Carbohydrates

Noor Ullah
M.Phil Biochemistry& Molecular Biology
Lecturer IPMS, KMU

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 Carbohydrates
Carbohydrates- Carbon hydrates ( C- H20)

Polyhydroxy aldehyde or ketones.

Many, but not all, carbohydrates have the empirical formula (C- H 20)n

Three major classes of carbohydrates:

Monosaccharides, oligosaccharides, and polysaccharides

(The word saccharide is derived from the Greek sakcharon,

meaning sugar).

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 Monosaccharides
Monosaccharides are the simplest carbohydrates. They
are colorless, crystalline solids that are freely soluble in
water but insoluble in nonpolar solvents.

The simplest monosaccharides are the two three-carbon

trioses: glyceraldehyde and dihydroxyacetone.

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 Monosaccharides

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 Monosaccharides
Monosaccharides with four, five, six, and seven carbon
atoms in their backbones are called, respectively, tetroses,
pentoses, hexoses, and heptoses.

The D-glucose and D-fructose are the most common

monosaccharides in nature.

The aldopentoses, D-ribose and 2-deoxy-D-ribose are

components of nucleotides and nucleic acids.
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 Monosaccharides

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 Asymmetric or Chiral Centers
Carbon to which four different atoms or groups are attached is
called asymmetric.

All the monosaccharides except dihydroxyacetone contain one or

more asymmetric (chiral) carbon atoms and thus occur in optically
active isomeric forms- Enantiomers or Mirror images.

To represent three-dimensional sugar structures on paper, we

often use Fischer projection formulas.

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 Epimers
Two sugars that differ only in the configuration around
one carbon atom are called epimers. Examples are D-
glucose and D-mannose, which differ only at C-2 and D-
glucose and D-galactose (which differ at C-4) .

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 Epimers

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 Hemiacetals or Hemiketals
In aqueous solution monosaccharides with five or more carbon
atoms in the backbone occur predominantly as cyclic (ring)
structures in which the carbonyl group(aldehyde or keto) has
formed a covalent bond with the oxygen of a hydroxyl group along
the chain.

The formation of these ring structures is the result of a general

reaction between alcohols and aldehydes or ketones to form
derivatives called hemiacetals or hemiketals.
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 Hemiacetals or Hemiketals

An aldehyde or ketone can react with an alcohol in a 1:1 ratio to

yield a hemiacetal or hemiketal, respectively creating a new chiral
center at the carbonyl carbon.
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 Anomers and ring structure
Isomeric forms of monosaccharides that differ only in their configuration about

the hemiacetal or hemiketal carbon atom are called anomers, and the

carbonyl carbon atom is called the anomeric carbon.

Pyranose is a six-membered ring with Oxygen bridge between C no.1 and 5.

Furanose is a five-membered ring with oxygen bridge between C no.1 and 4.

The systematic names for the two ring forms of D-glucose are therefore alpha-

D-glucopyranose and beta-D-glucopyranose.

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Pyranose and Furanose ring
structure

Pyranoses and furanoses. The pyranose forms of D-glucose and the furanose forms of
D-fructose are shown here as Haworth perspective formulas. The edges of the ring
nearest the reader are represented by bold lines. Pyran and furan are shown for
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comparison.
 Mutarotation
The alpha and beta anomers of D-glucose interconvert in aqueous
solution by a process called Mutarotation.

In this process one ring form (say, the alpha anomer) opens briefly
into the linear form, then closes again to produce the beta anomer.

Thus, a solution of beta-D-glucose and a solution of alpha-D-

glucose eventually form identical equilibrium mixtures having
identical optical properties.

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 Racemic Mixture
The solution in which equal amount of levo and
dextrorotatory isomers are present, the optical rotation
of plane polarized light will be equal but in opposite
direction.

The net rotation will be zero. Such a mixture is called

racemic mixture

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 Mesocompounds
Compounds which do not rotate the plane polarized
light although they are having asymmetric carbon
atoms are called Mesocompounds.

It is due to internal compensation in which the d and l

forms are balanced. Example Mesotartaric acid.

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 Glycosides
When the hydroxyl group of one monosaccharide reacts
with the hydroxyl group of another monosaccharide, it
forms glycosidic linkage.

Glycosides are compounds in which a monosaccharide is

attached at the anomeric carbon to an alcohol residue of
non carbohydrate. The non carbohydrate residue is called
aglycon. Clinically important glycosides are Digitalis.
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 Reducing Sugars
Monosaccharides can be oxidized by relatively mild oxidizing
agents such as cupric (Cu2) ion. The carbonyl carbon is oxidized
to a carboxyl group.

Glucose and other sugars capable of reducing cupric ion are

called reducing sugars.

Cupric ion oxidizes glucose and certain other sugars to a complex

mixture of carboxylic acids. This is the basis of Fehlings reaction.

