CARBOHYDRATES

Structure
2.1 Introduction
Objectives
2.2 Classification
2.3 Monosaccharides
Stereochemistry of Monosaccharides
Glucose (Dextrose) :An Aldohexose
Ring Structures of Monosaccharides
Fructose and Other Monosaccharides
Reactions of Monosaccharides
2.4 Disaccharides
Maltose
Lactose
Sucrose
2.5 Polysaccharides
Storage Pol ysaccharides
Cellulose : A Structural Polysaccharide
2.6 Complex Polysaccharides
Glycosaminoglycans
GIycoproteins
Blood Group Substances
2.7 Summary
2.8 Terminal Questions
2.9 Answers

2.1 INTRODUCTION
/
/
In Unit 1,we described the structure of a typical cell, and the function of its various
organelles. Besides this, we also outlined the Average chemical compwition of a
cell. You will recall that the dry weight ofla cell mainly comprises of proteins,
lipids, nucleic acids and carbohydrates..these are all important biomolecules
required to su$tain a living organism. In Unit 2 you will be introduced to
carbohydrates. These important molecules, in addition to being part of the structure
of a cell, also provide energy for its functioning. We shall classify carbohydrates
into various types and describe their chemical structures. You shall also briefly
learn about the stereochemistry of sugars, and the biological role carbohydrates
play. In Unit 3 you will study another important biomolecule, namely lipids. These
molecules form part of thc structure of membranes, store energy for the cell, and
perform other functions also.
0bjectives
After studying this unit, you should be able to,

define monosaccharides, oligosaccharides and polysaccharides,

identify a monosaccharide as an aldose or a ketose, ' ,
describe stereochemistry and anomeric forms of sugars,
draw the straight chain (Fischer projection) and ring structure (Haworth
formula) of sugars,
describe the dhemical naturelproperties of carbohydrates and their biological
roles, .
describe storage and structural polykiccharides, and
describe some complex polysaccharides and their biological significance.
 CLASSIFICATION
Before we describe the classification of carbohydrates, let us first know more about
the general nature and functions of these biomolecules. Carbohydrates are the most
abundant of all forms of biomolecules. They comprise of polyhydroxy aldehydes,
polyhydroxy ketones, and their derivatives which can be hydrolysed to yield
polyhydroxy aldehydes and polyhydroxy ketones. Carbohydrates include
saccharides or sugars, glycogen, starches, cellulose, dextrins, etc. In addition to
these, carbohydrates are also found in combination with other molecules, in the
form of glycosaminoglycans, lipopol ysaccharides, glycoproteins and glycolipids.
Carbohydrates, together with fats and proteins, constitute three major components
of our food.
Carbohydrates generally serve as a source of energy for the living organism. In
plants, these molecules (e.g., cellulose) are also components of the supporting tissue
(such as the wood in trees). Certain carbohydrates like ribose in nucleic acids,
galactose in cerebrosides, lactose in milk and cell surface carbohydrates are
responsible for highly specialised functions. Monosaccharides, which are the
simplest of sugars, serve as building blocks for the more complex sugars, and are
the immediate source of energy for the cells. Large amount of energy is stored in
more complex carbohydrates, like starch in plants and glycogen in animals. This
energy is utilised by breaking these molecules into simpler molecules within the
living system. While plants synthesise carbohydrates by photosynthesis, animals
cannot do so and must get their carbohydrate supply from plants, which serve their
energy requirements. Carbohydrates along with fatty acids are the most important
metabolic fuels in the cells of animals.
Let us now study the classification of carbohydrates. These biomolecules can be
classified into monosaccharides, oligosaccharides and polysaccharides, according to
the size of the molecule. Monosaccharides are carbohydrates that cannot be broken
into smaller units upon hydrolysis, e.g., glucose. Oligosaccharides upon hydrolysis
yield between 2-6 monosaccharide units and, depending upon the number of
monosaccharide units so obtained, are known as disaccharides, trisaccharides, etc.
Polysaccharides produce a large number of monosaccharide units (more than six)
upon hydrolysis. They may contain as many as 3000 monosaccharide units.

-ose is the cha;acteristic

suffix used Monosaccharides, which are also known as simple sugars, Are further classified by
to denote a sugar. the number of carbon atoms in the molecule, i.e., a three carbon monosaccharide is
known as a triose, and four, five and six carbon monosaccharides as tetroses,
pentoses, hexoses and so on. Depending upon the nature of the carbonyl function, a
monosaccharide is further classified as an aldose (containing an aldehyde functional
group) or a ketose (containing a ketone functional group). For example, ribose is an
aldopentose (a 5-carbon sugar molecule containing an aldehyde group), glucose is
an aldohexose (a 6-carbon sugar with an aldehyde group) and fructose is a
ketohexose (a 6-carbon sugar with a ketone group).
W e shall now describe monosaccharides in detail.

2.3 MONOSACCHARIDES

I
MOSI disaccharides are reducing AS outlined above, monosaccharides usually contain a 3-6 carbon atom chain with
sugars, sucrose (common table an aldehyde or a ketone group. These simple sugars are white crystalline solids.
sugar) being an as it is a They are highly soluble in water, due to the presence of polar hydroxyl groups. This
nonreducing sugar.
implies that these sugars will have low solubility in nonpolar solvents. Most
nosaccharides have a sweet taste. All monosaccharides whether aldoses or ketoses
Before we describe some individual monosaccharides, let us have a look at the
stereochemistry of these molecules first.

2.3.1 Stereochemistry of Monosaccharides

Study the structures of some monosaccharides which are shown below:

CHO CHO CHO CHO

I I I I
CHOH (CHOH)2 (CHOW3 (CHOH),
1 I I I
CH, OH CH, OH CH20W CIH, OH
Aldotriose Aldotetrose Aldopentose Aldohexose

You would observe that aldotriose (glyceraldehyde) has one chiral carbon atom.
Therefore, it exists in two enantiomeric forms, with optical activity of opposite sign,
namely, dextrorotatory and levorotatory glyceraldehydes. Higher sugars have two
or more chiral carbon atoms and, therefore, have a larger number of stereoisomers.
The number of stereoisomers is equal to 2", where n is the number of chiral carbon A tetral~edralcarbon. wit11li)i~r
atoms. Those aldoses which are related to dextrorotatory glyceraldehyde (also different atonis or group of alonls
carbon. It isge~~erallydcsignalcd
called D-(+)-glyeraldehyde), i.e., those aldoses which can be synthesised from, or wit11 an asterisk(*).
chemically degraded to this compound, are said to belong to the D-series of sugars. arc s~crcoisonlersI I I ~ : I
Ella~~rion~ers
Similarly, the L-series sugars are related to the levorotatory glyceraldehyde (also are ooti-superimlwsaldcn~irnir
called L-(-)- glyceraldehyde). You should note that the capital letters D and L, as images of each olber.

applied to the higher sugars, do not refer to the actual sign of their optical activity. Stereoiwn~ersthal are 1101 mirro~
images of e;lcl~otlier ;Ire c;~llcd
These refer only to their structural relationship to D-or L-glyceraldehyde. As you diastereomers.
will see later, D or L notations also refer to the configuration around the chiral
arbon, next to CH20H group, which is also the chiral carbon larthest from the
aldehyde group. Since the carbon atoms of aldoses are numbered starting with the
aldehyde carbon, the configuration around the chiral carbon, with the highest
position number, determines whether a sugar belongs to the D or the L series.
Emil Fischer, who described assignment of configuration around all chiral carbon
atoms of glucose and some other sugars, proposed a method (convention) for
representing configuration of carbohydrates, called Fischer's projection formula.
This is explained below for D-glyceraldehyde.

