Carbohydrate

BBC1

Biochemistry
Medical Faculty USU
 Discussion
1. Cane sugar is:
a. Glucose ✓
b. Sucrose
c. Fructose
d. Maltose
2. Which of the following is not a polymer of
glucose:
a. Amylose
b. Inulin ✓ Fmkwsa lpoumer)
c. Cellulose
d. Dextrins ougosakarida
e. Glycogen
 Carbohydrate are the most
abundant organic molecules that
provides a significant fraction of the
dietary calories for most organisms,
acting as a storage form of energy in
the body, and serving as cell membrane
components that mediate some forms
of intercellular communication.
Glucose is the precursor for synthesis of
all the other carbohydrates in the body,
including glycogen for storage, ribose an
deoxyribose in nucleic acids, galactose for
synthesis of lactose in milk, in glycolipids,
and in combination with protein in
glycoproteins and proteoglycans
 Classification of Carbohydrate
1. Monosaccharides are those sugars that cannot be
hydrolyzed into simpler carbohydrates. They may be
classified as trioses, tetroses, pentoses, hexoses, or
heptoses, depending upon the number of carbon
atoms (3-7), and as aldoses or ketoses, depending
on whether they have an aldehyde or ketone group.

Monosaccharides Aldehyde Ketone

Trioses (C3H6O3) Glyceraldehyd Dihydroxyacetone
e
Tetroses (C4H8O4) Erythrose Erythrulose
Pentoses (C5H10O5) Ribose Ribulose
Hexoses (C6H12O6) Glucose Fructose
Heptoses (C7H14O7) - Sedoheptullose
 Classification of Carbohydrate
2. Disaccharides are condensation
products of two monosaccharide units, for
example, lactose, maltose, isomaltose,
sucrose, and trehalose.
3. Oligosaccharides are condensation
products of three to ten monosaccharides.
Most are not digested by human enzymes.
Disaccharides Source
Lactose Galactose+glucose
Sucrose Glucose+fructose
Maltose Glucose+glucose
Polusaccharides
Glycogen Animal sources
Starch Plant sources
Unbranched cellulose Plant souces

Reference: Lippincott’s Illustrated Reviews Biochemistry 5thed

 Classification of Carbohydrate
4. Polysaccharides are condensation products
of more than ten monosaccharide units.
Polysaccharides are further divided into two
groups:
a. Homopolysaccharides (homoglycans):
Polymer of same monosaccharide units.
Examples—Starch, glycogen, inulin, cellulose,
dextrins, dextrans.
b. Heteropolysaccharides (heteroglycans):
Polymer of different monosaccharide units or
their derivatives.
Example—Mucopolysaccharides
(glycosaminoglycans).
 Various form of Sugars Isomer
1. D and L isomerism: The
designation of a sugar
isomer as the D form or
its mirror image as the L
form is determined by its
spatial relationship to
the parent compound of
the carbohydrates, the
three-carbon sugar
glycerose
(glyceraldehyde).
D- and L-isomerism of glycerose and gluco

Reference: Harper’s Illustrated Biochemistry 31st edition

2. Optical Isomer
The presence of asymmetric carbon atoms also
confers optical activity on the compound. When a
beam of plane polarized light is passed through a
solution of an optical isomer, it rotates either to
the right, dextrorotatory (+), or to the left,
levorotatory (−). For example, the naturally
occurring form of fructose is the d(−) isomer. In
solution, glucose is dextrorotatory, and glucose
solutions are sometimes known as dextrose.
3. Pyranose and furanose ring structures.
The ring structures of monosaccharides are
similar to the ring structures of either pyran (a
six-membered ring) or furan (a five membered
ring). More than 99% glucose is pyranose form
 Pyranose and furanose forems of glucose

4. Alpha and beta anomers: The ring structure of

an aldose is a hemiacetal, since it is formed by
reaction between an aldehyde and an alcohol
group. Similarly, the ring structure of a ketose
is a hemiketal. Crystalline glucose is α-d-
glucopyranose.
Reference: Harper’s Illustrated Biochemistry 31st edition
5.Epimers: Isomers differing as a result of
variations in configuration of the —OH and —H
on carbon atoms 2, 3, and 4 of glucose are
known as epimers. The most important
epimers of glucose are mannose (epimerized
at carbon 2) and galactose (epimerized at
carbon 4)
6. Aldose-ketose isomerism: Fructose has the
same molecular formula as glucose but differs
in that there is a potential keto group in
position 2, the anomeric carbon of fructose,
whereas in glucose there is a potential
aldehyde group in position 1, the anomeric
carbon.
Examples of aldoses of physiological significance

