CHAPTER 6

MONOSACCHARIDES

CARBOHYDRATES

consist
Carbohydrates are the organic compounds with the general formula C,(H2O),',.Ihey
atom
ratio.
onty oi carbon, hydrogen and orygen atoms with the last two in the 2:1
however,
CaiUohydrates can be viewed as hydrates of carbon, hence their name. Structurally
it is moie accurate to view them as polyhydrory aldehydes and ketones.
are
The term carbohydrates is a synonym of saccharide. The carbohydrates (saccharides)
divided into foui chemicat groupings: monosaccharides, disaccharides, oligosaccharides,
are smaller
and polysaccharides. !n general, the monosaccharides and disaccharides, which
as sugars. The names of
iio*.r molecular weighticarbohydrates, are commonly referred to
and disiccharides very often end in the suffix -ose. (glucosg

ih, ,onoraccharides
lactose).

serve for the

Carbohydrates perform numerous roles in living things. Polysaccharides
(cellulose
in plants ).
storage of energy (starch and glycogen) and as structural components
(ATP, FAD, and NAD)
The rionosacchiride ribose is an important component of coenzymes
related deoryribose is a
and the backbone of the genetic molecule known as RNA. The
component of DNA.

Monosaccharides
Natural saccharides are generally built of simpte carbohydrates called monosaccharides with generd
forrngh (GHrO), where n is three or more. A typica! monosaccharide has the strucfirre

H.(CHO H),(G=O)-(G HOH)r.H,

that is, an aldehyde or ketone with many hydroryl groups added, usually one on each carbon atom that is
not part ofthe aldehyde or ketone functional group.
Monosaccharides (or simple sugars) are the simplest compounds that retain the characteristics of sugars.
There cannot be hydrolyzed to simple sugars, such as otigosaccharides or potysaccharids.
Monosaccharides are classified according to three different characteristics:
the placement of its carbonyl group,
the number of carbon atoms it contains,
and its chiral handedness. 3
lf the carbonyl group is an aldehyde, the monosaccharide is an atdose;
if the carbonylgroup is a ketone, the monosaccharide is a ketose.

Monosaccharides with three carbon atoms are called trioses, those with four are called tetroses, five are
called pentoses six are hexoses, and so on.

Monosaccharide (cont.)

Monosaccharides are the major source of energy for metabolism (glucose) and in
biosynthesis. When monosaccharides are not immediately needed by many celts they are
often converted to more space efficient forms, such as polysaccharides (glycogen, siarch)
and are stored in liver and muscle cells (animals). ln ptants, starch is used for the same
purpose.
Some examples:

Trioses . intermediate metabolites of biosynthesis and degradation of other sugars.

Tetroses

e.g. erythrose, the intermediary in the conversion of gtucose.

Pentoses. such as ribose (component RNA), deoxyboze (component DNA), xylose,

rytulose.
Hexoses - such as glucose, galactose, mannose, fructose (energy sources).

Heptoses. only sedoheptulose occurs in living organisms.

Monosaccharides

TRIOSES and TETROSES

ooc-H

ooc-H

H2f-oH
H-C:O

H-C-OH

H-C-OH
H-C-OH
H2c-oH

H2C-OH

HzG-OH

H29-oH
l-r-C:O

Fr-c-oH

Hz

G-OH

dihydroxyacetone

D-glyceraldehyde

D-erythrulose

D-erythrose

PENTOSES

H2?_oH

\,

H_?_OH

H-?{

H_?-OH
H-?-OH
H2c-oH

r+?-oH

D-ribose

D-ribulose

\,

\,

FF-?-oH
HO-?_H

rf9-oH

I.F?-H
r{-?-oH
FF9-oH

H2c-oH

H2c-oH

H2C-OH

H-?-oH

D-deoxyribose

D-ryloze

\,
?-o

HO-?_H
Fr--c-oH
H2 6-on
D-xyluose

Monosaccharides (cont.)

HEXOSES

\,
r{--?-oH
Ho-?+{
Fr--?-oH

FF?-oH
Hz

C-OH
D-glucosa

oo?"

oo?r,

HO-?-H
HO-?-H

r-F9-oH
Ho-?-+r
HO-?-H
FF?-oH

Fr--?-oH
Fr--?-oH
Hz G-OH
D-mannose

H2

C-OH

D-galaktose

o\^Jl
Y

HT?-H
r-rT-oH
H-?-OH
HO_?-H
Hz C-Fl
D-fucose

11r?

?'-o

HO-?_H

FF?-oH
FF?-oH
Hz

C-OH

D-fructose

lsomerism

of

monosaccharides

Sugars, especially the pentoses and hexoses, occur in the form of isomers. Sugars are
charac{erized by specific forms of isomerism.
EPIMERISM . The two monosaccharides differ in the position of substituents (.H and -OHlat
the same carbon atom, with the exception of the carbonyl group. These forms of isomers are called
epimers. Glucose and galactose are G{-epimers (different position of-OH at Ca atom), glucose and
mannose are C2.epimers.

\,

HO-C-H

rfroH
rF?-oH

FF?-oH
HO-C-H
la

l-F-?-oH
FF?-oH

Ho-f+t
FF?-oH

H2C-OH
D-glucose

*+toH
Ho-?-Fr

Fr--?-oH

H2

oocj

ooG-H

o\^,H

H2

c-oH

FF?-9H
FF?-9H

C-OH

H2C-OH

D-glucose

D-galactose

,*+4

,*?-H

Ca-epimers

D-mannose

C2-epirners

lsomerism

of

monosaccharides (cont.)