D-Glyceraldehyde : For arriving at the Fischer's projection fonllula is n two-

projection formula, the tetrahedron dunensional projection(on paper) of the
containing the chiral carbon at its center ( n d molecule when it is held as explained in the
shown in the drawing on extreme left) is held accompanying drawing. Thus horizontal
with CHO on the top, CH2OH at the bottom lies represent bonds above the plane of
and the line joining them (ie. the edge of the paper, and vertical lines represent bonds
tetrahedron) is below the plane ofthe paper. below the plane of paper.
Hand OH point towards the viewer.
Fischer's projection formulae are specially helpful for representing the
configurations of higher sugars having several chiral carbon atoms. In each case, it
is a two-dimensional projection of the molecule, when the latter is held with CHO
on the top, CH20H at the bottom, all the carbon-carbon bonds below the plane of
the paper, and H & OH on all chiral carbon atoms pointing towards the viewer.
Inter-relationship of various D-aldoses is shown in Fig. 2.1, using the Fischer's
projection formulae. The L-aldoses are simply mirror images of their
 D-counterparts, as is shown below for D- and L-glucoses. The L-sugars are much
less abundant than the D-sugars in nature.

2 I 2I
H-C -OH HO-C-H
I 3 3
I
HO-C-H H-C-OH I

4I 4I
H-C-OH HO-C-H
51 51
H-p - OH HO-C-H
61 61
CH20H CH20H
D-Gluccse L-Glucose
D- and L-sugars are referred to as enantiomers. As can be seen there are several
pairs of isomeric aldoses which differ from each other at only one of the several
chiral carbon atoms, e.g. glucose and mannose (differing at C - 2 only) and glucose

CHO
I
H-C-OH
I Aldotriose
CHzOH

CHO CHO
I I
H-C-OH HO-C-H
I I
H-C-OH H-C-OH

CHO CHO CHO CHO

I I I I
H-C-OH HO-C-H H-C-OY HO-C-H
I
B-C-OH
I
H-C-OH
I
HO-C-H
I
HO-C-H Aldopentoses
I I I I
H-C-OH H-C-OH H-C-OH H-C-OH
I I I I
CHIOH CHIOH CHzOH CHzOH
D-Ri bose D-Ara bi nose D-Xylose D-Lyxose

CHO CHP CHO CHO CHO CHO CHO CHO

I I I I I I I I
H-C-OH HO-C-H H-C-OH HO-C-H H-C-OH HO-C-H H-C-OH HO-C-H
I
H-C-OH
I
I
H-C-OH
I
I
HO-C-H
1
I
HO-C-H
I
H-L-OH
I
I
H-C-OH
1
HO-C-H
I
I
I
HO-C-H
I Aldw
H-C-OH H-C-OH H-C-OH H-C-OH HO-C-H HO-C-H HO-C- H HO-C-H hexoses
I I I I I I I I
M-C-OH H-C-OH H-C-OH H-C-OH H-C-OH H-C-OH H-C-OH H-C-OH
I I I I I I I I
CH&H CHzOH CHzOH CHzOH CHIOH CH~OH CHzOH CHIOH

Fig. 2.1: Stereochen~icdrelationship mioog the D-aldosa with 3 to 6 carbon atonls

and galadose (differing at C-4). Such isomers are referred to as epimers. Note that
mannose and galactose are not epimers of each other.
In a similar manner, ket~sesmay be related to dihydroxy acetone (ketotriose). In
, this case also, the capital letters D and-L are used to denote the configuration
around the chiral carbon farthest from the keto group, i.e., the one with the highest
position number since the numbering starts from the end nearer to the keto group.
Inter-relationship of various keto sugars is shown in Fig. 2.2. You would observe
that for the same chain length, the ketoses have one chiral carbon less than the
aldoses. For example, an aldohexose has four chiral carbons and a ketohexose has
only three. Therefore, the number of stereoisomers of ketoses will be half of those
of the corresponding aldoses.
The D and L configurational notation has been retained in sugar chemistry. For
other organic compounds, it has been replaced by a more convenient and
unambiguous R (rectus) and S (sinister) notation. In the latter system, it becomes
necessary to give configurational notation for each chiral carhon atom. It can be
shown that D- and L-glyceraldehydes are R- and S-glyceraldehydes, respectively.
As mentioned above, the capital letters D and L do not provide any information
about the direction of optical activity. Wherever necessary, the latter is shown by
(+) and (-) which stand for the dextrorotation and levorotation, respectively, e.g.
D-(+)-glucose and D-(-)-fructose.
The difference in the arrangement of atoms between the D and L isomers is small
and appears to be unimportant to us. However, to our body and its cells, it is quite
critical. This minor difference is recognised by the cells, which often use only one
of the isomers. For example, yeast can ferment D-glucose to produce alcohol, but it
cannot ferment L-glucose.

C =o
I
H- C-OH
I
CH,OH

C =O C =O
I I
H-C-OH HO- C-OH
I I
H- C-OH
I

HO- C-H H - C-OH H -- C-OH HO - C-QLI

I I I
H- C-OH H- C-OH HO - C-OH HO - C-OH
II II I I
H - ?-OH H- C-OH H- C-OH
I H- $--OH

Fig. 22: Stereochemical relationship among Chc D-ketoseswith thm to six carbon atoms 1
 ,
Let us now describe glucose first, as it is a common aldohexose.
.
2.3.2 Glucose (Dextrose): An Aldohexose
Glucose, also known as b l k d sugar and grape sugar, is the most common hexose
and is found in fruit juices, grape juice in particular, in the saps of plants, in the
blood and tissue of animals. As already mentioned, it is the immediate source of
energy for all metabolic reactions in the animals. Adult human body contains about
1teaspoon (5-6 grams) of glucose in the blood, which supplies energy needs of the
body for around fifteen minutes. Glucose in the blood is continuously replaced from
glycogen stored in the liver.
D-glucose is a part of many oligo/polysaccharides. Because of its presence in a
large number of living cells, its chemistry is very important. A study of glucose can
help in learning about other monosaccharides as well. Elemental analysis and
molecular weight determination indicates that glucose has a molecular formula of
G H 1 2 0 6 . Further, its chemical behaviour supports a six carbon, pentahydroxy
aldehyde structure. These chemical reactions, supporting an aldohexose structure,
are summarised in Fig. 2.3.

Br: + H,O COOH

C,l 1,NH .NH, CHO (bromine water) I
CT1 =NNHC6H, 4 + (CHOH),
I (Phenylhydrazine) 1
7HOH mild oxidation I
ICHOH) .
I I

(Glucose, C6H,,U,) I
COOH
Glucaric acid
(Saccharic acid)
Gluci to1
(Sorhitol)

5"' (CHOAC),
I
AC,O (acetic
anhydride)
(C.H2)3 CH,OAC a~tylation
1 Hexa-0-acetylgluci tok
CH, I

1) HCN

H<'(OH)<'N (indicates t~ve-UH groups

1 ( ~ y d r oysis
l in glucose molecules)
v
HC(0H)COOH COOH
I HI, heat 1
CH,
 Carbohydrates
The open chain structure of glucose, which we have describedlso far, does not
explain many of its properties. So let us study other possible structures of glucose.
But before that attempt the following SAQs.