Examples of ketoses of physiological significance

Reference: Harper’s Illustrated Biochemistry 31st edition

Pentoses are important in
nucleotides, nucleic acids, and
Pentose
several coenzymes.
The addition of a pentose sugar
to a base produces a nucleoside.
If the sugar is ribose, a
ribonucleoside is produced; if the
sugar is 2-deoxyribose, a
deoxyribonucleoside is produced.
D-ribose is a constituent of
nucleic acidRNA; also as a
constituent of certain
coenzymes, e.g. FAD, NAD,
coenzyme A.
The ribonucleosides of A, G, C,
and U are named aden osine,
guanosine, cytidine, and uridine,
respectively. The
deoxyribonucleo sides of A, G, C,
and T have the added prefix, Pentose found in nucleic acid
“deoxy-,” for example,
deoxyadenosine. Reference: Lippincott
 Glycosides: examples of N- and O-glycosidic
bonds.

Reference: Lippincott’s Illustrated

Reviews Biochemistry 5th edition
 Monosaccharides
(a) Trioses: Both D-glyceraldehyde and dihydroxyacetone
occur in the form of phosphateesters, as intermediates
in glycolysis.They are also the precursors glycerol, which
the organism synthesises and incorporates into various
types of lipids.
(b) Tetroses: Erythrose-4-P occurs as an intermediate in
hexosemonophosphate shunt which is an alternative
pathway for glucose oxidation.
(c) Pentoses
D-ribose is a constituent of nucleic acidRNA and
coenzymes.
D-2-deoxyribose is a constituent ofDNA.
Phosphate esters of ketopentoses—D-ribulose and D-
xylulose occur as intermediates in HMP shunt.
L-xylulose is a metabolite of D-glucuronic acid and is
excreted in urine of humans afflicted with a hereditary
abnormality in metabolism calledpentosuria.
L-fucose (methyl pentose): occurs in glycoproteins.
D-Lyxose: It forms a constituent of lyxoflavin isolated
from human heart muscle whose function is not clear.
(d) Hexoses
1. D-Glucose: (Synonyms: Dextrose, Grape Sugar)
Physiological sugar present in normal blood continually and at fairly
constant level, i.e. about 0.1 per cent.
All tissues utilise glucose for energy, erythrocytes and brain cells use
glucose solely for energy purposes.
Stored as glycogen in liver and muscles mainly.
Shows mutarotation.

2. D-galactose: Seldom found free in nature. In combination it occurs both

in plants and animals.
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 and shows mutarotation.

3. D-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
laevorotatory and hence is also called laevulose.
Exhibits mutarotation.

4. D-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.
5. Sedoheptulose: It is a ketoheptose found in plants of
the sedum family. Its phosphate is important as an
intermediate in the HMP-shunt and has been identified
as a product of photosynthesis.
 Important Properties of Monosaccharides
1. Iodocompounds: An aldose when heated with conc. HIloses
all of its oxygen and is converted into an iodocompound.

2. Acetylation or ester formation: The ability to form sugar

esters, e.g. acetylation with acetyl chloride (CH –COCl)
3

indicates the presence of alcohol groups.

3. Osazone formation: It is a useful means of preparing
crystalline derivatives of sugars.
4. Interconversion of sugars: Glucose, fructose and mannose are
interconvertible in solutions of weak alkalinity such as Ba(OH)
2

or Ca(OH)2

5. Oxidation to produce sugar acids: When oxidised under

different conditions, the aldoses may form monobasic Aldonic
acids, Dibasic Saccharic acids, or Monobasic uronic acids.
6. Reduction of sugars to form sugar alcohols: The
monosaccharides may be reduced to their corresponding
alcohols by reducing agents such as Na-Amalgam. Similarly,
ketoses may also be reduced to form ketoalcohol. In
microbiology sugar alcohols have been used to identify type of
 7. Action of acids on carbohydrates: Polysaccharides and the compound
carbohydrates in general are hydrolyzed into their constituent
monosaccharides by boiling with dilute mineral acids (0.5 to 1.0 N) such
as HCl or H2SO4.
8. Action with alkalies: With alkalies, monosaccharides react in various ways:
(a) In dilute alkali: The sugar will change to the cyclic α and β forms with an
equilibrium between the two isomeric form.
(b) In conc. alkali: The sugar caramelises and produces a series of
decomposition products, yellow and brown pigments develop, salts may
form, many double bonds between C-atoms are formed, and C bond C
bonds may rupture.
9. Reducing action of sugars in alkaline solution: All the sugars that contain
free sugar group undergo enolisation and various other changes when
placed in alkaline solution. 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
Ag+. Hg+, Bi+++, Cu++ (cupric) and Fe(CN)6– – –. which dissociate
sufficiently to provide supply of readily available Cu++ (cupric) ions for
oxidation.
 Disaccharides
The general molecular formula is C H O and they are
12 22 11

hydrolysed by hot acids or corresponding enzymes as

follows:

