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Carbohydrates
Polyhydroxy aldehydes or ketones, or
substances that yield such compounds on
hydrolysis
Many, but not all, carbohydrates have the
empirical formula (CH2O)n; some also contain
nitrogen, phosphorus, or sulfur
Most abundant organic molecule in nature
Photosynthesis converts CO2 and H2O into
Functions of
carbohydates
1) Are the major source of energy for man as
the oxidation of carbohydrates is the central
energy-yielding pathway in most
nonphotosynthetic cells. For example,
glucose is used in the human body for
energy production.
2) Some carbohydrates serve as reserve food
material in humans and in plants. For
example, glycogen in animal tissue and
starch in plants serves as reserve food
materials.
Classification of
carbohydrates
Are often referred to as saccharides
( Greek: sakcharon- sugar)
Carbohydrates are usually classified in 3
groups
Monosaccharides
Oligosaccharides
Polysaccharides
O
CH2OH
OH
HO
HO
OH
OH
OH
OH
CH2OH
D-glucose
CH2OH
D-fructose
Eg;
Disaccharides Sucrose, Lactose, Maltose,
Cellobiose, Trehalose, Gentiobiose, Melibiose
Trisaccharides Rhamninose, Gentianose,
Raffinose
Rabinose, Melezitose
Tetrasaccharides Stachyose, Scorodose
Pentasaccharide Verbascose
Homopolysaccharides Starch,
Glycogen, Inulin,
Cellulose,
Pectin, Chitin
Heteropolysaccharides Hyaluronic
acid,
Chondrotin sulfate,
dermatan sulfate,
keratan sulfate,
heparin
The Structure of
Glucose Can Be
Represented in
Three Ways
D-Glucose
A: straight chain form.
B: -D-glucose; Haworth
projection.
C: -D-glucose; chair form.
PROPERTIES OF MONOSACCHARIDES
1) Optical Isomerism
) All the monosaccharides except
dihydroxyacetone contain at least one
asymmetric carbon atom and hence they
exhibit optical isomerism.
(The smallest monosaccharides, for which n =
3, are dihydroxyacetone and D and Lglyceraldehyde)
D vs L Designation
D&L
designations are
based on the
configuration
about the single
asymmetric C in
glyceraldehyde.
OH
HO
D-glyceraldehyde
OH
CH2OH
D-glyceraldehyde
L-glyceraldehyde
CHO
C
CH2OH
CH2OH
The lower
representations
are Fischer
CHO
CHO
CHO
HO
CH2OH
L-glyceraldehyde
Sugar Nomenclature
For sugars with
more than one
chiral center, D or
L refers to the
asymmetric C
farthest from the
aldehyde or keto
group.
C
H C OH
HO C H
H C OH
H C OH
CH2OH
D-glucose
Most naturally
occurring sugars
C
HO C H
H C OH
HO C H
HO C H
CH2OH
L-glucose
C
They have the same H C OH
name, e.g., D-glucoseHO C H
& L-glucose.
H C OH
H C OH
Other stereoisomers
CH2OH
C
HO C H
H C OH
HO C H
HO C H
CH2OH
L-glucose
2) Optical Activity
Monosaccharides except dihydroxy acetone
exhibit optical activity because of the
presence of asymmetric carbon atom.
If a sugar rotates plane polarized light to
right then it is called as dextrorotatory and
if a sugar rotates the plane polarized light
to the left then it is called as levorotatory.
3) Epimers
Are those monosaccharides that differ in the
configuration of single specific carbonOH
group on carbons other than the 1st carbon
(anomeric carbon)
4) Functional Isomerism
Functional isomers have same molecular formulae
but differ in their functional groups.
Eg; Glucose and Fructose have same molecular
formulae C6H12O6, but glucose contains aldehyde as
functional group and fructose contains keto group.
Hence, glucose and fructose are functional isomers.
This type of functional isomerism is also called as
aldose-ketose isomerism because aldose is an
isomer of ketose and vice versa.