SAQ 1
Tick [ d ] mark the following statements as true or false
a) All aldose sugars are derived from glyceraldehyde. [True/False]
b) D-Ribose is an aldose. [TrueFalse]
c) Monosaccharides are insoluble in water. [TrueFalse]
d) Polysaccharides upon hydrolysis yield 2-6 monosaccharide units. [True/False]

SAQ 2
Fill in the blanks with appropriate words
a) D-Glucose is an epimer of .............................................................
b) ....................sugars are less abundant than .......................sugars.
c) Ketoses have less number of ....................................than aldoses.
d) .........................................is a part of many oligo/polysaccharides.
2.33 Ring Structures of Monosaccharides
In an aqueous solution, glucose actually exists in three forms, which are in A general reaction of a carbny I
equilibrium and are readily converted into one another. The straight chain makes up group(a1dehydeor ketone) with a[!
alcohol, is lo form a l~en~iacetal
01 ,I
only 0.02% of these molecules. The rest of the molecules are the other two ring hen~iketal.
forms that result from an internal (intramolecular) hemiacetal formation. Since 0
monosaccharides (aldoses and ketoses) contain both carbonyl as well as an 11
alcoholic function within the same molecule, the two groups combine R- C-H + H-o-R'*
intramolecularly to give a cyclic hemiacetalhemiketal. In glucose, the hemiacetal R OH
'G'
will be formed between the aldehyde group on C-1 and the alcohol group on C-5.
~
'
0' h

The bemiacetal/hemiketal~s m
equilibrium with the aldehyde/
ketone.

In addition to the Fischer projection formula for sugars, the configuration of the
substituents at each carbon atom can also be conveniently represented by Haworth
projection formula. In fact, these formulas are often used to simplify the drawing
of sugar ring structures, discussed above. According to this convention, a sugar with
a 6-membered ring is a pyranose and a sugar with a 5-membered ring a furanose.
The ring structure in the two cases is similar to pyran and furan, respectively.
\

In Haworth projections, the ring formed by the sugar molecule (after internal
hemiacetalbemiketal formation) is shown in a manner as if we are looking at it
from the side, instead of looking down at the ring from above. The side nearer to us
is shown by thickened lines and the groups attached to each carbon atom are then
shown as above or below the plane of the ring. The cyclic forms of glucose and
fructose, as represented by Haworth projections, are known as glucopyranose and
fructofuranose, respectively (Fig. 2.4).
 6 2'
H-k-OH ~ H ~ O H c=o
IIO-~-H
I H'{-OH~
I = 4C'IHH C
4
H-C-OH-
I
I\?" 1 / 1 \ ~
HO C-C
H-C
' -OH 2AlI
H 01-1 OH H
61 a - D - Glucopyranose CHzOH - D - Fructofuranose
CH20H
(Haworth projection) D - F~~~~~~~ (Haworth projection)
-
D Glucose (linear form)
(linear form)
Fi.2.4: Rings fornls of glucose and f ~ d 0 5 e

Anomeric forms of sugars

The carbonyl carbon of a monosaccharide, which has no chirality, becomes
asymmetric following cyclisation and the resultant diastereoisomers are known as
anomers, i.e., the a-anomer and the p-anomer. The hemiacetal (C-1) or hemiketal
(C-2) carbon in these ring- forms is called the anomeric carbon. The two anomeric
ring forms depend on the placement of the hydrogen and hydroxyl group on the
anomeric carbon. If the - OH group is below the plane of the ring, it is cis or
the a form and if it is above the plane of the ring it is trans or the fJ form. The
process of ring formation, as shown for glucose below indicates why the hemiacetal

4 1
H-C-OH

A model of the above coils as sown'

The direction of the arrows indicates how the group

attached to C-4 is pivoted

-
L

H OH
U-D-(+)-Glucose (36%)
or Open form of fl-D-(+)-Glucose (641)
D-glucose (0.02%) or
a-D-(+)-glucopyranose fl-D-(+)-gltlcopyranose
Scheme depicting the formation of the hemincetnl forms or D-glucose
can exist in two anomerii: forms. A simple rotation of the bond between C-4 and
C-5 in a counterclockwise manner brings the C-5 hydroxyl into a position for
reaction with the carbonyl group. Thus, the -OH group will now occupy the
position originally occupied by the hydrogen at C-5. Since C-1 becomes an
asymmetric carbon in the hemiacetal, two diastereomeric molecules are possible.
The a-anomer has the anomeric hydroxyl group below the plane of the ring. In the
p-anomer, the hemiacetal hydroxyl group is above the plane of the ring. The structures
of the two anomers of D-glucose in Fischer and Haworth projections are shown below:

Fischer projection formulas Haworth formulas

1 I I 6

HO-CH
I

- .H-C '2 H-C

1 a-D-glucose

6~ 6~
CH,OH CH,OH

You may ask as to what difference the position of just one hydroxyl group on the
ring could possibly make. Well, it is this very small difference which determines
whether a cell can utilise a molecule in the metabolic process of a living organism.
For example, the position of hydroxyl group on C-1 of glucose units in starch
(polysaccharide made up of a-glucopyranose units) and cellulose (polysaccharide
made up of P-glucopyranose units) is responsible for large differences in their
properties. For example, starch is digested by humans but cellulose is not digestible.
The a and f3 anomers of D-glucose possess different properties. a-D-Glucose melts
at 419K and has a specific rotation of +112.2". P-D-Glucose melts at 423K and has
a specific rotation of +18.7". If either a-D-glucose or P-D-glucose is dissolved in
water, the specific rotation changes slowly until it reaches an equilibrium value of
+52.7". This gradual change in specific rotation from +112.2" or 18.7"to +52.7", is
called as mutarotation and results from an interconversion of and P-glucose to an
equilibrium mixture containing 36% a-anomer and 64% p-anomer. The two forms
undergo interconversion through the open form of glucose (0.02%).
Another important aspect of the structure of monosaccharides is in relation to their
conformation. The C-O-C bnght C bond angle in the herniacetal ring is 111' and is ~ o n f o r n ~ a t l oisn a parttcular
similar to that of the C-C-C ring angle (109') of the cyclohexane ring. The orientatloll o f the atonls 111 .I
molecule. differing from other
pyranose ring of glucose, rather than forming a true planar ring, is puckered in a possible orie~ltatiollsby rotation
manner similar lo the cyclohexane ring which exists in the chair and boat forms.m e chair around single bond5
conformation of glucose minimises the ring strain and it is this ring form that is preferred:

. a-D - ( + ) -Glucopymmosc $-D - ( + ) -Glucopyrmose

 You might have observed that although Haworth projections are easy to draw, they
do not correctly represent the true shape of a sugar ring. But for easy and simple
representation of a sugar ring, we shall continue to use them in this unit. The
knowledge you gained about D & I. isomers as well 3s a and P anomers will make
it easier to understand about other carbohydrates. Now let us describebriefly home
other important monosaccharides.

2.3.4 Fructose and Other Monosaccharides

Fructose, also called levulose or fruit sugar (mol. formula C6H1206), is found in
many fruit juices and in honey. It is a ketohexose and the sweetest sugar known,
much sweeter than sucrose, which is the common table sugar or cane sugar. It is
also a component of sucrose and is produced by hydrolysis of the polysaccharide
inulin. Fructose molecules also form internal hemiketals and
furanose ring structures (Fig.2.4). Although its structure can
fructopyranose as well as a fructofuranose, it is the furanose
present in solution:
Y

Galactose (mol. formula CjH1206) does not occur as a free m This

aldohexose can be formed by hydrolysis of larger
of milk sugar, lactose.

a - Galact~seor a - Glactopyranosc f3 - Galactose or f3 - Glactopyranose

Glycolipids, which are components of the brain and nervous system, also contain
Sugars in which an -OH group is
replaced by hydrogen, are known as
galactose. D-galactose as well as D-glucose exist in nature as their 2-amino
. -
deoxysugars. m e carbon at which derivatives and are commonly referred to as amino sugars. f%-Drmm Glucosamine
this replacement occurs is denoted is a component of chitin, which is the major component of the exoskeleton of
by the number of that carbon in the
deoxysugar. insects and crustaceans. D-Galactosamine is an important component of cartilage.
Among the pentose sugars, that play a major role in human metabolism, are
D-ribose and deoxyribose. D-Ribose which exists as a furanose is a component of
RNA while 2-deoxyribose is a compopent of DNA.

