CHEMISTRY OF CARBOHYDRATES FOR BDS STUDENTS

1. Chemistry of Carbohydrates
Unit-1
BDS YEAR -1
SONY PETER
DEPARTMENT OF BIOCHEMISTRY
PMS COLLEGE OF DENTAL SCIENCE AND RESEARCH

2. Content
• Definition
• Biological importance and classification
• Monosaccharide’s –Glucose, fructose, galactose, mannose
• Reactions: Reducing property, oxidation, Osazone, Molisch test
• Define anomerism, epimerism with examples
• Disaccharides-lactose, maltose, sucrose
• Glycosidic bond
• amino sugars
• deoxy sugars
• Polysaccharides. Structures of starch and glycogen, Mucopolysaccharides (definition, name, components,
biochemical significance)
• Dietary fibers.

3. What are Carbohydrates?
• Organic molecules primarily composed of carbon, hydrogen and oxygen.
• literally means ‘hydrates of carbon.
Carbohydrates may be defined as polyhydroxyaldehydes or ketones or
compounds
which produce them on hydrolysis.
General Functions of Carbohydrates
Carbohydrates participate in a wide range of functions
1. They are the most abundant dietary source of energy (4 Cal/g).
2. Carbohydrates are precursors for many organic compounds
(fats, amino acids).
3. Carbohydrates (as glycoproteins and glycolipids) participate in the
structure of cell membrane and cellular functions such as cell growth, adhesion and fertilization.

4. 4. They are structural components of many organisms. These include the fiber (cellulose) of plants, exoskeleton
of some insects and the cell wall of microorganisms.
5. Carbohydrates also serve as the storage form of energy (glycogen) to meet the immediate energy demands of
the body.
Biomedical Importance of Carbohydrates
1. Chief source of energy.
2. Constituents of compound lipids and conjugated proteins.
3. Certain carbohydrate derivatives are used as drugs like cardiac glycosides/antibiotics.
4. Lactose principal sugar of milk—in lactating mammary gland.
5. Degradation products utilized for synthesis of other substances such as fatty acids, cholesterol, amino acid,
etc.
6. Constituents of mucopolysaccharides which form the ground substance of mesenchymal tissues.
7. Inherited deficiency of certain enzymes in metabolic pathways of different
carbohydrates can cause diseases,
• e.g. galactosemia, glycogen storage diseases (GSDs),
lactose intolerance, etc.
8. Derangement of glucose metabolism is seen in diabetes mellitus.

5. Classification of Carbohydrates
Three major groups—
• Monosaccharides, Oligosaccharides and Polysaccharides.
This categorization is based on the number of sugar units. Mono- and oligosaccharides are sweet to taste,
crystalline in character and soluble in water, hence they are commonly known as sugars.
Monosaccharides
simple sugars and cannot be further hydrolysed.
The monosaccharides are divided into different categories based on:-
a) Functional group--------------------------------------------------------
b) Number of carbon atoms

6. • Based on the number of carbon atoms, the monosaccharides are regarded as:-

7. • The common monosaccharides and disaccharides of biological importance are given in the Table below:-

9. Oligosaccharides
Contain 2-10 monosaccharide molecules which are liberated on hydrolysis.
Based on the number of monosaccharide units present, the oligosaccharides are further subdivided to
disaccharides, trisaccharides
Polysaccharides
are polymers of monosaccharide units with high molecular weight (up to a million).
They are usually tasteless (non-sugars) and form colloids with water.
The polysaccharides are of two types –
Homopolysaccharides and Heteropolysaccharides

10. Monosaccharides –Glucose, fructose, galactose, mannose

11. Glucose [Dextrose]
• It is the chief physiological sugar present in normal blood continually and at fairly constant level.
• All tissues utilize glucose for energy. Erythrocytes and Brain cells utilize glucose solely for energy
purposes.
• Occurs as a constituent of disaccharide and polysaccharides.
• Stored as glycogen in liver and muscles mainly.
Fructose: It is a ketohexose and commonly called as fruit sugar, as it occurs free in fruits.
• It is very sweet sugar, much sweeter than sucrose and more reactive than glucose.
• It occurs as a constituent of sucrose and also of the polysaccharide inulin.
• It is levorotatory and hence is also called laevulose.
• Galactose: Occurs as a constituent of milk sugar lactose and also in tissues as a constituent of
galactolipid and glycoproteins.
• It is an epimer of glucose and differs in orientation of H and OH on carbon-4.
• It is less sweet than glucose and less soluble in water.
• It is dextrorotatory

12. Mannose: It does not occur free in nature but is widely distributed in combination as the polysaccharide
mannan, e.g. in ivory nut.
In the body, it is found as a constituent of glycoproteins.