The disaccharides are formed by the union of two

constituent monosaccharides with the elimination of one
molecule of water.If both of the two potential aldehyde/or
ketone groups are involved in the glycosidic linkage the
sugar will not exhibit reducing properties and will not be
sucrose. But if one of
able to form osazones, e.g. them is
not bound in this way, it will permit reduction and osazone
formation by the sugars, Lactose
e.g. and Maltose.
 Properties of disaccharides
1. Maltose:Maltose or malt sugar is an intermediary in acid hydrolysis
of starch and can also be obtained by enzyme hydrolysis of starch.
In the body, dietary starch digestionby Amylase in gut yields
maltose, which requires a specific enzyme maltase to form glucose.
It is a rather sweet sugar and is very soluble in water. As anomeric
carbon of one glucose is free, can form α and β forms and exhibit
On hydrolysis Maltose yields two molecules of
mutarotation.
glucose.

2. Lactose:Lactose is milk sugar and found in appreciable quantities in

milk to the extent of about 5 per cent and occurs at body temperature
as an equilibrium mixture of the α and β forms in 2:3 ratio. It is not
dextrorotatory. Specific enzyme
very soluble and is not so sweet. It is
which hydrolyses lactase
is present in intestinal juice. On hydrolysis it
yields one molecule of D-Glucose and one molecule of D-Galactose.
Because it contains galactose as one of its constituents, it yields
mucic acid on being treated with Conc HNOafter hydrolysis.It has
reducing properties and can form osazones. Lactosazone crystals
3