Ficher pl-ojectious H a w d h projections

H\c/ 0 H\c/o 5 5

H-C-OH
I H-C-H
I
-
I
H-C-OH H-C-OH
I
PC-OH
I H-C-OH
1 OH OH OH H

I I
CH2OH
p - D - Ribose
CH20H - Ribofurnose
( P-D ) 2- L)eoxy - p -'I)-ribose
D - whose -
2 - Deoxy - D ribose

Both the a and f3 forms of ribose exist in solution, however, it is the (3 Corm that is
found in nucleic acids and other metabolically active compounds.
Some metabolically active forms of sugars are present as phosphate esters ol' the
primary alcohol group. For example, glucose-6-phosphate and fructose .

diphosphate are some important sugar phosphates.

tx-D-Glucose -6-phosphnie(G6P) Fructose 1,6dipbospbnie (FDP)

SAQ 3
Tick mark [ \/ ] the following statements as true or false.
a) A fresh solution of glucose has a specific rotation of 52.7". [TrueIFalse]
b) Fructose is present mostly as a furanose. [TrueIFalse]
c) Ribose is a ketopentose [TrueIFalse]

d) The common form of glucose, as represented by Haworth projection, is known

as glucopyranose. [TrueIFalse]
SAQ 4
What do the notations D & L refer to in sugars. Draw the Fischer projections for D
and L glucose.

We shall now study some reactions of monosaccharides.

2.3.5 Reactions of Monosaccharides

Presence of a large number of functional groups in sugar molecules gives rise to
diverse chemical reactions. Some of these were outlined in Fig.Z.3 for glucose. We
shall now describe some general reactions of monosaccharides in this subsection.
Monosaccharides, when treated with dilute alkali for several hours, undergo
isomerisation. For example, D-glucose undergoes isomerisation to D-fructose and
D-mannose:

H-C=O HO-C-H HO -CH2

I II I
H-C -OH C-OH

-
C=O
I I
I
II
HO-C-H \HO-C-H -HO-C-H L

I I 7 II 7
H- C-OH H- C-OH
I I

Euetliol iutennediate D-Fructose

Irons couliguratiou

HO-C-H O=C-H
II I
HO- C -H HO-C
I I
HO-C-H ,HO-C-H
I 7 I
H- C-OH H-C-OH
I I
H-C-OH H-C-OH
I I
CH20H CH20H

. Enediol intermediate D-Maunose

c b couliguraliou

Isuu~erisatiwof D-glucose in dilute alkali

Monosaccharides are generally more stable to dilute mineral acids. However, aldose
sugars, e.g., glucose when heated in strong mineral acids, undergo dehydration to
form hydroxymethyl furfural. Pentose sugars, under the same conditions yield
This reaction forms the basis for a qualitative test (Molisch test) for sugars, as
furfural and its derivatives, can react with a-naphthol to form a coloured product.
Sugars that contain a free aldehyde or ketone group, reduce solutions of mild Moliah lest - An alcoholic solution
of a-naphthol is mixed with the
oxidising agents such as, cu2 (Benedict's solution, Fehling's solution) or A ~ +
+
carbol>ydratesolution in a test tube
(Tollens' solution). Benedict's solution, which is an alkaline solution of CuS04, is and ,old ,o,lcentrated H~SO,is
widely used for the detection of reducing sugars. It forms the basis of clinical poured along the sides a red-violel
ring is formed where the two
detection of glucose in urine samples, when glucose, if present, reduces c u 2 + ions so~utionsmeer.
to CU+ ions, and a brick red precipitate of cuprous oxide is formed:

COOH
I
I
H-C -OH H-C -OH
I II
HO-C-H
HO-C-H + ,Cu20
I + 2 cu2+ N a O H ! I

D-Glucose D-Gluconic acid

In general, mild oxidising agents and some enzymes, convert sugars to YOU will recollect from Fig.2.3 !hat
monocarboxylic acids, called aldonic acids. For example, D-gluconic acid, bromine water also oxidises the
aldehyde function lo the carboxylic
D-galactonic acid and D-mannonic acids are products of mild oxidation of glucose, function, However, i t does ,lol
galactose and ..tnnose, respectively. oxidise a ketose and therefore, is
used to differentiale an aldose from
a ketose.

COOH COOH
I I
H-C- -OH HO-C- H
I I
H-C-OH
I I
H-C-OH H-C-OH
I I
H-C-OH H-C-OH
I I

D-Gdnctonic acid D - M a ~ o n i acid

c

Carbohydrates undergo oxidative cleavage with periodic acid ( HI04 ), like other
compounds that contain two or more hydroxyl or keto groups on adjacent carbon
atoms. This reaction, which was introduced by Malaprade in 1928, is very useful in
the structure determination of carbohydrates.
 CHO
I

HO- cI -H 5HI04
H
I
0
11
I 3 H- C=O t 5 H-C-OH
H-C-OH
I
H-c-OH
I
CHzOH
-
D Glucse
Specific oxidation of the primary alcoholic function with enzymes results in the
formation of uronic acids, some of which are key components of several
polysaccharides:
D - Glucose D '- Galactose D - Mannose
Enzymatic
oxidation
1
Enzyma~ic
oxidation 1Enzyniatic
oxidalio~i

HO-C-H

H-C-OH H-C-OH
I I I
COOH ,
COOH COOH
D-Glucurmic acid DGdactumnic acid D - M n ~ u r o n i cncid

Glucuronic acid is one of the principal carrier, with the help of which the
metabolites of drugs and toxins are excreted from our bodies. The usually nonpolar
toxins form polar complexes with it andare excreted in urine.

SAQ 5
Fill in the blanks:
a) D-Ribose, on heating with HC1 gives ..............................................................

b) An alkalipe solution of glucose contains ........................ and ........................as

is omirisation products.
c) Mild oxidation of glucose gives .......................................................................

d) Enzymatic oxidation-ofprimary alcoholic group of sugars gives

. A lactone is an internal ester Both aldonic acidsand w n i c acids undergo cyclisation to form 5 and 6 membered lactones:
compound formed by elimination of
water, from an -013 group and a
-COOHgroup, in the salile

H OH H H

D-Gluconod-Isclone D-GlucurmoGlactone
D-Glucono-a-lactone and D-glucurono-Glactone are, respectively, the lactones of Cubohydrata

D-gluconic acid and D-glucuronic acid. An important naturally occuring lactone is

ascorbic acid or vitamin C. It is a a-lactone, which is synthesised by all plants and A~~~~~ acid is a carhllydrate
many animals. metabolite. Human beingscannot
synthesise $. They obtain it by
eating foods that contain vitamin C.
e.y., vegetables. 011 the other hand.
carnivores, such as, catscau
synthesise vitamin C. Prolonged
dietary deficiency in v i ~ a n ~C
i nleads
to scurvy.