13. Reactions of Monosaccharides
1. Reducing properties
The sugars are classified as reducing or nonreducing.
The reducing property is attributed to the free aldehyde or keto group of anomeric carbon.
• Many tests are employed to identify the reducing action of sugars, like Benedict’s test, Fehling’s
test, Barfoed’s test etc.
• The reduction is much more efficient in the alkaline medium than in the acid medium.
[The anomeric carbon is the carbon derived from the carbonyl
carbon compound (the ketone or aldehyde functional group) of
the open-chain form of the carbohydrate molecule.]
Points to
remember

14. • Sugars reduce cupric ions (Cu2+) of copper sulphate to cuprous ions (Cu+), which form a yellow precipitate of
cuprous hydroxide or a red precipitate of cuprous oxide.
• The enediol forms of the sugars are highly reactive and are easily oxidised by
O2 and other oxidising agents and forms sugar acids. As a consequence they readily
reduce oxidising ions such as Cu++ (cupric) to cuprous.
The process of shifting a hydrogen atom from
one carbon atom to another to produce enediols
is known as tautomerization.
Sugars possessing
anomeric carbon atom undergo tautomerization
in alkaline solutions.

16. Benedict’s test : This is a test for the identification of reducing sugars, which form enediols
(predominantly under alkaline conditions).
The enediol forms of sugars reduce cupric ions (Cu2+) of copper sulfate to cuprous ions (Cu+) which form a yellow
precipitate of cuprous hydroxide or a red precipitate of cuprous oxide.
2. Oxidation

17. 3. Reduction

18. 4. Osazone formation
Phenylhydrazine in acetic acid, when boiled with reducing sugars, forms osazones.
• The first two carbons (C1 and C2) are involved in osazone formation.
• Glucose, fructose and mannose give the same type (needle-shaped)
osazones.
• Reducing disaccharides also give osazones
maltose sunflower-shaped
lactose powderpuff shaped.

19. 5. Molisch test : It is a general test for the detection of carbohydrates. The strong H2SO4
hydrolyses
carbohydrates (poly- and disaccharides) to liberate monosaccharides. The monosaccharides get dehydrated to
form furfural (from pentoses) or hydroxy methylfurfural (from hexoses) which condense with α-naphthol to form
a violet coloured complex.

20. Anomerism and Epimerism
Anomers—mutarotation
If the open-chain form of D-Glucose, which may be called as Aldehydo-D-Glucose is taken, and condense the
aldehyde group on carbon-1, with the alcoholic-OH group on carbon-5, two different forms of glucose are
formed.
When the OH group extends to right, it is α-D-Glucose and it extends to left, it is β-D-Glucose.

21. Mutarotation :Mutarotation is defined as the change in the specific optical rotation
representing the interconversion of α and β forms of D-glucose to an equilibrium mixture.
• The α and β anomers of glucose have different optical rotations. The specific optical rotation of a freshly
prepared glucose (α anomer) solution in water is +112.2° which gradually changes and attains an equilibrium
with a constant value of +52.7°.
• The optical rotation of β -glucose is +18.7°.
• The equilibrium mixture contains 63% β -anomer and 36% α -anomer of glucose with 1% open chain form. In
aqueous solution, the β form is more predominant due to its stable conformation.

22. Epimers
If two monosaccharides differ from each other in their configuration around a single specific carbon (other
than anomeric) atom, they are referred to as epimers to each other.
• For instance, glucose and galactose are epimers with regard to carbon 4 (C4-epimers). That is, they differ in
the arrangement of OH group at C4.
• Glucose and mannose are epimers with regard to carbon 2 (C2-epimers).
• The interconversion of epimers (e.g. glucose to galactose and vice versa) is known as epimerization, and a
group of enzymes—namely—epimerases catalyse this reaction.

23. Disaccharides-lactose, maltose, sucrose
Among the oligosaccharides, disaccharides are the most common.
A disaccharide consists of two monosaccharide units (similar or dissimilar) held together by a glycosidic
bond.
They are crystalline, water-soluble and sweet to taste.
The disaccharides are of two types
1. Reducing disaccharides with free aldehyde or keto group e.g. maltose, lactose.
2. Non-reducing disaccharides with no free aldehyde or keto group e.g. sucrose, trehalose.

26. The intestinal enzyme—sucrase—hydrolyses
sucrose to glucose and fructose which are
absorbed.
sucrose

27. Differentiation of lactose from sucrose

28. Glycosidic bond
A glycosidic bond or glycosidic linkage is a type of covalent bond that joins a carbohydrate (sugar)
molecule to another group, which may or may not be another carbohydrate.
A substance containing a glycosidic bond is a glycoside.
• Glycosides are formed when the hemiacetal or hemiketal hydroxyl group (of anomeric carbon) of a
carbohydrate reacts with a hydroxyl group of another carbohydrate or a noncarbohydrate (e.g. methyl
alcohol, phenol, glycerol).

30. Amino sugars
When a hydroxyl group of a sugar is replaced by an amino group, the resultant compound is an amino
sugar.
• The important amino sugars are glucosamine, galactosamine, mannosamine, sialic acid etc.
They are essential components of glycosaminoglycans, glycolipids (gangliosides) and glycoproteins.
They are also found in some oligosaccharides and certain antibiotics. e.g. erythromycin
Summary of the synthesis of amino sugars

32. Deoxy sugars
These are the sugars that contain one oxygen less than that present in the parent molecule.
The groups -CHOH and -CH2OH become -CH2 and -CH3 due to the absence of oxygen.
• D-2-Deoxyribose is the most important deoxysugar since it is a structural constituent of DNA (in contrast to D-
ribose in RNA).
• Fucose is a deoxy L-galactose found in blood group antigens, and certain glycoproteins.

