CARBOHYDRATES CHEMISTRY:

Objectives
 Define carbohydrates in chemical terms.
 Classify carbohydrates into three major groups with examples of each group.
 List the monosaccharides of biological importance and learn their properties.
 List the disaccharides of biological importance and learn their properties.
 List the polysaccharides of biological importance and learn their properties.
 Study the chemistry and functions of glycoproteins.

Introduction
 Carbohydrates are the most abundant macromolecules in nature. They are the main source and storage of
energy in the body.
 They serve also as structural component of cell membrane.
 The general molecular formula of carbohydrate is CnH2nOn or (CH2O)n, where n > 3. Chemically,
they contain the elements Carbon, hydrogen and oxygen. Thus they are Carbon compounds that
contain large quantities of Hydroxyl groups.
 Carbohydrates in general are polyhydroxy aldehydes or ketones or compounds which give these
substances on hydrolysis.

CLASSIFICATION AND STRUCTURE

Classification
There are three major classes of carbohydrates
I. Monosaccharides (Greek, mono = one)
II. Oligosaccharides (Greek, oligo= few) 2-10 monosaccharide units.
III. Polysaccharides (Greek, Poly = many) >10 monosaccharide units.
I. MONOSACCHARIDES
Monosaccharides also called simple sugars. They cannot be further hydrolysed. They consist of a single
polyhydroxy aldehyde or ketone units. The most abundant monosaccharides in nature are the 6-carbon sugars
like D-glucose and fructose.
Structure
Monosaccharide has a backbone, which is un- branched, single bonded carbon chain. One of the carbon atoms
is double bonded to an oxygen atom to form carbonyl group. Each of the other carbon atoms has a hydroxyl
group. Example: Structure of Glucose

(Open chain (Alpha D-Glucose (Alpha D-Glucose

D- Glucose) Fisher Projection) Haworth Formula)

Fig 1: Structure of D-Glucose.

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There are two families of monosaccharides. Monosaccharides having aldehyde groups are called Aldoses and
monosaccharides with Ketone group are Ketoses. Depending on the number of carbon atoms, the
monosaccharides are named trioses (C3), tetroses (C4), pentoses (C5), hexoses (C6), heptoses (C7).
No of carbon Generic name Aldose Family Ketose Family
atoms
3. Triose Aldotriose Eg.Glyceraldehyde. Ketotriose Eg. Dihydroxyacetone

4. Tetrose Aldotetrose Eg. Erythrose Ketotetrose Eg. Eyrthrulose

5. Pentose Aldopentose Eg. Ribose Ketopentose Eg. Ribulose,Xylulose

6. Hexose Aldohexose Eg. Glucose, Ketohexose Eg. Fructose

Galactose, Mannose
Table 1: Common Biologically important monosaccharides with their families.

PHYSICAL AND CHEMICAL PROPERTIES OF MONOSACCHARIDES

PHYSICAL PROPERTIES
Physical properties of Monosaccharides
They are colorless, crystalline compounds, readily soluble in water. Their solutions are optically active and
exhibit the phenomenon of mutarotation (the change in specific rotation of a chiral compound due to
epimerization). Carbohydrates spontaneously change between α and β configuration.
Asymmetric Center and Stereoisomerism
 Asymmetric carbon is a carbon that has four different groups or atoms attached to it and having
optically activity in solution.
 Isomers: same structural formula but differing in spatial configuration.
 All the monosaccharides except dihydroxyacetone contain one or more asymmetric or chiral carbon
atoms and thus occur in optically active isomeric forms. Monosaccharides with n number of asymmetric
centers will have (2n) isomeric forms. (n= number of asymmetric carbon atoms).

Fig 2: The two isomeric forms of glyceraldehydes.

 The designation of a sugar isomer as the D- form or of its mirror images the L- form is determined by
the spatial relationship to the parent compound of the carbohydrate family. The D and L forms of
Glyceraldehyde are shown in the Figure 2.