I
HO-C-H
I
CH20H

L-Ascorbic acid
Enzyme systems in many animals modify glucose to ascorbic acid. It can easily
undergo oxidation - reduction and, therefore, it participates in biological redox
reactions as a cofactor.

L-Ascorbic acid Dehydro-1,-ascorbic acid

(reduced form) (oxidised fonn)
The aldehyde and ketone function of monosaccharides are reduced by sodium
borohydride to the corresponding sugar alcohols. D-Sorbitol and D-mannitol are the
two important naturally occurring sugar alcohols:

CH20H CH20H
I I -H
H-C-OH HO-c
I I-
HO-C -H H-c - OH
I I
H-C -OH H-C-OH
I I
R-C-OH H-C-OH
I I
CH20H CH20H
D-Sorbitol D-Mnnnitol
All the hydroxyl grodps in sugars can be acetylated. For example, D-glucose gives a
penta acetyl derivative on treatment with acetic anhydride:

Penha-acetyla-D-glucose( Ac - CH3 - C -)
II
0
 Aldehyde group in the aldoses reacts with phenyl-hydrazine to form
phenylhydrazone (Fig.2.3). However, in excess of phenylhydrazine, the reaction
proceeds to yield crystalline osazones:
Phenylhydrazine is a powerful
reagentin the study of sugars and
osaione formation provides an easy CHO CH =NNHC6H5
identificationof different sugars I 3C6HSHN.NH2 I
through t'reir characteristic- CHOH C= NNHC6HS + C6HSNH2+ NH3
crystalline forms and melting points.
An osa~one,more importantly,
alsogives anideaof configuration of
1 1 osazme
various sugars. For example, aldose
(+)-glucoseand (+)-mannose give
the same ozasone, which means that Osazone formation is typical of all carbohydrates with an-hydroxy aldehyde or
they are epirneric at C-2, as ozasone a-hydroxy ketone function.
formation destroys the chirality only
at C-2 of an aldose. (-)-Fructose also A very important reaction of monosaccharides is the formation of acetals, more
forms an osazone which is identical
with that obtained from (+)-glucose, commonly known as glycoside formation. For example, D-glucose (a hemiacetal)
thereby, implying that (-)-fructose combines with a molecule of methanol in the presence of an acid to form an acetal.
h?s similar configuration ;IS In this reversible reaction,.the anomeric hydroxyl group ( C - l , 4 H ) condenses with
(+)-glucose at C-3. C-4 and C-5.
an alcohol to form a and P glycosides. The bond that connects the anomeric carbon
to the acetal oxygen, is known as the glycosidic bond:
glycosidic

CHzOH
I

H OH
You may recall the forn~ationof a
hemiacetal 1 hemiketal. These are
basically not very sable and can
The acid catalysed'condensation of a-D-glucose with melbanol to fornl an anon~ericpair of ~nethyl-D-
react with one more n~oleculeof an
glucosides. D-Glucose in solution will be a nlixture of, a, fi and linear structures
alcohol to form a stable cetalketal.
with the elimination of a water
molecule. These bonds are labelled a and P, depending on whether the oxygen atom in the
R OH acetal (glycoside) is below or above the plane of the sugar ring. Glycosides can be
\c' + R"OH >- hydrolysed to monosaccharides and alcohols, with dilute acids or enzymes.
R'O' \H Glycosides do not undergo mutarotation, nor are they readily oxidised. Both these
ktcnuacetal r?l~~bol
R OR" properties require the presence of a frec -OH group at the anomeric carbon.
+ IIzO .
R'O' \H The acetalkehl (or glycoside) formation is an important reaction, because it helps in
AR'taJ
understanding the structure of oligo- and polysaccharides in which the constituent
monosaccharide units are held together by glycosidic bonds. Generally, C-1 (anoineric
carbon) of one monosaccharide reacts with the 4 H on C-4 or C-6 of another
monosaccharide molecule. This will be clear from the representations in Fig.2.5.

fi - 1, 4 - glucosidic bond

+ H20
OH

Fig.2.S: 'Ibe other groups on the sugar ring, nave been omitted for the sake of convenience and c l r i t y
 As is clear from reactions of Fig.2.5, the acetal linkage is a C-1 and C-4 bond and
can be termed as a-1,4-glycosidic or p-1,4- glycosidic bond, depending on whether When the henliacetal is g l u a d c ;.
the starting hemiacetal has an a or a f M H group. Besides, you would observe that acetal formation, the resultant acetal
linkage is referred to asglucosidic
the resulting disaccharide (or polysaccharide, as the case may be) has only one bond, i.e.. an acetal bond to glucose.
anomeric carbon (C-1) left intact, and, therefore, the disaccharidelpolysaccharide Ho*ever. generally. this bond is
called a glycosidic bond, i.e.. an
can exist in either an a or fl anomeric form. acetal bond in any carbohydrate and
Now try the following SAQs first, and then we shall describe other carbohydrates. not just glucose.

SAQ 6
The bond between C-1 o f glucose
Match the following in A with those given in B and the oxygen aton] of methanol is
called a glycosidic bond-specifically,
an 0-glycmsidic bond.

1) D-Sorbitol a) Anomeric carbon

2) L-Ascorbic acid b) A disaccharide
3) Glycoside c) A sugar lactone
4) C-1 of glucose d) Sugar alcohol

SAQ 7
How are monosaccharide units held together in a disaccharide? Can a
dilpolysaccharide exist in a and P anomeric forms?

2.4 DISACCHARIDES
The disaccharides are the most commonly occurring oligosaccharides in nature and
on hydrolysis yield two monosaccharide molecules. Maltose, lactose and sucrose
are the three widely found disaccharides and each has a molecular formula of
' C12H22011. Now let us study these carbohydrates briefly. We shall mainly describe
the nature of monosaccharides and the linkages which hold them together.
2.4.1 Maltose
Maltose or mall sugar exists in small amounts in nature. It is obtained mainly by the
incomplete hydrolysis of starch, glycogen or dextrins. This disaccharide is made up
,of two glucose units (or residues), linked through the C-1 hydroxyl of one res~duein
a-form and C-4 hydroxyl of the other, by an a,1,4-glycosidic bond. Maltose
undergoes'mutarotation and its solution has an equilibrium mlxture of a and P
maltose (with a small quantity of the aldehyde form of maltose). It is a reducing .
sugar.
a - 1, 4 - glucosidic bond
6
CH20H

( a -D- Glucose unit )

a-Maltose
( a
-
- D - Glucose unit
-

)
 bond

H OH H OH
( a - D - Glucose u n i t ) ( fl -D- Glucose unit)

2.4.2 Lactose
Lactose or milk sugar is a disaccharide present in the milk of mammals and is
synthesised in the mammary glands after child birth, from glucose and galactose
under hormonal regulation. Cow's milk contains on an average 4% lactose while
human milk contains 6-8%. It is a white powder that is nearly tasteless. It is,
therefore, used in special high calorie diets.
Lactose is formed by the condensation reaction between anomeric hydroxyl of
p-galactose and C-4 hydroxyl of glucose, in a P-1,4- glycosidic link. Lactose also
undergoes mutarotation and is a reducing sugar.
fl - 1, 4 - glucosidic bond
6
CH20H
I - CH20H

I I I3 21
H OH
( fl - D - <;slactose unit)
-
H
-
OH

-
( a D ~ l u c o s \ eu n i t )

fl - 1. 4 - glucosidic bond

.-
I - - H GH
( fl D (;alnctose unit)
P-Lactose
( f~ - D - Glucose u n i t )