33. Polysaccharides
Polysaccharides consist of repeat units of monosaccharides or their derivatives, held together by glycosidic
bonds.
• They are primarily concerned with two important functions-structural, and storage of energy.
• Polysaccharides are linear as well as branched polymers.
• The occurrence of branches in polysaccharides is due to the fact that glycosidic linkages can be formed at any
one of the hydroxyl groups (-OH) of a monosaccharide.
Polysaccharides are of two types
1. Homopolysaccharides on hydrolysis yield only a single type of monosaccharide. They are named based on
the nature of the monosaccharide. Thus, glucans are polymers of glucose whereas fructosans are polymers of
fructose.
2. Heteropolysaccharides on hydrolysis yield a mixture of a few monosaccharides or their derivatives.

34. Structures of starch and glycogen
Starch
• Starch is the carbohydrate reserve of plants.
• High content of starch is found in cereals, roots, tubers, vegetables etc. Starch is a homopolymer composed
of D-glucose units held by α-glycosidic bonds. It is known as glucosan or glucan.

38. Glycogen
Glycogen is the carbohydrate reserve in animals, hence often referred to as animal starch.
• It is present in high concentration in liver, followed by muscle, brain etc.
• It is deposited in the liver and muscle as storage material
which are readily available as immediate source of
energy.

40. MUCOPOLYSACCHARIDES

43. Chondroitin sulfates
Chondroitin 4-sulfate is a major constituent of various mammalian tissues (bone, cartilage, tendons, heart,
valves, skin, cornea etc.).
Structurally, it is comparable with hyaluronic acid.
Chondroitin 4-sulfate consists of repeating disaccharide units composed of D-glucuronic acid and N-acetyl
D-galactosamine 4-sulfate.
Heparin
Heparin is an anticoagulant (prevents blood clotting) that
occurs in blood, lung, liver, kidney, spleen etc.
Heparin helps in the release of the enzyme lipoprotein lipase
which helps in clearing the turbidity of lipemic plasma.
Heparin is composed of alternating units of N-sulfo D-
glucosamine 6-sulfate and glucuronate 2-sulfate

44. Dermatan sulfate
Mostly found in skin, dermatan sulfate is structurally related to chondroitin 4-sulfate. The only difference is that
there is an inversion in the configuration around C5 of D-glucuronic acid to form L-iduronic acid.
Keratan sulfate
It is a heterogeneous GAG with a variable sulfate content,
besides small amounts of mannose, fructose, sialic acid etc.
Keratan
sulfate essentially consists of alternating units of
D-galactosamine and N-acetylglucosamine 6-sulfate.

46. Summary
1. Carbohydrates are the polyhydroxy aldehydes or ketones, or compounds which produce them on hydrolysis.
The term sugar is applied to carbohydrates soluble in water and sweet to taste. Carbohydrates are the major
dietary energy sources, besides their involvement in cell structure and various other functions.
2. Carbohydrates are broadly classified into 3 groups—monosaccharides, oligosaccharides and
polysaccharides.
The monosaccharides are further divided into different categories based on the presence of functional groups
(aldoses or ketoses) and the number of carbon atoms (trioses, tetroses, pentoses, hexoses and heptoses).
3. Glyceraldehyde (triose) is the simplest carbohydrate and is chosen as a reference to write the configuration
of all other monosaccharides (D- and L- forms). If two monosaccharides differ in their structure around a single
carbon atom, they are known as epimers. Glucose and galactose are C4 – epimers.
4. D-Glucose is the most important naturally occurring aldose/monosaccharide. Glucose exists as α and β
anomers with different optical rotations. The interconversion of α and β anomeric forms with change in the
optical rotation is known as mutarotation.
5. Monosaccharides participate in several reactions. These include oxidation, reduction, dehydration, osazone
formation etc

47. 6. Among the oligosaccharides, disaccharides are the most common. These include the reducing disaccharides
namely lactose (milk sugar) and maltose (malt sugar) and the non-reducing sucrose (cane sugar).
7. Polysaccharides are the polymers of monosaccharides or their derivatives, held together by glycosidic bonds.
Homopolysaccharides are composed of a single monosaccharide (e.g., starch, glycogen, cellulose, inulin).
Heteropolysaccharides contain a mixture of few monosaccharides or their derivatives (e.g.,
mucopolysaccharides).
8. Starch and glycogen are the carbohydrate reserves of plants and animals respectively.
9. Mucopolysaccharides (glycosaminoglycans) are the essential components of tissue structure. They provide the
matrix or ground substance of extracellular tissue spaces in which collagen and elastin fibers are embedded.
Hyaluronic acid, chondroitin 4-sulfate, heparin, are among the important glycosaminoglycans.

48. Dietary fibers
• The complex carbohydrates that are not digested by the human enzymes are collectively referred to as
dietary fibers.
• Once regarded as a nutritional waste, a lot of importance is now given to dietary fiber in human health.