Structure and Chemical
Properties of Carbohydrate
Carbohydrate are widely distributed in plant and animal tissues.
In some cases they are referred to as sugars
In photosynthesis, the sun’s radiant energy is used to build
carbohydrates by utilizing water and CO2.
These food substances represent a greater part of the caloric
intake for animals and microorganism
Carbohydrates have various important functions. They serve as
structural and supportive elements(eg cellulose, chitin in the
cell walls of microorganisms, plants and animals)
Some serve as lubricants between skeletal joints(hyaluronic
acid)
CONDT
Others are associated with proteins
(glycoproteins and proteoglycans), while
others are associated with lipids
(lipopolysaccharides)
Some carbohydrates have highly specific
functions eg galactose in milk and ribose in
nucleoproteins
Classification
Carbohydrates may be defined as polyhydroxy aldehydes or
ketones or substances which produce such compounds on
hydrolysis
They are generally composed of the elements, carbon,
hydrogen and oxygen
The empirimal formula of most carbohydrates suggest that
they are hydrates of carbon. The ratio of carbon to hydrogen
to oxygen atoms being 1:2:1 (CH2O).
Thus, the empirical formula of many common carbohydrates
is Cn(H2O)n, for example D-glucose is C6H12O6.
CONDT
There are however others which do not conform to
the ratio and contain substances such as nitrogen,
phosphorus and sulphur
Carbohydrates have molecular weights ranging from
less than 100 to well over 1 million.
They are generally white solids, soluble in water but
not in polar solvents
Carbohydrates are classified into three major groups
namely; monosaccharides, oligosaccharides, and
polysaccharides
Monosaccharides
They are simple sugar and therefore cannot be hydrolyzed
into any simpler form
D-glucose is the most abundant monosaccharides in
nature
Monosaccharides have the general formula (CH2O)n
where n ranges from 3 to 9
They are soluble in polar solvents (eg water) but insoluble
in non polar solvents
The family of monosaccharides includes trioses, pentoses,
hexoses and heptoses indicating that they have 3, 4, 5, 6
and 7 carbon atoms in their backbone
CONDT
Monosaccharides has carbonyl group (˃C=O)
at the end of the chain, called aldehydes and
aldoses, if the carbonyl group is in any other
position , it is called ketone or ketose
Thus, monosaccharides can further be sub-
divided into aldoses and ketoses
Classification of Important Sugars
Aldoses ketoses
Trioses Glycerose Dihydroxyacetone
(glyceraldehyde)
Tetroses(C4H8O4) Erythrose Erythrulose
Pentoses(C5H10O5) Ribose Ribulose
Hexoses(C6H12O6) Glucose Fructose
Heptoses(C7H14O7) - Sedoheptulose
Disaccharides
Are condensation products of two monosaccharide
units for example, lactose, maltose, isomaltose, sucrose
and trehalose
Oligosaccharides- are condensation products of three to
ten monosaccharides. Most are not digested by human
enzymes
Polysaccharides- are condensation products of more than
ten monosaccharide units, examples are the starches and
dextrins, which may be linear or branched polymer
Polysaccharides are sometimes classified as
hexosans or pentosans depending on the
constituent monosaccharides(hexoses and pentoses
respectively)
In addition to starches and dextrins(which are
hexosans), foods contain a wide variety of other
polysaccharides that are non starch polysaccharides
They are not digested by human enzymes and are
major component of dietary fiber. Examples are
cellulose from plant cell wall(a glucose polymer)
and inulin, the storage carbohydrate in some plants(
a fructose polymer)
The structure of glucose can be
represented in three ways
Straight chain
Cyclic structure(a hemiacetal formed by
reaction between the aldehyde group and a
hydroxyl group)- The Harworth projection: The
molecule is viewed from one side and above
the plane of the ring; the bonds nearest to the
viewer are bold and thickened and the hydroxyl
group are above or below the plane of the ring
The chair form
H OH
H O
CHO
CHO
HO
H
H OH
OH HO OH
H OH
HO
HO H
H
H H
H
H OH
OH β-D-glucose; Chair form OH
H
H
H OH
OH
H O
CH2
CH OH
2OH
HO
D-glucose(Straight chain form) HO H
H OH
H OH
α-D-glucose; Chair form
Monosaccharides Have Asymmetric Centers
All the monosaccharides except
dihydroxyacetone contain one or more
asymmetric (chiral) carbon atoms and thus
occur in optically active isomeric forms. The
simplest aldose, glyceraldehyde, contains one
chiral center (the middle carbon atom) and
therefore has two different optical isomers, or
enantiomers.