Sweetness of sugars is measured 2.43' Sucrose

relative to the sweetness of sucrose,
which has been assigned a value of Sucrose (table sugar, cane sugar, beet sugar) is the most widely employed
100.nesweetnessvalueof other sweetening agent and is found in higher plants (e.g., in juices of fruits, vegetables)
sugars relative to sucrose are as
~OIIOWS: and also in honey. It is commercially obtained from sugar cane or sugar beet. Upon
hydrolysis, sucrose yields one molecule each of glucose and fructose. In .
Relative sweetness value
comparison to maltose and lactose, it has properties which are unique. It does not
Lactose 16
undergo mutarotation and is a nonreducing sugar. This is because, a-glucose and
Galactose 32
Maltose 33 a-fructose are held in an a-1,2 glycosidic link instead of the more common
~~ucose 74 1,4-glycosidic bond. As a result the anomeric carbons of both the constituent sugars
Sucrose 100 are involved in the linkage formation. Therefore, none of these is available for
Fructose 173 mutarotation or for undergoing oxidation reaction.
 6 / Q - 1 . 2 - glucosdic bond

- AH
OH H
( Q -D- (;lucose u n i t ) '( Q D - Fructose unit)

Sucrose Sucrose can be hydrolysed, by acids or enzymes found in intestines and in

yeast, to ;I mixture of fructose and glucose. This mixture is known as invert sugar.

SAQ 8
Which of the following is the correct structure of sucrose? Tick [ d ] mark your
answer
a) 1-a-D-glucosyl-4-fructose [ 1

2.5 POLY SACCHARIDES

We have already described monosaccharides and disaccharides in sections 2.3 and
2.4. You have been introduced to some general reactions of monosaccharides as
well, including the glycosidicbond formation. This helped you in understanding the
formation of disaccharides also. Now let us describe polysaccharideswith emphasis
on the linkages that hold the monosaccharide units in them. Polysaccharides, also
known as glycans, are large polymers of hundreds or thousands of monosaccharide
units held together by glycosidic linkages. The polysaccharide chaills may be linear
or branched and may be composed of only one type of monosaccharide
(homopolysaccharide, e.g., starch) or two or more types of monosaccharides
(heteropolysaccharides, e.g., in cell wall). In nature, polysaccharides are employed
as part of the structural tissues (known as structural polysaccharides) or may be
used for storing energy (known as storage polysaccharides). Polysaccharides are
not sweet and do not mutarotate. They are generally unreactive as most of their
hemiacetal groups are bonded in the glycosidic bonds. We shall now describe more
about some storage polysaccharides.

25.1 Storage Polysaccharides

A solution of iodine and Kl is used
Starch is the principal storage polysaccharide in plants. It not only serves as a to test for the presence of starch and
the degree to which it is hydrolysed.
reserve food in plants but is also a major source of carbohydrates for human beings. Stmch-igdinewmplexcJ range in
It is a glucose polymer and when excess enters a plant cell, it is linked by colour from blue black to red.
an enzyme to the end of starch molecules. In case of shortfall of glucose in the cell, Amy"segives a blackwlour
and amylopectin a red wlour with
starch is hydrolysed within the cell to release glucose. Dietary starches are present iodine.
in potatoes, rice, wheat, corn and many other plant sources.
Partial hydrolysis of starch by acids,
Natural starch ( W l o O s ) , is a mixture of two components, namely, amybse and enzymesor dry heat, produces
amybpectin. The proportion of amylose and amylopectin varies in starches from ~ ' ~ , " ~ ~ ~ ~ ' , "
different sources, but usually consists of 25% arnylose and 75% apylopectin. are, therefore, employed as
Amylose (molecular weight 50,000-60,000) consists of D-glucose units linked in a adhesives.negol&nwlourof
bread crust is due to the formation of
linear manner by a-1,4-glycosidic bonds: dwrtrins.
 A segment d amylose m o k d e

The average chain length is 300-350 glucose units. you would observe that due to
a-1,4 linkage, amylose has a nonreducing as well as a reducing end. In solution
amylose assumes a helical structure as shown below. It is soluble in hot water,
which is due to the formation of a colloida~suspension.

-
Amylosc h e l i d structun

Amylopectin (molecular weight larger than 500,000) is a highly branched glucose

polymer. The linear chains have glucose molecules bonded by a-1,4-glycosidic
links. Branching occurs every 20-24 glucose units on an average and is a result of
a-1,6- bonds between the glucose units. Amylopectin molecules are significantly
larger than amylose molecules, and are insoluble in hot water.
 ~ m ~ l oiss hydrolysed
e by an enzyme, amylase, present in saliva and pancreatic cubobydmt-

juice, to a mixture of maltose and glucose. p- Amylase, hydrolyses amylose from

the nonrcducing end to yield successive units of maltose only. Amylopectin, resists Glycogen is alw by
hydrolysis with and P-amylase a1 branch points and also at u-1,6-linkages, (1and amylases 10 glucose.
resulting in a highly branched core of amylopectin called the limit dextrin, as one nlaltose and 'inlit dexlrin.
of the products of digestion.
Glycogen is the storage form of glucose in animals and is the equivalent of plant
starches. It is mainly concentrated in the liver and muscles. A well nourished body
has enough glucose in the form of glycogen, to supply it with energy for about 18
hours. Glycogen is similar iristructure to amylopectin, except that the branching
occurs much more frequently every 8-10 glucose units. Most glycogen molecules
have molecular weights higher than one million.

Glycogeu
Each circle io the above cbaiu represeuls a D-glucose uuit, Linked by u-1 , 4, bouds iu the main chain and
by a-1,6-bonds at the brauches

When required for metabolism in the body, glucose units are removed one by one
from glycogen, by a process of phosphorylation (i.e., bond rupture with the addition
of a molecule of phosphoric acid) in the presence of an enzyme, glycogen
phosphorylase, to yield glucose-1-phosphate. This is utilised tbr the metabolic
needs of the body.

GI, t HPO:- -* Glucose - 1 - phosphate t GI,- 1

Glycogen having Phosphate ion Glycogen having
n glucose units 11- 1 glucose unils

SAQ 9
Tick [ d ] mark the appropriate statement.
Limit dextrin is
a) Product left after digestion of starch by amylase.
b) Highly branched portion of amylose.
c) Non~.cducingend of amylopectin.
r
SAQ 10
Polysaccharides do not mutarotate, why?

We shall now describe a common structural polysaccharide.

2.5.2 Cellulose: A Structural Polysaccharide

Cellulose is a structural polysaccharide and the rigid cell wall of plants is composed
B~O~OI~CUI~S-I primarily of this substance. It constitutes nearly one half of the carbon in the
biosphere. Cellulose occurs almost in pure form iri cotton ( 9 8 % ) and to a lesser
The difference between amylose and extent in jute (50-7096) and wood (40-5O%).Celh1lose molecules are insoluble in
cellulose is in the nature of the water, due to their size and structure.
glycosidic bond holding glucose
units together. In amyIose.it isa-1,4 Cellulose is a linear polymer of D-glucose units bonded by p-1,4-linkages as shown
link*while in cellulose it is a 8-194- below. It has a molecular formula of (CijH1o0s),,, where n = 500 to 5,000,
linkage.
depending on the source, method of extraction and treatment.