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Ring structure- Haworth formula
Cyclic structures of sugars are more accurately represented in
Haworth perspective formulas than in the Fischer projection
commonly used for linear sugar structures.

In Haworth projections the six-membered ring is tilted to make its

plane almost perpendicular to that of the paper, with the bonds
closest to the reader drawn thicker than those farther away and
numbering of the carbons is done in a clockwise direction
beginning with the anomeric carbon.

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 Haworth projections

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 Disaccharides
Disaccharides (such as maltose, lactose, and sucrose)
consist of two monosaccharides joined covalently by an
O-glycosidic bond, which is formed when a hydroxyl
group of one sugar molecule, typically cyclic, reacts
with the anomeric carbon of the other .

Because maltose has a free OH group at C-1 of glucose,

it is a reducing sugar.
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 Maltose

Formation of maltose. A disaccharide is formed from two monosaccharides (here,

two molecules of D-glucose) when an OH (alcohol) of one monosaccharide molecule
(right) condenses with the intramolecular hemiacetal of the other (left), with
elimination of H2O and formation of a glycosidic bond.
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 Lactose
The disaccharide lactose is formed by joining of D-
galactose and D-glucose.

It occurs naturally in milk. The anomeric carbon of the

glucose residue is available for oxidation, and thus
lactose is a reducing disaccharide.

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 Lactose

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 Sucrose
Sucrose (table sugar) is a disaccharide of glucose and
fructose.

In contrast to maltose and lactose, sucrose contains no

free anomeric carbon atom; the anomeric carbons of both
monosaccharide units are involved in the glycosidic bond.

Sucrose is therefore a non reducing sugar.

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 Sucrose

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 Polysaccharides
Most carbohydrates found in nature occur as polysaccharides

Polysaccharides, also called glycans, differ from each other in the

identity of their recurring monosaccharide units, in the length of
their chains, in the types of bonds linking the units, and in the
degree of branching.

Homopolysaccharides contain only a single monomeric species

Heteropolysaccharides contain two or more different kinds

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 Starch and glycogen
The most important storage polysaccharides are starch in plant cells and glycogen in
animal cells.

Starch contains two types of glucose polymer, amylose and amylopectin.

Amylose consists of long, unbranched chains of D-glucose residues connected by (alpha 1

4) linkages. Such chains vary in molecular weight from a few thousand to more than a
million.

Amylopectin is highly branched and has a high molecular weight (up to 200 million).

The glycosidic linkages joining successive glucose residues in amylopectin chains are
(alpha 1 4); the branch points (occurring every 24 to 30 residues) are (alpha 1 6) linkages.

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 Amylose

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 Glycogen
Glycogen is the main storage polysaccharide of animal
cells. Like amylopectin, glycogen is a polymer of (alpha
1 4)-linked subunits of glucose, with (alpha1 6)-linked
branches, but glycogen is more extensively branched
(on average, every 8 to 12 residues) and more compact
than starch.

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 Glycogen

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 Glycogen
Glycogen is especially abundant in the liver, where it
may constitute as much as 7% of the wet weight; it is
also present in skeletal muscle.

In hepatocytes glycogen is found in large granules,

which are themselves clusters of smaller granules
composed of single, highly branched glycogen
molecules with an average molecular weight of several
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million.
 Dextran
Dextrans are bacterial and yeast polysaccharides made
up of alpha 1 6-linked poly-D-glucose.

Dental plaque, formed by bacteria growing on the

surface of teeth, is rich in dextrans, which are adhesive
and allow the bacteria to stick to teeth and to each
other.

Dextrans also provide a source of glucose for bacterial

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 Cellolose
Cellulose, a fibrous, tough, water-insoluble substance, is found in the cell walls of plants,
particularly in stalks, stems, trunks, and all the woody portions of the plant body.

Cellulose molecule is a linear, unbranched homopolysaccharide, consisting of 10,000 to

15,000 D-glucose units.

The glucose residues in cellulose are linked by (beta 1 4) glycosidic bonds, in contrast to the
(alpha 1 4) bonds of amylose. This difference causes individual molecules of cellulose and
amylose to fold differently in space, giving them very different macroscopic structures and
physical properties.

The tough, fibrous nature of cellulose makes it useful in such commercial products as
cardboard and insulation material, and it is a major constituent of cotton and linen fabrics.

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 Cellolose
Glycogen and starch ingested in the diet are hydrolyzed by alpha
amylases and glycosidases, enzymes in saliva and the intestine that
break (alpha1 4) glycosidic bonds between glucose units.

Most vertebrate animals cannot use cellulose as a fuel source, because

they lack an enzyme to hydrolyze the (beta 1 4) linkages.

Termites readily digest cellulose (and therefore wood), but only because
their intestinal tract harbors a symbiotic microorganism, Trichonympha,
that secretes cellulase, which hydrolyzes the (beta 1 4) linkages.