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  The orientation of -OH and -H groups around the carbon atom adjacent to the terminal primary alcohol
carbon determines its D or L form .When the -OH group on this carbon is on the right, the sugar is a
member of the D-series, when it is on the left, it is a member of the L-series. These D and L
configuration are also called Enantiomers (each of a pair of molecules that are mirror images of each
other).

Optical Activity
 The presence of asymmetric carbon atom causes optical activity. When a beam of plane polarized light
is passed through a solution of carbohydrate it will rotate the light either to right or to left. Depending on
the rotation, molecules are called dextrorotatory (+) (d) or levorotatory (-) (l).
 Thus, D- glucose is dextrorotatory but D- fructose is levorotatory. When equal amounts of D and L
isomers are present, the resulting mixture has no optical activity, since the activities of each isomer
cancel one another. Such a mixture is called racemic or DL mixture.

Epimers
 When sugars are different from one another, only in configuration with regard to a single carbon atom
(around one carbon atom) they are called epimers of each other.
 For example glucose and mannose are epimers. They differ only in configuration around C2. Mannose
and Galactose are epimers of Glucose.

Fig 2.1: Structure of D - glucose, D-mannose and D- Galactose.

Anomers (the alpha and beta cyclic forms of D-glucose are known as anomers)
The two stereoisomers at the hemiacetal (anomeric) carbon are:
a. The alpha anomer: Where- OH group is down (Haworth).
b. The beta anomer:Where- OH group is up (Haworth)
Anomers are diastereomers (having different physical properties)

Mutarotation
The change in the optical rotation because of the change in the equilibrium between two anomers, when the
corresponding stereocenters interconvert. Cyclic sugars show mutarotation as α and β anomeric forms
interconvert. The optical rotation of the solution depends on the optical rotation of each anomer and their ratio
in the solution.

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Cyclization of Monosaccharides
 Monosaccharides with five or more carbon atoms in the backbone usually occur in solution as cyclic or
ring structure, in which the carbonyl group is not free as written on the open chain structure but has
formed a covalent bond with one of the hydroxyl group along the chain to form a hemiacetal or
hemiketal ring. In general, an aldehyde can react with an alcohol to form a hemiacetal or acetal.

 The C-1 aldehyde in the open-chain form of glucose reacts with the -5th carbon atom containing
hydroxyl group to form an intramolecular hemiacetal. The resulting six membered ring is called
pyranose because of its similarity to organic molecule Pyran.
 Two different forms of glucose are formed when the OH group extends to right it is α-D-Glucose and
when it extends to left, it is β-D-Glucose commonly called as Anomers. Similarly, a ketone can react
with an alcohol to form a hemiketal or ketal. The C-2 keto group in the open chain form of fructose can
react with the 5th carbon atom containing hydroxyl group to form an intramolecular hemiketal. This five
membered ring is called furanose because of its similarity to organic molecule furan.

Fig 2.2: α and β forms of Fructose.

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REACTIONS (CHEMICAL PROPERTIES)
1. TAUTOMERISATION OR ENOLISATION:
 The process of shifting hydrogen atom from one carbon to another to produce enediols is known as
tautomerisation.

2. REDUCING PROPERTIES:
 The enediol forms (explained above) or 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.

3. OXIDATION:
Depending on the oxidizing agent used, the terminal aldehyde (or keto) or the terminal alcohol or both the
groups may be oxidized. For instance, consider glucose:
 Oxidation of aldehyde group (CHO ------> COOH) results in the formation of gluconic acid.
 Oxidation of terminal alcohol group (CH2OH ------> C OOH) leads to the production of glucuronic
acid.

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 4. REDUCTION:
 When treated with reducing agents such as sodium amalgam, the aldehyde or keto group of
monosaccharide is reduced to corresponding alcohol, as indicated by the general formula :

 The important monosaccharides and their corresponding alcohols are given below.

5. DEHYDRATION:
 When treated with concentrated sulfuric acid, monosaccharides undergo dehydration with an
elimination of 3 water molecules. Thus hexoses give hydroxymethyl furfural while pentoses give
furfural on dehydration. These furfurals can condense with phenolic compounds (a-naphthol) to
form coloured products. This is the chemical basis of the popular Molisch’s test.

