH OH HO CH HO CH CH OH CH2OH D-Galactose CHO HO CH HO CH CH OH CH OH CH2OH D- Mannose

 Glucose and Fructose have the same molecular formula C6H12O6. They have different structures with different function groups. They are described as Structural Isomers.
Structural isomers: CHO CH OH HO CH CH OH CH OH CH2OH D-Glucose CH2OH CO HO CH CH OH CH OH CH2OH D-Fructose

Chemical Reaction Related to Colour Tests for Carbohydrates

Effect of conc. acids:
Treatment with conc. mineral acid (HCl or H2SO4) leads to dehydration of sugars and formation of the corresponding furfural.
Furfural Volatile

Pentoses

CHO

Hexoses

HOH 2C

CHO

5-Hydroxymethyl furfural less volatile

 Reaction of furfural with amines resulted in Shiffs bases with different colours used as colour tests such as:

Molischs test:
Any carbohydrate + Alcoholic -naphthol then add conc. H2SO4 on the wall of the test tube Violet ring between the two layers.

Resorcinol test (for keto-hexoses):

Sugar solution + few crystals of Resorcinol + Equall volume of conc. HCl and warm on water bath Rose Red Colour.

Furfural test (Differentiate between Pentoses and Hexoses):

Pentose + Coc. Acid and heat, expose the vapours to Aniline acetate paper Red colour Hexoses give negative result.

Effect of Alkalis
Strong alkalis:
Polymerization.

Weak alkalis:
Isomerization.
H C=O CH OH HO CH CH OH CH OH CH2OH D-Glucose

CHOH C OH HO CH CH OH CH OH CH2OH

CH2OH C=O HO CH CH OH CH OH CH2OH

D-Fructose

CHO HO CH HO CH CH OH CH OH CH2OH
D- Mannose

Oxidation
Mild Oxidation: These are oxidizing agents like Bromine water that convert the CHO group to COOH to produce onic acids. Colour tests based on this reaction: Fehlings reduction test:
Sugar solutions + Fehlings A (CuSO4) + Fehlings B (NaOH, NaK tartarate rochell salt), heat on water bath Red Precipitate

RCHO + Cu++

RCOOH + Cu2O

CHO CH OH HO CH CH OH CH OH CH2OH
D-Glucose

I2 or Fehling's

COOH CH OH HO CH CH OH CH OH CH2OH
Gluconic acid

Barfoeds test:
Sugar solution + Barfoeds reagent (Cu Acetate/Acetic acid), heat for 3 minutes on boiling water bath Red ppt with monosaccharides only.
Acidic medium decreases the oxidation power of Cu++.

Strong Oxidation
These are oxidizing agents like HNO3 that convert the CHO and CH2OH group to COOH to produce aric acids.
CHO CH OH HO CH CH OH CH OH CH2OH
D-Glucose

HNO 3

COOH CH OH HO CH CH OH CH OH COOH
Saccharic acid

 Glalactaric acid (Mucic acid) test:

Oxidation of galactose resulted in the formation of Galactaric acid. It is a meso compound insoluble in water and have zero optical rotation.

CHO CH OH HO CH HO CH CH OH CH2OH
D-Galactose

HNO 3

COOH CH OH HO CH HO CH CH OH COOH
Galactaric acid

Enzymatic oxidation
Takes place in plants and resulted in the oxidation of the primary alcohol group only producing uronic acids.
CHO CH OH HO CH CH OH CH OH CH2OH
D-Glucose

CHO CH OH HO CH CH OH CH OH COOH
Glucuronic acid

COOH O H H OH OH H OH H H OH

Reduction
This resulted in the reduction of the CHO to CH2OH producing Sugar Alcohols. Sodium borohydride or H2/Pt are examples of reducing agents.
Glucose Galactose Mannose Sorbitol Dulcitol Mannitol

