Carbohydrates

CarbohydrateS
(Hydrates of carbon') or

saccharides (Greek meaning "sugar")

Carbohydrates
Polyhydric alcohols having potentially active aldehyde and ketone groups

Carbohydrates

Monosaccharides
Aldoses (e.g., glucose) have an aldehyde group at one end.
H C H HO H H C C C C OH H OH OH O

Ketoses (e.g., fructose) have a keto group, usually at C2.

CH2OH C HO H H C C C O H OH OH

CH2OH

CH2OH

D-glucose

D-fructose

 A chain-form monosaccharide that

has a carbonyl group (C=O) on an end carbon forming an aldehyde group (CHO) is classified as an aldose. When the carbonyl group is on an inner atom forming a ketone, it is classified as a ketose.

 The basic carbohydrate unit is

called Monosaccharide The general formula of an unmodified monosaccharide is (CH2O)n, where n is any number of three or greater

Carbohydrates
Include large group of compounds commonly known as starches or sugars which are widely distributed in plants and animals

Carbohydrates or hydrates of carbon Empirical formula :

Cn(H2O)n
2 to 1 ratio of hydrogen to oxygen

Biological Significance
1. Carbohydrates are the main source of energy in the body.

When oxidized in the body, they liberate CO2, water and energy.

Biological Significance
1.Carbohydrates are the main source of energy in the body.

Supply the major portion of energy required by living cells. Brains cells and RBCs are almost wholly dependent on carbohydrates as energy source.

Biological Significance
2. Certain products of carbohydrate metabolism act as catalysts to promote oxidation of foodstuffs.

Biological Significance
3. Certain carbohydrates are the starting materials for the biological synthesis of fatty acids and amino acids.

Biological Significance
4. Carbohydrates save proteins from being used for the production of energy.

Sources
Foods that are high in carbohydrates

include breads, pastas, beans, potatoes, bran, rice and cereals.

Occurrence
Carbohydrates are widely distributed in plant and animal tissues.

Occurrence
In plants, they are produced by photosynthesis and include the starches of the plant framework and plant cells.

Occurrence
Glycogen is the storage form of carbohydrates in animals found abundantly in the liver and muscles Sucrose cane sugar; also present in the nectar of flowers and in fruits

Occurrence
Glucosides which are derivatives of carbohydrates are found in certain plants

Glucose is the sugar in the blood and other body fluids

Lactose milk

General Properties
Physical Properties: Forms: The monosaccharides and disaccharides are white crystalline substances. Starches are amorphous powder. Complex cellulose is fibrous

General Properties
Solubility: Monosaccharides and disaccharides readily dissolve in water. Higher carbohydrates like starch dissolve only slightly. Cellulose is practically insoluble.

General properties
Relative Sweetness: fructose invert sugar Sucrose glucose galactose Maltose
Lactose xylose starch

Carbohydrates with lower molecular weight have sweet taste.

Other Properties
Many saccharide structures differ only in the

orientation of the hydroxyl groups (-OH).

This slight structural difference makes a big

difference in the biochemical properties, organoleptic properties (e.g., taste), and in the physical properties such as melting point and Specific Rotation (how polarized light is distorted).

Other Properties
Stereoisomerism : Same structural formula but

differ in spatial configuration With respect to the Penultimate Carbon atom glucose has 2 stereoisomers D-glucose and Lglucose

D-Glucose

L-Glucose

C H C OH HO C H H C OH H C OH CH2OH
D-glucose

C HO C H H C OH HO C H HO C H CH2OH
L-glucose

D & L sugars are mirror images of one another. They have the same name, e.g., D-glucose & L-glucose.

 Optical Activity :

Rotation of Plane polarized light and (+)glucose or ()glucose respectively

D-glucose

L-glucose

Epimers
Structures that have opposite

configurations of a hydroxyl group at only one position (C2 or C4) such as glucose and mannose; glucose and galactose

D-glucose

Chemical Properties
Osazone formation with phenylhydrazine
Benedicts test Oxidation

Reduction to Alcohols, etc.

Structural Representation of Carbohydrates

Open Chain Structure / Linear Structure/

Fischer Structure

Hemi-acetal Structure
Haworth Structure

Open Chain Structure

Long Straight chain form of

carbohydrates

Haworth Structure
Presence of a Pyranose Ring

Pentoses and hexoses can cyclize as the ketone or aldehyde reacts with a distal OH. Glucose forms an intra-molecular hemiacetal, as the C1 aldehyde & C5 OH react, to form a 6-member pyranose ring, named after pyran.

CHO C C C C OH H

H HO H H

2 3 4 5 6

D-glucose

OH (linear form) OH

CH2OH
6 CH2OH

6 CH2OH

H
4

O H
2

H
1

H
4

O H
2

OH
1

H OH
3

H OH
3

OH

OH

OH

OH

OH

-D-glucose

-D-glucose

CH2OH O H OH OH HOH2C 6
5

2C

HO H H

C C C

O H HO
3

1 CH2OH 2

4 5 6

CH2OH

OH

OH

D-fructose (linear)

-D-fructofuranose

Fructose forms either a 6-member pyranose ring, by reaction of the C2 keto group with the OH on C6, or a 5-member furanose ring, by reaction of the C2 keto group with the OH on C5.