6. OSAZONE FORMATION:
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  Phenylhydrazine in acetic acid, when boiled with reducing sugars, forms osazones.

7. FORMATION OF ESTERS:
 The alcoholic groups of monosaccharides may be esterified by non-enzymatic or enzymatic
reactions. Esterification of carbohydrate with phosphoric acid is a common reaction in metabolism.
Glucose 6-phosphate and glucose 1-phosphate are good examples.

II. OLIGOSACCHARIDES
Oligosaccharides contain 2 to 10 monosaccharide units. The most abundant oligosaccharides found in nature are
the DISACCHARIDES.
Disaccharides
When two monosaccharides are covalently bonded together by glycosidic linkages a disaccharide is formed.
Glycosidic bond is formed when the hydroxyl group on one of the sugars reacts with the anomeric carbon on
the second sugar. Biologically important disaccharides are sucrose, maltose, and Lactose.
Maltose
Maltose contains two D glucose residues joined by a glycosidic linkage between OH at the first carbon atom of
the first glucose residues and OH at the fourth carbon atom of the second glucose forming a α-(1,4) glycosidic
linkage as shown in Figure below. Maltose is the major degradative product of Starch.Maltose is hydrolyzed to
two molecules of D- glucose by the intestinal enzyme maltase, which is specific for the α- (1, 4) glycosidic
bond.
Source for maltose:
Maltose is present in germinating cereals and in barley. Commercial malt sugar contains maltose. It may be
formed during the hydrolysis of starch.

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Fig 2.3: Structure of Maltose.

Lactose
Lactose is a disaccharide of β-D galactose and β-D- glucose which are linked by β-(1,4) glycosidic linkage.
Lactose acts as a reducing substance since it has a free carbonyl group on the glucose.
Source for lactose:
Lactose is synthesized in mammary gland and hence it occurs in milk.

Fig 2.4: Structure of Lactose.

Sucrose (Cane sugar)

Sucrose is a disaccharide of α- D- glucose and β-D-fructose. It is obtained from cane sugar. It is also present in
various fruits. In contrast to other disaccharides sucrose contains no free anomeric carbon atom. Since the
anomeric carbons of both its component monosaccharide units are linked to each other. For this reason sucrose
is non reducing sugar.
Source of sucrose:
Ripe fruit juices like pineapple, sugar cane, juice and honey are rich sources for sucrose. It also occurs in juices
of sugar beets, carrot roots and sorghum.

Fig 2.5: Structure of sucrose α-(1, 2) β-Glycosidic bond.

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Other Disaccharides
Isomaltose
It contains two glucose units. Glycosidic linkage is α(1→6). Isomaltose is the disaccharide unit present in
glycogen, amylopectin and dextran.
Cellobiose
It also contains two glucose units but they are joined in β(1→4) linkage. It is formed from cellulose.
Trehalose
It also contains two glucose units. The glycosidic linkage is α(1→1). So, it is a non-reducing disaccharide. It is
a major sugar of insect hemo lymph. In fungi it serves as reserve food material.
Other Oligosaccharides
Beans and peas contain some oligosaccharides. These oligosaccharides contain 4 to 5 monosaccharide units.
Stachyose and verbascose are a few such oligosaccharides. Usually these oligosaccharides are not utilized in
human body. Oligosaccharide chains are also found in glycoproteins where they have important functions.
Oligosaccharides are also important constituents of glycolipids present in cell membrane.