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 Chitin
Chitin is a linear homopolysaccharide composed of N-
acetylglucosamine residues in (beta 1 4) linkage.

Chitin forms extended fibers similar to those of cellulose, and like

cellulose cannot be digested by vertebrates.

Chitin is the principal component of the hard exoskeletons of nearly a

million species of arthropodsinsects, lobsters, and crabs, for
exampleand is probably the second most abundant
polysaccharide, next to cellulose.

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 Heteropolysaccharides
These heteropolysaccharides, the glycosaminoglycans, are a family of linear polymers
composed of repeating disaccharide units. They are unique to animals and bacteria and are
not found in plants.

Hyaluronic acid forms clear, highly viscous solutions that serve as lubricants in the
synovial fluid of joints and give the vitreous humor of the vertebrate eye its jellylike
consistency (the Greek hyalos means glass.

Hyaluronan is also a component of the extracellular matrix of cartilage and tendons, to

which it contributes tensile strength and elasticity.

Hyaluronidase, an enzyme secreted by some pathogenic bacteria, can hydrolyze the

glycosidic linkages of hyaluronan, rendering tissues more susceptible to bacterial invasion.

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 Chondroitin Sulfate
Chondroitin sulfate (Greek chondros, cartilage)
contributes to the tensile strength of cartilage, tendons,
ligaments, and the walls of the aorta.

Dermatan sulfate (Greek derma, skin) contributes to

the pliability of skin and is also present in blood vessels
and heart valves.

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 Agar
Agar is a complex mixture of polysaccharides.

The remarkable gel-forming property of agarose makes it useful in the

biochemistry laboratory.

Agarose gels are used as inert supports for the electrophoretic separation of
nucleic acids, an essential part of the DNA-sequencing process.

Agar is also used to form a surface for the growth of bacterial colonies.

Another commercial use of agar is for the capsules in which some vitamins
and drugs are packaged.

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 Biomedical Importance of
Carbohydrates
Chief source of energy.

Constituents of compound lipids and conjugated proteins.

Certain carbohydrate derivatives are used as drugs like cardiac

glycosides/antibiotics.

Lactose principal sugar of milkin lactating mammary gland.

Degradation products utilised for synthesis of other substances

such as fatty acids, cholesterol, amino acid, etc.

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 Biomedical Importance of
Carbohydrates
Constituents of mucopolysaccharides which form the ground substance of
mesenchymal tissues.

Inherited deficiency of certain enzymes in metabolic pathways of different

carbohydrates can cause diseases, e.g. galactosemia, glycogen storage
diseases (GSDs), lactose intolerance, etc.

Derangement of glucose metabolism is seen in diabetes mellitus.

Seminal fluid is rich in fructose and sperms utilise fructose for energy.
Fructose is formed in the seminiferous tubular epithelial cells from glucose.

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 Biomedical Importance of
Carbohydrates
Various food preparations, such as baby are produced by hydrolysis of grains and
contain large amounts of maltose.

From nutritional point of view they are thus easily digestible.

In lactating mammary gland, the lactose is synthesised from glucose by the duct
epithelium and lactose present in breast milk is a good source of energy for the
newborn baby.

Lactose is fermented by Coliform bacilli (E. coli) which is usually non-pathogenic

(lactose fermenter) and not by Typhoid bacillus which is pathogenic (lactose non-
fermenter). This test is used to distinguish these two microorganisms.

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 Biomedical Importance of
Carbohydrates
Souring of milk: Many organisms that are found in milk, e.g. E. coli, A.
aerogenes, and Str. lactis convert lactose of milk to lactic acid (LA) thus causing
souring of milk.

Sucrose if introduced parenterally cannot be utilised, but it can change the

osmotic condition of the blood and causes a flow of water from the tissues into
the blood.

Thus clinicians use it in oedema like cerebral oedema.

If sucrose or some other disaccharides are not hydrolysed in the gut, due to
deficiency of the appropriate enzyme, diarrhoea is likely to occur.

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 Biomedical Importance of
Carbohydrates
Glycosides are found in many drugs, spices and in the constituents of animal
tissues.

Cardiac glycosides:

It is important in medicine because of their action on heart and thus used in

cardiac insufficiency. They all contain steroids as aglycone component in
combination with sugar molecules. They are derivatives of digitalis,
strophanthus and squill plants, e.g.

Ouabain: A glycoside obtained from strophanthus sp. is of interest as it inhibits

active transport of Na+ in cardiac muscle in vivo (Sodium Pump inhibitor).

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 Biomedical Importance of
Carbohydrates
Agar

In human: Used as laxative in constipation. Like cellulose,

it is not digested, hence add bulk to the faeces (roughage
value) and helps in its propulsion.

In microbiology: Agar is available in purified form. It

dissolves in hot water and on cooling it sets like gel. It is
used in agar plate for culture of bacteria.
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