- 1, 4 - glucosidic bond

0-

11 OH H OH H OH
Segment of cellulose chain

Unlike starch, it is highly resistant to acidic or enzymatic hydrolysis. However,

rumen bacteria in grazing animals and also termites, possess an enzyme, cellulase,
which hydrolyses cellulose to glucose. Other animals, such as man, lack this
enzyme and cannot utilise cellulose as a source of energy. Any cellulose we eat,
therefore, passes through the digestive tract undigested, providing the roughage we
require for proper elimination.
Cellulose is a valuable commercial compound and as cotton it is used in clothing.
On chemical treatment, cellulose forms a wide variety of products, such a s
celluloid, rayon, guncotton (an explosive), cellulose acetate, methyl and ethyl
cellulose, etc. These derivatives are useful plastics that can be spun into fibres and
spread into films. Cellulose in wood is iilso used to manufacture paper and a
number of paper products.

2.6 COMPLEX POLYSACCHARIDES

In the preceding sections, we have described polysaccharides essentially made up of

hexose monomer units. In addition to these, there are many complex carbohydrate
molecules that contain amino nitrogen, which is either acetylated or combined with
sulphuric or phosphoric acid. These complex polysaccharides are important as
intercellular substances and exist either free or in combination with proteins or
lipids.
Let us describe the structure and role 01' some of these important complex
molecules.
2.6.1 Glycosarninoglycans
The extracellular spaces, especially of connective tissues like cartilage, tendon, skin
and the walls of blood vesseis, consist of proteins collagen and elastin, embedded in
a gel like matrix called the ground substance. This ground substance is mostly
made up of complex polysaccharides called glycosaminoglycans or
mucopolysaccharides. These complex molecules have a slimy, mucus likc
consistency, which makes them highly viscous and elastic.
Glycosaminoglycans are made up of alternating glucuronic acid and hexosamine
residues. Hyaluronic acid is an example of a glycosaminoglycan. It is an important
component of the ground substance present in the synovial fluid of joints and
vitreous humour of eyes. It consists of about 250-25,000 repeating units of
f3-D-glucuronic acidand N-acetyl-P-D-glucosamine linked by f3- 1,3 bonds. The
repeating units are, in turn, joined by (j-1,4 bonds as shown:
 8 - 1. 3; gluwsidic bond
~nrbohydra~~

H NHCOCHJ
A scction of hyaluronic acid

Hyaluronic acid tightly binds ions like ~ a ' ,K' and c,i2 It is a rigid and highly
+.

hydrated molecule. In solution, it occupies a volume about 1000 times of that in its
dry statc. These properties make it highly suitable as an excellent biological shock
absorber in the joints and also as a lubricant. Another glycosaminoglycan,
chondroitin-4-sulphate is a major component of cartilage and other connective
tissues. Its structure is similar to hyaluronic acid, except that the N-acetyl-
D-glucosamine residue is replaced by N-acetyl-D-glucosamine-4-sulphate.
Dermatan sulphate present in the skin tissue, keratan sulphate found in the keratin
of nails and hooves, and heparin are other examples of complex polysaccharides.
Heparin is a variably sulphated glycosaminoglycan, consisting mostly of alternating
a - 1 , 4 linked residues of D-glucuronate-2-sulphate and D-glucosamine sulphated at
N and at C-6. It occurs almost exclusively in the arterial walls and inhibits blood
clotting. It is, therefore, a widely used powerful blood anticoagulant.

2.6.2 Glycoproteins
Many proteins in the cells are covalently associated with carbohydrate molecules,
resulting in a type of biomolecule known as glycoproteins. The carbohydrate
content of such glycoproteins varies from 1% (e.g., in immunoglobulins) upto 85%
(e.g., in blood group substances). These molecules occur in almost all forms of life
and include most of the plasma proteins, enzymes, hormones, etc. Most of the
proteins in membranes, e.g., lipid bilayers, are glycoproteins. In general,
glycoproteins consist of a core protein to which the carbohydrates like
glycosan~inoglycans,or N-acetyl amino sugars are covalently linked.
Glycoproteins serve diverse functions, but in general they act as recognition sites Antigensare foreignsublances
for various biological interactions. Glycoproteins like immunc~globulinsact as that invade the body aid a~itibodiea
antibodies; y- globulins fight infectious diseases, and mucin in saliva and gastric are substances that cou~iteractthem.
juice aids in the digestive process. Another glycoprotein, interferon, is produced by
cells in response to viral infection. Some glycoproteins in the antarctic fishes
protect them against freezing.

2.6.3 Blood Group Substances

Plasma membranes of animal cells are linked to a number of carbohydrates, and L - F U W S is
~an uncommon
literally appear as "sugar coated". These carbohydrates, basically components of carbohydrate,where -CHIOH group
glycoproteins and glycolipids, are a part of the mechanism by which various cell is replaced by a -CH3 group.

types identify (recognise) each other and act as biochemical markers (antigenic
determinants). These membrane bound carbohydrates contain as many as 4 to 20
monosaccharide units, predominant among which are D-galactose, L-fucose,
N- acetyl-D-glucosamine and N-acetyl-D-galactosamine.
Blood group substances were the first-discovered and well- understood of all
membrane-bound carbohydrates. They are chiefly found on the surface of
erythrocytes, but can also be found on proteins and lipids in other parts of the body.
In thc A130 group system, put forth in 1900 by Karl Landsteiner, four blood groups
have been identified~heseare A, B, AB and 0.The chemical basis for this
classification is the relatively small, membrane bound carbohydrate. The
carbohydrate composition on the erythrocytes of A, B, AB and 0 blood groups is
Biou~okules-1
b - 1. ... bond wilh
last monosaccharide -
a 1.3 bond OH on erythrocy~c
The ABO grouping is very
important in blood transfusion.
Bbod fron individualsofIbe m e - - 'f
N aEetyl- D galactosamine -D
f
- galaclosc -N -"1*4"nd 4
acetyl -D - gluc0Sanline - cell wall
type can be mixed wilhout clumping ( NAG^) ( Gal ) (NAGID)
(agglutination) of crytbrocytcs.
However, if ~enunof typc A blood
a - 1.2 bond
-1 L-fucose
is mixed with type B blood or vice
verse, the erythrocytes will clump. (Fuc)
The following transfusion
possibilities exist.
Universal donor
Fi26 Carbohydratecomposition of erythrocytes (dtype A blood)

Gal In type B b l o o d
Universal acceptor

NAGal In
I
type A blood

Mlsslng In type 0 blood

Last sugar in type AB is NaGal as well as Gal as shown:

Gal - G a l -

SAQ 11
How does type A blood differ from type 0 blood?
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................

2.7 SUMMARY

Carbohydrates are polyhydroxy aldehydes or ketones of the approximate

composition C, (HzO),,.
Various monosaccharides, such as, ribose, fructose, glucose and mannose differ
in their number of carbon atoms, the position of the carbonyl group and
diastereomeric configuration.
 Cubohydrmta
Sugars undergo intramolecular cyclisation to form hemiaatals or hemiketals
and exist in two anomeric forms. The five and six membered rings that are
formed are called furanoses and pyranoses, respectively.
Sugars can be oxidised to uronic acids or aldonic acids or reduced to alditols.
Sugars also form acetyl and ammo derivatives.
Disaccharides and polysaccharides have glycosidic bonds, which hold the
monosaccharide units together.
The different disaccharides can be distinguished by the nature of the sugars
present and the position and orientation of the glycosidic bond.
Starch and glycogen, the chief storage polysaccharides, are branched glucose
polymers with a-1,4 linkages in the chains and a-1,6 linkages at branch points.
Cellulose the most important structural polysaccharide of plants is a linear
polymer of D-glucose with 8-1,4 linkages.
Starch and glycogen are easily hydrolysed by acids and enzymes, while
cellulose is resistant to acids and is hydrolysed only by cellulase.
Complex polysaccharides are important as components of intercellular ground
substances and may exist either free or complexed with proteins.
The glycosaminoglycans-hyaluronic acid, chondroitin sulphate, keratan
sulphate and heparin are high molecular weight polymers consisting of uronic
acids, and sulphated or amino substituted acetyl sugars.
Glycosaminoglycans are excellent shock absorbers and lubricatig compounds in
tissues.
The glycoproteins on the external surface of the erythrocyte membranes are
important as blood group antigens.