III. POLYSACCHARIDES
Most of the carbohydrates found in nature occur in the form of high molecular polymers called polysaccharides.
There are two types of polysaccharides .These are:
a. Homopolysaccharides that contain only one type of monosaccharide building blocks.
b. Heteropolysaccharides, which contain two or more different kinds monosaccharide building blocks.

a. Homopolysaccharides
Example of Homopolysaccharides: Starch, glycogen, Cellulose and dextrins.
Starch
Structure
 It consists of two parts. A minor amylose component and a major amylopectin component.
 Amylose is a straight-chain polymer of glucose units. α(1→4) glycosidic linkage is present between
glucose units.
 In contrast amylopectin is a branched molecule (Fig. below). In the linear portion of amylopectin (1→4)
glycosidic linkage exists between glucose units whereas (1→6) glycosidic linkage exists at branch
points between glucose residues. The branching occurs in amylopectin for every 2-30 glucose units.
 Amylose has helical coiled secondary structure and usually 6 glucose residues make one turn (Fig. 5.12).
Because of branching secondary structure of amylopectin is a random coil structure.
Function
1. It is the major polysaccharide present in our food.
2. It is also called as storage polysaccharide because it serves as reserve food material in plants.
3. It is present in food grains, tubers and roots like rice, wheat, potato and vegetables.

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Fig: Structure of Amylose and Amylopectin.
Glycogen
 Glycogen is the main storage polysaccharide of animal cells (Animal starch).
 It is present in liver and in skeletal muscle.
 Like amylopectin glycogen is a branched polysaccharide of D-glucose units in α - (1, 4) linkages, but it
is highly branched.
 The branches are formed by α -(1,6) glycosidic linkage that occurs after every 8 -12 residues. Therefore
liver cell can store glycogen within a small space. Multiple terminals of branch points release many
glucose units in short time.

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Cellulose
Cellulose is the most abundant structural polysaccharide in plants. It is fibrous, tough, water insoluble.
Cellulose is a linear unbranched homopolysaccharide of 10,000 or more D- glucose units connected by β-(1, 4)
glycosidic bonds. Humans cannot use cellulose because they lack of enzyme (cellulase) to hydrolyze the β-( 1-
4) linkages.

Fig 2.6: Structure of Cellulose.

Dextran
Structure
 It has structure similar to amylopectin.
 In the linear part, glucose units are linked by α(1,6) glycosidic bond and α(1,3) glycosidic linkage is
present between glucose unit at branch points.
Function
 It is polysaccharide present in bacteria.
Medical importance
 To maintain plasma volume dextran is used in clinical medicine.
 Dental plaque is due to dextran synthesized from sucrose by oral bacteria.

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Inulin
Structure
 It is a polysaccharide composed of fructose. beta(1,2) glycosidic linkage is present between fructose
units.
Function
 It is present in tubers of chicory, dhalia and in the bulb of onion and garlic.Inulin is used to determine
glomerular filteration of kidney.

Chitin
Structure:
 A polysaccharide composed of N-acetyl glucosamine. Glycosidic linkage is beta(1,4).
Function:
 It is an important structural polysaccharide of invertebrates like crabs, lobster and insects.

b. Hetero polysaccharides
These are polysaccharides containing more than one type of sugar residues GLYCOSAMINOGLYCANS,
(GAGs or MUCOPOLYSACCHARIDES), They are long, usually unbranched, composed of repeating
disaccharide units.
* They are negatively charged heteroplolysaccharid chains (polyanions)
 The amino sugar is either D-glucosamine or D-galactosamine in which the amino group is usually
acetylated, thus eliminating its positive charges.
 The amino sugar may also be sulfated on carbon 4, 6, or on a monoacetylated nitrogen.
 The acidic sugar is either D-glucuronic acid or its carbon 6 epimer, L-uronic acid. For example
Hyaluronic acid, Heparin and chondatin sulphate.

Function of GLYCOSAMMOGLYCANS. (GAGS) or MUCOPOLYSACCHARIDES

 They have the special ability to bind large amounts of water, there by producing the gel-like matrix that
forms the basis of the body’s ground substance.
 Since they are negatively charged, for example, in bone, glycosaminoglycans attract and tightly bind
cattions like ca++, they also take-up Na+and K+.
 GAGs stabilize and support cellular and fibrous components of tissue while helping maintain the water
and salt balance of the body.
 It is an essential components of the extra cellular matrix, GAGs’ play an important role in mediating
cell-cell interactions.
 Ground substance is a part of connective tissue, which is a gel like substance containing water, salt,
proteins and polysaccharides.
An example of specialized ground substance is the synovial fluid, which serves as a lubricant in joints,
and tendon sheaths.
They are also called as mucopolysaccharides and glycosaminoglycans. Mucopolysaccharides consist of
repeating disaccharide units. The disaccharide consist of two types monosaccharides. The mucopolysaccharides
are component of connective tissue. Hence, they are often referred as structural polysaccharides. The
mucopolysaccharides are also found in mucous secretions. The mucopolysaccharide combines with proteins