ENANTOOMERIS. lt is the presence of sugars in the two mirror forms. Enantiomers (L and D) differ in the
position of substituents at the chiral carbon atom. ln the human body the D.sugars are dominated forms,
L-enantiomers occur sporadically.

ooctH

t*+-oH
HO-?'1-1

FhoH

r{-?-oH
Hz

C-OH

D-glucose

oocj
Ho-E*

,o-+;+l

F?;oH
r{-?-oH
H2

C-OH

L-glucose

Gyclisation of monosaccharides
The aldehyde or ketone group of a straighhchain monosaccharide will reast reversibly with a hydroryl
group on a different carbon atom to form a hemiacetal or hemiketal. The heterocyclic ring is formed with an

orygen bridge between two carbon atoms. Rings with five and six atoms are called furanose and pyranose
forms, respectively, and exist in equilibrium with the straight-chain form. Most of the sugars are present in
the ring forms (5lu 6 membered). Fructose forms only furanose ring.

1f"

I}T--OH

HofH

Iry-OH

Iry-{H
HT{H
H
D-glucos

u-D-glucopyrenos

'fH2oH

;?'o
Ho#{

IryH
IfpH
HflH

OHH
o-D-l'ru kto fu ra no s e

H
D-fru kto

se

Gyclisation

of

monosaccharides

anomerism

Most of the sugars are present in the ring forms (5 or six membered) The transition of sugars from a chain
on the ring results in the formation of additional chiral G-atom, called anomeric carbon. The a and B

monosaccharide arise which have different optical rotation. These anomers are
distinguished by the enzymes. Glycogen and starch arise only from the cr,-D-glucose, cellulose only with p'
D-glucose. ln the solution the o and B anomers are in equilibrium. The transition from one form into another
is called mutorotation. lt changes the optical rotation of the monosaccharides in solution.

anomers

of given

1f"
rrfln

H%TH

HflH
HpH

HflH
H
o-l)-glueopyrallose

D-glucos

F-n-gluco pyr?nos

10

Conformation of hexoses
Glucose is sometimes illustrated as a "chair
form" because it is a more accurate representation
of the
bond angles of the morecure. The "boat"
form of grucor. i. unrt.ui..'

tfehairtf form

"bo att' fo rm

11

Disaccharides
Two joined monosaccharides are catled
a disaccharide and these are the simplest polysaccharides.
They
are composed of two monosaccharide

units b.ound

t"gr*"i iy .

covalent uona inown as a glycosidic

lt is formed via a dehydration reactior, r.r-rttinf
in'ti.
loss of a hydrogen atom from one
monosaccharide and a hydroryl group from
the other. irre tormut. of unmodifiid disaccharides
is
or disacch.JJ.', ir'. widerv ,.p,.i.nt ire
rour
susars;
SalflS;,i|||,'r111,:f;:.'j|r"[ffi'.",,:'rj''os

linkage'

Hzo

t\
I

isomaltase
glucose

isomaltose

glucose

maltose

t2

Digestion of the starch

maltose

Digestion of the starch

The process begins in the mouth wtren an enzyme
in sativa (amylase)
begins to break dovrrn starchy carbohydrates.

A{9t swallowing, the starchy carbohydrates reach the stomach

where hydrochloric
acid combines with them and acts on ttre protein
in the food. The stomach atso
acts as a reservoir for food, squirting out small amounts
into the intestines at
intervals.

ln the smal! intestine (where most carbohydrates-digestion

occurs) the starch is
processed by the enzyme amylase and converted
into maltose and isomaltose .
lsomaltose is a disaccharide similar to maltose
but with a o-(1-6).linkage instead of
the o.(1-4)-linkage.
The maltose and isomattose are then absorbed into
the lining cells of the intestine
and are further simplified, being converted into glucose
molecules that can be
absorbed into the blood. Glucose is carried through the
bloodstream to the tiver,
where it is stored or used to provide energy for the work
of the body.

Lactose

is formed

Disaccharides (cont.)
with B-galac'tose and glukose linked by p.l,4.glicoside

bond. Saccharose is
disaccharide formed by glicoside linkage between anomeric Gr-a-glucose and G2. p.fruktose. Saccharose
is the example of non.reductive disaccharide.
Hzo

\,,H
Iactose

galactose

glucose

Hzo

\,,
*ccharase

fructose
saccharose

13

POLYSAGCHARIDES
Polysaccharides usually contain hundreds orthousands of monosaccharide units.
Classification of polysaccharides:
Homopolysaccharides (homoglicanes) - are composed of identical units of sugar (starch, glycogen,
cellulose).
Heteropolysaccharides (heteroglikanes) - are made up of various units and non.sugar components.
The human the

most important energy sources are starch and glycogen.

Starch is the major form of carbohydrate stored in plants. Starch is composed of a mixture of two
substances: amylose, an essentially linear polysaccharide, and amylopectin, a highly branched
polysaccharide. Both forms of starch are polymert of eD-glucose. Natural starches contain 10-20o/o
amylose and 80-90% amylopectin.

Amylose molecules consist typically of 200 to 20,000 glucose units which fonn a helix as a result of
the bond angles beturcen the glucose units.

Amylopectin consists of glucose residues linked with a -1,4-glycosidic bonds, but the polysaccharide
chains are branched and the branches are the binding sites connected via c-1,6.glycosidic bonds.
Cellulose is a linear polymer linked with a -1,4-glycosidic bonds and is not degraded by a.amylase. lt is
not absorbed and has no part in human energy metabotism. However, the presence of cellulose in
digestion food is important for positive intestinalfunction.