2.8 TERMINAL QUESTIONS

1) Define the terms enantiomer, diastereomer, anomer and mutarotation, giving

specific examples from carbohydrates.
2.) Name and give the structure of a naturally occurring (a) sugar alcohol, (b)
amino sugar, (c) sugar phosphate, (d) deoxy sugar.
3) Name the storage polysaccharides present in animals and plants. Indicate the
structural differences between them.
4) Why is maltose a reducing sugar and sucrose a non-reducing sugar?
5) Why is cellulose insoluble in water and why is it not used as an energy source
by human beings?
6) Give.the structures of sucrose, lactose and maltose. What are the sources of
these common disaccharides?
7) How is the classification of polysaccharides related to their composition and
function?

2.9 ANSWERS

Self Assessment Questions

1) a) True b) True c) False d) False

3) a)False b) True c) False d) True

 B~OIIIOI~CUI~S-I
4 In sugars the symbols D & L are used to denote the contiguration at the chiral
carbon, farthest from the carbonyl group. Whether a sugar is D or L
enantiomer, is arrived at by making a comparison to the configuration of
glyceraldehyde. Structure of D and L glucose are given in subsection 2.3.1.
I 5) a) Furfural b) Fructose and Mannose c) Gluconic acid d) Uronic acids
9

7) In a dilpolysaccharide, the constituent monosaccharide units are held by acetal

linkages, known as glycosidic bonds. These are formed between C-1-OH of
one sugar unit and usually the C-4 or C-6 -OH of another sugar molecule.
These bonds can be or f3 glycosidtc bonds, depending on the starting
hemiacetal. The resulting dilpolysaccharide does have one anomeric carbon
left as such and the -OH group on it can have and f3 orientation, i.e., the
dilpolysaccharide can be in or f3 anomeric forms.

9) a
10) In polysaccharides, the anomeric carbon of the constituent sugar units is not
free to mutarotate, as it is linked in a glycosidic bond with another sugar
molecule.
11) In type A blood the last monosaccharide in the carbohydrate chain is
N-acetyl-D-galactosamine, where as in type 0 blood it is missing.

Terminal Questions
1) Enantiomers are those stereoisomers whose structures are non-
superimposable mirror images of each other, e.g. D- and L- glyceraldehydes
and D- and L-glucoses. When a pair of stereoisomers have more than one
chiral centres and their structures are not related to each other as an object and
its mirror image, they are said to be diastereomers, e.g. D-mannose and
D-galactose. Those monosaccharides and their derivatives which differ from
each other with respect to the configuration around the anomeric carbon atom
only (i.e. the carbon responsible for the aldehyde or keto function) are
referred to as anomers, e.g. a - and f3-glucoses or methyl-a-glucoside and
methyl+- glucoside. When a freshly prepared solution of a monosaccharide
or a reducing di- (or oligo-) saccharide is allowed to stand, its optical activity
changes gradually with t'ime to a constant value. This phenomenon is called
mutarotation. For example, a freshly prepared solution of the common
commercial D-glucose shows a specific rotation equal to +112.2O. With time it
changes to +52.7O.

2.) a) Mannitol b) Glucosamine c) Glucose-Qphosphate d) Deoxy ribose Their

structures are given in subsections 2.3.9 dnd 2.3.5.
3) Glycogen and starch are the reserve polysaccharides iy animals and plants
respectively. While starch is a mixture of the linear polymer amylose (made
of glucose units linked by a-1,4 glycosidic linkages) and branched polymer
amylopectin (which consists of short a-1,4 glucose chains linked by a-1,6
glycosidic bonds and the branching is not extensive). Glycogen is similar to
amylopectin in structure excepting that the branching is more frequent (at
every 8-10 glucose units).
4) Although maltose is a glycoside, the second glucose unit has an -OH group on
its anomeric carbon atom and its ring can open to give an aldehyde and hence
acts as a reducing sugar. Sucrose, on the other hand has its a-D-glucose unit
condensed with the anomeric hydroxyl of g-D-fructose. Since neither unit
possesses an anomeric hydroxyl and the rings cannot open to give an
aldehyde, the sugar is nonreducing.
 Cellulose molecules are insoluble in water, due to their size and structure. In Carbohydrates
5)
cellulose, glucose units are linked to each other by 8-1,4 linkages to form
large linear polymers. Human beings do not possess the enzyme required to
hydrolyse this bond. Amylase present in human saliva and pancreatic juice are
suited for the hydrolysis of a-1,4 glucosidic bonds only. Hence, the glucose
present in cellulose is unavailable to human beings as an energy source.
6) Structures of maltose, lactose and sucrose are given in section 2.4. Sucrose is
the major disaccharide present in sugarcane, lactose is present in milk and
maltose is a product obtained during incomplete (enzymatic) hydrolysis of
starch, glycogen or dextrins and is present naturally in barley malt.
7) Polysaccharides can be classified on the basis of their composition as
homopolysaccharides (starch) and heteropolysaccharides (Peptidoglycan of
cell wall). Functionally, two types of polysaccharides are distinguished,
namely, storage polysaccharides like starch and glycogen, and structural
polysaccharides, like cellulose and chitin.
UNIT 3 : LIPIDS
Structure
3.1 Introduction
Objectives
3.2 Biological Importance of Lipids
3:3 Classification of Lipids
Fatty Acids
Acylgl ycerols
Waxes Phospholipids
Glycolipids
Lipoproteins
Terpenoids
Prostaglandins
Ketone Bodies
3.4 Lipids and Biomembranes
Composition of Biornernbraries
Membrane Structure
-
Functions of Biornernbranes
3.5 Summary
3.6 Terminal Questions
3.7 Answers

3.1 INTRODUCTION

In Unit 2 we described carbohydrates, an important class of biomolecules, which

are a source of energy for the cell. These molecules also form part of the structure
of the cell. Another class of biomolecules, namely lipids, which are extremely
hydrbphobic in nature, are essential constituents of all living cells. You will recall
that we briefly introduced you to the structure of membranes in Unit 1. You learnt
that lipids form part of the structure of cell membranes. These molecules also store
energy for the cell, and, in addition, perform some other tasks also. In Unit 3 we
will describe the biological importance of lipids and classify them into various
types. We will also illustrate their chemical composition. Besides this you shall
learn more about the structure and function of biomembranes. In the next unit we
will describe nucleic acids. Like carbohydrates, nucleic acids are biopolymers and
are important components of the cell.

0bjectives
After studying this unit you should be able to:

describe the main functions of lipids in the organism,

classify lipids into various groups,
describe the essential structural features and major functional roles of various
classes of lipids, and
describe the role of lipids iri the formation and functioning of biomembranes.

3.2 BIOLOGICAL IMPORTANCE OF LIPIDS

Lipids constitute a very heterogeneous group of biological compounds, which have

a common property of being sparingly soluble in water but being freely soluble in
organic (lipophilic) solvents, such as ether, chloroform and benzene. They include
such diverse compounds as fatty acids, acylglycerols, phosphoglycerides, steroids,