Hemi-acetal Structure
The 1st Carbon in glucose condenses with

the OH group of the 5th Carbon to form a ring

Classification :
1) The most useful Classification Scheme

divides the carbohydrates into groups according to the number of individual simple sugar units

1)Monosaccharide 2)Disaccharides 3)Polysaccharides

2) Number of Carbons 3) Functional Groups

MONOSACCHARIDE
Monosaccharides are the simplest

carbohydrates in that they cannot be hydrolyzed to smaller carbohydrates. The general chemical formula of an unmodified monosaccharide is (CH2O)n, where n is any number of three or greater.

The Killiani Synthesis

Tetroses

D-Erythrose

D-Threose

Pentoses

 The ring form of ribose is a component of

ribonucleic acid (RNA).Deoxyribose, which is missing an oxygen at position 2, is a component of deoxyribonucleic acid (DNA). In nucleic acids, the hydroxyl group attached to carbon number 1 is replaced with nucleotide bases.

Hexoses
Hexoses, such as the ones illustrated

here, have the molecular formula C6H12O6.

German chemist Emil Fischer (1852-

1919) identified the stereoisomers for these aldohexoses in 1894. He received the 1902 Nobel Prize for chemistry for his work.

Heptoses
Sedoheptulose has the same structure

as fructose, but it has one extra carbon.

Disaccharides
contain two sugar units. In almost all cases one of the sugars

is glucose, with the other sugar being galactose, fructose, or another glucose. lactose, and sucrose.

Common disaccharides are maltose,

Disaccharide descriptions and components

Trisaccharides
Raffinose, also called melitose, is

a trisaccharide that is widely found in legumes and cruciferous vegetables, including beans, peas, cabbage, brussels sprouts, and broccoli. It consists of galactose connected to sucrose via a 16 glycosidic linkage.

Trisaccharides
Humans cannot digest

saccharides with this linkage and the saccharides are fermented in the large intestine by gasproducing bacteria.

Polysaccharides
contain many sugar units in long

polymer chains of many repeating units. The most common sugar unit is glucose. Common poly saccharides are starch, glycogen, and cellulose.

Classification
1. 2.

*starch, glycogen, inulin, dextrin

Starch Group

Cellulose Group a. cellulose b. hemicellulose Pentosans gum arabic Hexosans agar-agar Hexopentosans - pectins

According to nature of units

Homopolysaccharides

only one kind of monosaccharide unit

mixtures of monosaccharides + derived products

Heteropolysaccharides

According on the type of linkages

Linear polysaccharides

only one kind of glycosidic linkage two or more kinds of linkages

Branched polysaccharides

 Starch is the major form of stored

Starch

carbohydrate in plants. Starch is composed of a mixture of two substances: amylose, an essentially linear polysaccharide, and amylopectin, a highly branched polysaccharide. polymers of -D-Glucose. Natural starches contain 10-20% amylose and 80-90% amylopectin.

Amylose molecules -consist typically of 200 to 20,000 glucose units which form a helix as a result of the bond angles between the glucose units.

 Amylopectin -differs from amylose in

being highly branched.

Short side chains of about 30 glucose

units are attached with 16 linkages approximately every twenty to thirty glucose units along the chain.
two million glucose units.

Amylopectin molecules may contain up to

Inulin
Inulins are present in many vegetables

and fruits, including onions, leeks, garlic, bananas, asparagus, chicory, and Jerusalem artichokes. Inulins are polymers consisting of fructose units that typically have a terminal glucose.

Glycogen
Glucose is stored as glycogen in animal

tissues by the process of glycogenesis.

When glucose cannot be stored as

glycogen or used immediately for energy, it is converted to fat.

CH2OH H H OH OH H CH2OH H OH H OH O H OH H H O H OH CH2OH O H OH H H O H H O H

CH2OH O H OH H H OH H 1 O 6 CH2 5 H OH 3 H CH2OH O H 2 OH 1 O H H O H 4 OH H H O OH H H

glycogen

CH2OH O H OH H H OH OH H

H O

H 4

OH

Glycogen, the glucose storage polymer in animals, is similar in structure to amylopectin. But glycogen has more (16) branches. The highly branched structure permits rapid glucose release from glycogen stores, e.g., in muscle during exercise. The ability to rapidly mobilize glucose is more essential to animals than to plants.

Cellulose
polymer of -D-Glucose, which in

contrast to starch, is oriented with CH2OH groups alternating above and below the plane of the cellulose molecule thus producing long, unbranched chains.

CH2OH H OH H OH O H OH H 1 O H H

6CH OH 2 5 O

CH2OH H O H H OH O H OH H H O H

CH2OH O H OH H H H OH O H

CH2OH O H OH H H H OH OH

H 4 OH
3

H 1
2

OH

cellulose
Cellulose, a major constituent of plant cell walls, consists of long linear chains of glucose with (14) linkages. Every other glucose is flipped over, due to linkages.