have typical hedgehog shape or powder puff appearance. As

anomeric carbon of glucose is free, can form α and β forms and
3. Sucrose: Ordinary table sugar is sucrose,also called as
‘Cane sugar’, as it can be obtained from sugarcane. Also
obtained from sugar beet and sugar maple. Also occurs
free in most fruits and vegetables, e.g. pineapples, and
carrots. It is very soluble and very sweet and on
hydrolysis yields one molecule of D-Glucose and one
molecule of D-Fructose. The specific enzyme which
hydrolyses sucrose is sucrase present in intestinal juice.
As both aldehyde and ketone groups are linked together
(α 1 → 2), it does not have reducing properties, and
cannot form osazones. As both anomeric carbons are
involved in ‘linkage’, it does not exhibit mutarotation.
4. Lactulose: A ketodisaccharide
Structure: It is O-α-D-galctopyranosyl-(1→4)-β-
Dfructofuranose
Source: Heated milk (small amounts). Mainly obtained
synthetically.
Clinical significance: Not hydrolysed by intestinal
enzymes, but fermented by intestinal bacteria. It is used
clinically in medicine as anosmotice laxative.
 Oligosaccharides
Integral membrane proteins contain covalently
attached carbohydrate units, oligosaccharides, on
their extracellular face. Many secreted proteins,
such as antibodies and coagulation factors also
contain oligosaccharide units.
Carbohydrates participate in molecular targeting
and cell-cell recognition. The removal of
glycoproteins from the blood is accomplished by
Surface Protein Receptors on Liver cells, e.g.
Asialo-glycoprotein receptor. Many newly
synthesised glycoproteins such as,
immunoglobulins (antibodies) and peptide
hormones, contain oligosaccharide carbohydrate
units with terminal sialic acid residues.
 Polysaccharides
Polysaccharides are more complex
substances. Some are polymers of a
single monosaccharide and are termed as
Homopolysaccharides (Homoglycans), e.g.
starch, glycogen, etc.
Some contain other groups other than
carbohydrates such as hexuronic acid and
Heteropolysaccharides
are called as
(heteroglycans), e.g. Mucopolysaccharides.
 Polysaccharides
1. Starch/amylum is a homopolymer of glucose forming an α-
glucosidic chain, called a glucosan or glucan. It is the most important
dietary carbohydrate in cereals, potatoes, legumes, and other
vegetables. The two main constituents are amylose (13%-20%), which
has a nonbranching helical structure, and amylopectin (80%-87%),
which consists of branched chains consists of 24 to 30 glucose
residues with α1 → 4 linkages in the chains and by α1 → 6 linkages at
the branch points. The glycemic index of a starchy food is a measure
of its digestibility, based on the extent to which it raises the blood
concentration of glucose compared with an equivalent amount of
glucose or a reference food such as white bread or boiled rice.
Glycemic index ranges from 1 (or 100%) for starches that are readily
hydrolyzed in the small intestine to 0 for those that are not hydrolysed
at all.
2. Glycogen is the storage polysaccharide in animals and is
sometimes called animal starch. It is a more highly branched
structure than amylopectin, with chains of 12 to 15 α-dglucopyranose
residues (in α1 → 4 glucosidic linkage) with branching by means of α1
→ 6 glucosidic bonds. Muscle glycogen granules (β-particles) are
spherical and contain up to 60,000 glucose residues; in liver there are
similar granules and also rosettes of glycogen granules that appear to
be aggregated β-particles.
3. Inulin is a polysaccharide of fructose (a fructosan)
found in tubers and roots of dahlias, artichokes, and
dandelions. It is readily soluble in water and is used to
determine the glomerular filtration rate (see Chapter
48), but it is not hydrolyzed by intestinal enzymes, so
has no nutritional value.
4. Dextrins are intermediates in the hydrolysis of starch.
5. Cellulose is the chief constituent of plant cell walls.
It is insoluble and consists of β-d-glucopyranose units
linked by β1 → 4 bonds to form long, straight chains
strengthened by cross-linking hydrogen bonds.
Mammals lack any enzyme that hydrolyzes the β1 →
4 bonds, and so cannot digest cellulose. It is an
important source of “bulk” in the diet, and the major
component of dietary fiber. Microorganisms in the gut
of ruminants and other herbivores can hydrolyze the
linkage and ferment the products to shortchain fatty
acids as a major energy source. There is some
bacterial metabolism of cellulose in the human colon
6. Chitin is a structural polysaccharide in the
exoskeleton of crustaceans and insects, and also in
mushrooms. It consists ofN-acetyl-d- glucosamine
units joined by β1 → 4 glycosidic bonds.
7. Pectin occurs in fruits; it is a polymer of galacturonic
acid linked α-1→ 4, with some galactose an/or
arabinose branches, and is partially methylate.
8. Glycosaminoglycans (mucopolysaccharides) are
complex carbohydrates containing amino sugars and
uronic acids. They may be attached to a protein
molecule to form a proteoglycan. Proteoglycans
provide the ground or packing substance of
connective tissue. They hold large quantities of water
and occupy space, thus cushioning or lubricating other
structures, because of the large number of ´OH groups
and negative charges on the molecule, which, by
repulsion, keep the carbohydrate chains apart.
Examples are hyaluronic acid, chondroitin sulfate, and
heparin.
9.Glycoproteins (also known as mucoproteins) are
proteins containing branched or unbranched
oligosaccharide chains including fucose.They
occur in cell membranes and many proteins are
glycosylated. The sialic acids are N- or O-acyl
derivatives of neuraminic acid (Figure 15–15).
Carbohydrate Found in Glycoprotein

10. Neuraminic acid is a ninecarbon sugar derived

from mannosamine (an epimer of glucosamine)
and pyruvate. Sialic acids are constituents of
both glycoproteins and gangliosides.
 Glycosides
Glycosides are compoundscontaining a carbohydrate
and a noncarbohydrate residue in the same molecule.
The noncarbohydrate residue present in the glycoside is
called as Aglycone. The aglycones present in glycosides
vary in complexity from simple substances as methyl
alcohol, glycerol, phenol or a base such as adenine to
complex substances like sterols, hydroquinones and
anthraquinones. The glycosides are named according to
the carbohydrate they contain. If it contains glucose,
glucoside. If galactose, it forms galactoside and
forms
o on.
Glycosides are widely distributed in nature; the aglycone
may be methanol, glycerol, a sterol, a phenol, or a base
such as adenine. The glycosides that are important in
medicine because of their action on the heart (cardiac
glycosides) all contain steroids as the aglycone. These
include derivatives of digitalis and strophanthus such as
ouabain, an inhibitor of the Na –K -ATPase of cell
+ +

membranes. Other glycosides include antibiotics such

as streptomycin.
VIDEO
 REFERENCE
1. Harper’s Illustrated Biochemistry 31st
edition
2. Lippincott’s Illustrated Reviews
Biochemistry 5th edition
3. Textbook of Medical Biochemistry, 8th
edition, Jaypee (MN Chatterjea, Rana
Shinde)
4. https://www.youtube.com/watch?
v=LeOUIXbFyqk
TERIMA KASIH