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like collagen and elastin and forms extracellular medium or ground substance of connective tissue.
Mucopolysaccharides are also components of extracellular matrix of bone, cartilage and tendons. The complex
of mucopolysaccharide and protein is called as proteoglycan. Mucopolysaccharides also function as lubricants
and shock absorbers.
Few important MUCOPOLYSACCHARIDES OR GLYCOSAMINOGLYCANS (GAGs) are:

1. Heparin:
 Contains a repeating unit of D-glucuronic and D-gluconsamine, with sulfate groups on some of the
hydroxyl and aminx-groups.
 It is an important anticoagulant, prevents the clotting of blood by inhibiting the conversion of
prothrombin to thrombin. Thrombin is an enzyme that acts on the conversion of plasma fibrinogen into
the fibrin.
 It is found in mast cells in lung, liver skin and intestinal mucosa.

2. Chondroitin sulfate A and B chondroitin-4-sulfate and chondroitin-6-sulfate

Structure
 The repeating disaccharide unit of chondroitin sulfates consist of glucuronic acid and N-acetyl
galactosamine. N-acetyl galactosamine is sulfated.
 In chondroitin-4-sulfate, 4th carbon atom of N-acetyl galactosamine is sulfated where as in chondroitin-
6-sulfate the 6th carbon is sulfated.

Functions
 Chondroitin sulfates are components of cartilage, bone and tendons.
 They are also present in the cornea and retina of the eye.
 Chondroitin sulfate content decreases in cartilage as age advances.

3. Dermatan Sulfate
Structure
 The repeating disaccharide consist of Iduronic acid and N-acetyl galactosamine sulfate.

Functions
 It is present in skin, cornea and bone.
 It has a role in corneal transparency maintenance.

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 4. Keratan sulfates I and II
Structure
 The repeating disaccharide consist of galactose and N-acetyl glucosamine sulfate.
 Type I and II have different attachments to protein.

Functions
 They are components of cartilage, cornea and loose connective tissue.
 Keratan sulfate l is important for corneal transparency.

5. Hyaluronic acid:
 Important GAGS found in the ground substance of synovial fluid of joints and vitreous humor of eyes.
 Also present as ground substance in connective tissues, and forms a gel around the ovum.
 Serves as a lubricant and shock absorbant in joints.
Hyaluronidase:
 Enzyme that breaks (beta 1-4 linkage) hyaluronic acid and other GAGS. This enzyme is present
in high concentration in testes, seminal fluid, and in certain snake and insect venoms.
 Hyaluronidase of semen is assigned an important role in fertilization as this enzyme clears the
gel (hyaluronic acid) around the ovum allowing a better penetration of sperm into the ovum.
 Hyaluronidase of bacteria helps their invasion into the animal tissues.

Glycoproteins (Mucoproteins)
Glycoprotiens are proteins to which oligosaccharides are covalently attached. They differ from the
glycosaminoglycans in that the length of the glycoproteins carbohydrate chain is relatively short (usually two to
ten sugar residues in length, although they can be longer), whereas it can be very long in the
glycosaminoglycans. The glycoprotein carbohydrate chains are often branched instead of linear and may or may
not be negatively charged.
For example:
- Glycophorin, a glycoprotein found in human red cell membranes.
- Human gastric glycoprotein (mucin).
- Many protein hormones, receptors are glycoproteins.

Proteoglycans
When glycosamnoglycans are attached to a protein molecule the compound is called proteoglycan
[proteoglycans = Glycosaminoglycans + proteins]

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