Cellulose
Cellulose is the major structural

material of plants. Wood is largely cellulose, and cotton is almost pure cellulose. Cellulose can be hydrolyzed to its constituent glucose units by microorganisms that inhabit the digestive tract of termites and ruminants.

 Cellulose may be modified in the

laboratory by treating it with nitric acid (HNO3) to replace all the hydroxyl groups with nitrate groups (-ONO2) to produce cellulose nitrate (nitrocellulose or guncotton) which is an explosive component of smokeless powder.

 Partially nitrated cellulose,

known as pyroxylin, is used in the manufacture of plastics, lacquers, and nail polish.

Hemicellulose
applied to the polysaccharide

components of plant cell walls other than cellulose, or to polysaccharides in plant cell walls which are extractable by dilute alkaline solutions.

Hemicellulose
The chemical structure of

hemicelluloses consists of long chains of a variety of pentoses, hexoses, and their corresponding uronic acids.

Dextran
Dextran is a polysaccharide similar

to amylopectin, but the main chains are formed by 16 glycosidic linkages and the side branches are attached by 13 or 14 linkages.

Dextran
Dextran is an oral bacterial

product that adheres to the teeth, creating a film called plaque. It is also used commercially in confections, in lacquers, as food additives, and as plasma volume expanders.

Heteropolysaccharides

- monosaccharides and derived products

1. neutral mucopolysaccharide those occurring in bacteria mucoids including immunological, specific blood group substances

2. acid mucopolysaccharide cartilage tissues skin

D-glucuronate
6COO

CH2OH
5

H O H
2 1 4

O H
1 O

H
4

H OH
3

OH O

NHCOCH3

OH

N-acetyl-D-glucosamine

hyaluronate

Mucopolysaccharides- Glycosaminoglycans are linear polymers of repeating disaccharides.

The constituent monosaccharides tend to be modified, with acidic groups, amino groups, sulfated hydroxyl and amino groups, etc.

heteropolysaccharides
3. hyaluronic acid complex mucopolysaccharide main constituent of the ground substance of connective tissues abundant in:

synovial fluid vitreous humour aqueous humour

heteropolysaccharides
in

tissues, it serves as a cementing substance which allows the passage of metabolites fragmented by an enzyme, hyaluronidase, also called the spreading factor
bacteria sperms poisonous secretions of reptiles and other animals

Xylan -

HOMOPOLYSACCHARIDE

Digestion of Carbohydrates
Polysaccharides in the mouth are

broken through the introduction of amylase, a digestive enzyme in saliva. The high acid content of the stomach inhibits amylase activity, so carbohydrate digestion is suspended in the stomach.

 Pancreatic amylase is secreted by

Digestion of Carbohydrates

the pancreas into the duodenum and works with other enzymes to complete the breakdown of carbohydrate into a monosaccharide Is then absorbed into the surrounding capillaries of the villi.

Nutrition
Carbohydrates are not essential

nutrients The body can obtain all its energy from protein and fats Carbohydrates contain 3.75 Kilocalories An essential diet contains between 40-65% of dietary energy from carbohydrates

Glycemic Index
A measure of the effects of

carbohydrates on blood glucose levels. Carbohydrates that break down rapidly have a high GI; Those that break down slowly, releasing glucose gradually into the bloodstream, have a low GI

Glycemic Index
A lower glycemic response is

often thought to equate to a lower insulin demand, better long-term blood glucose control and a reduction in blood lipids.

Classification

GI range

Examples

Low GI

>55 %

Moderate GI

55 69 %

High GI

70 and above

most fruit and vegetables, grainy breads, pulses wheat bread, whole wheat products, brown rice, orange corn flakes, baked potato, white bread

Structure of monosaccharides, disaccharides and polysaccharides

Formation of maltose and sucrose from their monosaccharides

Structure:Function of polysaccharides

Functions of Carbohydrates
Carbohydrates spare protein from

being used up as an energy source. If there are not enough carbohydrates, then large amounts of fat are used for energy. The body is not able to handle this large amount so quickly, so it accumulates ketone bodies

Functions of Carbohydrates
Carbohydrate is necessary for the

regulation of nerve tissue and is the source of energy for the brain. Some carbohydrates are high in fibre, which helps prevent constipation Structural components

 play a major role in promoting your

health fitness. Immediate respiratory substrates e.g. glucose Energy stores e.g. glycogen in mammals starch in plants

 Structural components e.g. cellulose

in plant cell walls chitin in arthropod exoskeletonnpentose sugars - ribose and deoxyribose are components of RNA and DNA respectively.

 Metabolites i.e. intermediates in

biochemical pathways Cell-to-cell attachment molecules e.g. combined with proteins to form glycoproteins or lipids to form glycolipids on plasma membrane Transport e.g. sucrose in plant phloem tissue