CHO CH OH HO CH CH OH CH OH CH2OH
D-Glucose

CH2OH CH OH HO CH CH OH CH OH CH2OH
Sorbitol

Pentoses
Examples:
-D-Ribose: found in all plant and animal cells as the carbohydrate part of nucleic acids e.g. ribonucleic acid (RNA). -D-Xylose (or wood sugar): prepared from corncobs, bran, straw (or any woody material) by boiling with acids, fermenting out any glucose present with yeast, and crystallizing the D-xylose from the evaporated solution. -L-Arabinose (or pectin sugar): found in gums, pectic substances, accompanying hemicelluloses and forms the sugar part of several glycosides.
CHO CH OH HO CH HO CH CH2OH L-Arabinose CHO CH OH CH OH CH OH CH2OH D-Ribose CHO CH OH HO CH CH OH CH2OH D-Xylose

Hexoses
1- -D-Glucose
(dextrose, grape sugar, blood sugar or cornmon sugar) Occurrence:
Widely distributed in nature. Present in Grape and blood.

Preparation:
D-Glucose is commercially prepared from starch by:
Autoclaving (at 150 0C) an aqueous starch suspension (15-20%) with dilute
acid (0.03 N hydrochloric acid) for 30 minutes (complete hydrolysis).
CHO CH OH HO CH CH OH CH OH CH2OH D-Glucose CH2OH O OH H H OH H H OH H OH D-Glucopyranose

 Uses:
As source of energy either by mouth or IV injection. IV solutions to restore blood volume. Shocks following insulin administration. As osmotic diuretic. Sweetening agent for Pharmaceutical preparations, ice-cream and candy.

Liquid glucose: Preparation:

It is prepared by partial acid hydrolysis of starch using dilute hydrochloric acid and heating for 20 minutes at about 30 pounds pressure.

Composition:
It consists of a mixture of glucose, dextrin, maltose and water.

Uses:
Used as sweetening agent, as substitute for sucrose and as an excipient in massing pills.

2- Fructose
(Levulose, Fruit Sugar)
Preparation:
Acid hydrolysis of Inulin. Hydrolysis of Sucrose.

Sucrose

Acid or Enzyme

Fructose + Glucose
Ca(OH)2

Ca fructosate ppt

Ca glucosate Solution

CH2OH C O HO CH CH OH CH OH CH2OH D-(-)-Fructose

HOH 2C

OH

HO CH2OH OH OH -D-(-)-Fructofuranose

Uses:
Infant food. Diabetic food. Diet control.

Some Monosaccharide derivatives in Pharmacy and Medicine

Gluconic acid and its salts:
Preparation:
Gluconic acid is prepared from glucose by mild oxidation using either dilute HNO3 or Br2/Na2CO3 or Electrically or by fermentation using
Acetobacter aceti.

Uses:
Ca gluconate is used (by i.v. or orally) for treatment calcium deficiency. Ferrous gluconate, (orally or by i.v.) is used in iron deficiency.

These salts are characterized by being more easily adsorbed than other Ca or Fe salts.

 Glucuronic Acid:
Naturally present in Gums and Mucilage's. It can be prepared by Enzymatic oxidation of glucose. Uses:
Treatment of certain arthritic condition as it is a component of cartilages, joint capsules and fluids, nerve sheath and tendons.

Aurothioglucose:
Treatment of rheumatic arthritis by IM injection.

CH2OH O H H H OH OH H H S OH Au

Aurothioglucose

 Auranofin:
It is the alkyl Phosphine Gold complex with Acetylated thioglucose. Treatment of rheumatic arthritis orally.
CH2OR O S H H OR H H OR

Au P(C2H5)3

Sorbitol and Mannitol:

Preparation:

OR H

R= COCH3

Sorbitol is prepared by reduction of glucose and mannitol by reduction of mannose.

Auranofin

Uses: Sorbitol is used as a mild laxative, in preparation of spans and tweens, sweetening agent, osmotic diuretic and in some food and cosmetics industries. Mannitol is used as an osmotic diuretic, laxative, , vasodilator (mannitol hexanitrate), antineoplastic (mannitol- (mannitol hexanitrate). nitrogen mustard) and in laboratory diagnosis of kidney function.