• When compounds have similar structural formula
but with different configuration in space they are
called stereoisomers
• The number of isomers of the compound will
depend on the number of asymmetric centres
present in the compound.
• The vant rule states that the maximum possible
number of optical isomers of a compound is 2 n (The
fishers projection formula), where the number of
assymetric centres is designated as n
• In general, a molecule with n chiral or asymetric
centers can have 2n stereoisomers.
Glyceraldehyde has 21= 2; the aldohexoses, with
four chiral centers, have 24 =16 stereoisomers.
The stereoisomers of monosaccharides.
• Most hexoses (eg glucose) and ketoses (eg
fructose) have four asymmetric centres
• Glucose with four asymmetric carbon atoms,
can form 16 isomers.
• The more important types of isomerism found
in glucose are as follows
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 3
carbon sugar(glyceraldehyde)
CHO CHO
H OH H OH
HO H
HO H
HO H
H OH
H OH
H OH
CH2OH
L-glucose
D-glucose CH2OH
• The orientation of the –H and –OH groups
around the carbon atom adjacent to the
terminal alcohol carbon(carbon 5 in glucose)
determines whether the sugar belongs to the
D and L series.
• When the –OH group on this carbon is on the
right, the sugar is the D isomer, when it is on
the left, it is the L isomer
• Most of the naturally occurring
monosaccharides are D sugars
• 2. The presence of asymmtric carbon atoms
also confers optical activity on the compound.
When a beam of polarized light is passed
through a solution of an optical isomer, it
rotates either to the right, dextrorotatory(+) or
to the left, levorotatory (-).
• The direction of rotation of polarized light is
independent of the stereochemistry of the
sugar
• In solution, glucose is dextrorotatory and
glucose solutions are sometimes known as
dextrose
• 3. Pyranose and Furanose ring structure: The
ring structure of monosaccharides are similar
to the ring structure of either pyran ( a six
membered ring) or furan (a five membered
ring). For glucose in solution more than 99% is
in the pyranose form
• 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.
• The cyclic structure is retained in the solution,
but isomerism occurs about position 1, the
carbonyl or anomeric carbon atom.
• Please check for Pyran and furan ring
Formation of the two cyclic forms of D- Pyranoses and furanoses
glucose
• For example, D-glucose exists in solution as an intramolecular hemiacetal
in which the free hydroxyl group at C-5 has reacted with the aldehydic C-1,
rendering the latter carbon asymmetric and producing two stereoisomers,
designated α and β.
• These six-membered ring compounds are called pyranoses because they
resemble the six membered ring compound pyran. The systematic names
for the two ring forms of D-glucose are α -D-glucopyranose and β -D-
glucopyranose.
• Aldohexoses also exist in cyclic forms having five membered rings, which,
because they resemble the five membered ring compound furan, are called
furanoses.
• However, the six-membered aldopyranose ring is much more stable than
the aldofuranose ring and predominates in aldohexose solutions. Only
aldoses having five or more carbon atoms can form pyranose rings.
• Isomeric forms of monosaccharides that differ only in their configuration
about the hemiacetal or hemiketal carbon atom are called anomers. The
hemiacetal (or carbonyl) carbon atom is called the anomeric carbon. The α
and β anomers of D-glucose interconvert in aqueous solution by a process
called mutarotation.
• Ketohexoses also occur in α and β anomeric forms. In
these compounds the hydroxyl group at C-5 (or C-6)
reacts with the keto group at C-2, forming a furanose
(or pyranose) ring containing a hemiketal linkage. D-
Fructose readily forms the furanose ring, the more
common anomer of this sugar in combined forms or
in derivatives is -D-fructofuranose.
• 5. Epimers: Isomers differing as a results of variations
in configuration of the –OH and –H on carbon atom
2, 3 and 4 of glucose are known as epimers.
Biologically the most important epimers of glucose
are mannose(epimerised at carbon 2) and galactose
(epimerised at carbon 4)
• Aldose-ketose isomerization: Fructose has the
same molecular formular 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