O
CH2OH
C
HO
OH
OH
OH
OH
OH
HO
CH2OH
CH2OH
D-glucose
D-fructose
5) Ring Structures
In solution, the functional aldehyde group of
glucose combines with hydroxyl group of 5th
carbon atom. As a result a 6 numbered
heterocyclic pyranose ring structure containing
5 carbons and one oxygen is formed.
The linkage between aldehyde group and
alcohol is called as hemiacetal linkage
However,
Fructose forms either
a 6-member pyranose ring, by reaction
of the C2 keto group with the OH on
C6, or
a 5-member furanose ring, by reaction
of the C2 keto group with the OH on
C5.
H
C
H
O
R'
OH
R'
OH
aldehyde
alcohol
hemiacetal
R
C
R
O
"R
OH
R'
ketone
"R
C
R'
alcohol
hemiketal
OH
6) Anomers
Those monosaccharides that differ in
configuration of OH groups on carbonyl
carbon (anomeric carbon) are called as
anomers.
Formation of ring structure of glucose
generates anomers of glucose, which are
designated as and forms.
These two forms of glucose differ in the
configuration of OH on carbonyl carbon or 1st
carbon atom.
H
HO
H
H
2
3
4
5
6
CHO
C
OH
D-glucose
OH
(linear form)
OH
CH2OH
6 CH2OH
6 CH2OH
5
H
4
OH
H
OH
3
OH
-D-glucose
OH
H
4
OH
H
OH
3
OH
OH
-D-glucose
H OH
4
HO
HO
H OH
H O
5
OH 1
OH
-D-glucopyranose
H O
HO
H
HO
H
H
OH
OH
-D-glucopyranose
7) Mutarotation
Mutatrotation is defined as the change
in specific optical rotation
representating the interconversion of
alpha and beta forms to form an
equilibrium mixture
and anomers of Glucose have different
optical rotations.
The specific rotation of a freshly prepared
glucose (anomer) solution in water is +
112.2 which gradually changes and attains
equilibrium with a constant value of +52.7.
Mutarotation of fructose
Fructose also exhibit mutarotation
The pyranose ring is converted to furanose
ring, till an equilibrium is attained
Fructose has specific rotation of -92
Configuration of D- Aldoses
The representation of the configuration of
D-Aldoses by increasing the chain length
of an aldose by one carbon at a time is
known as Killiani Fischer synthesis
Among the D-aldoses, D-Glucose is the
only aldose monosaccharide that
predominantly occur in nature
REACTIONS OF
MONOSACCHARIDES
1) Tautomerization or enolization
The process of shifting hydrogen atom from
one carbon atom to another to produce
enediols is known as tautomerism
Sugars possessing anomeric carbon undergo
tautomerism in alkaline solution
When glucose is kept in alkaline solution for
several hours, it undergoes isomerization to
form D-fructose and D-mannose
2) Reducing properties
Sugars are classified as reducing and nonreducing based on the presence of free
aldehyde or keto group on anomeric carbon
In lab many tests are employed to identify the
reducing action of sugars. These include
Benedicts test
Fehlings test
Barfoeds test
The reduction is much more efficient in
alkaline medium due to the formation of
enediols
3) Oxidation
Depending on the oxidizing agent
used, the aldehyde or the ketone group
or the terminal alcohol or both may be
oxidised
4) Reduction
When treated with reducing agents such as
sodium amalgum, the aldehyde or the ketone
froup of monosaccharide is reduced to
corresponding alcohol
D-Glucose : D- Sorbitol
D-Galactose: D-Dulcitol
D-Mannose:
D-Mannitol
D-Fructose: D-Mannito
D-Sorbitol
D-Ribose:
D-ribitol
5) Dehydration
When treated with conc sulfuric acid,
monosaccharides undergo dehydration with an
elimination of 3 water molecules
Hexoses form hydroxy methyl furfural and
pentoses form furfural
These furfurals can condense with phenolic
compounds (alpha naphtol) to give coloured
product (purple ring)
This is the chemical basis of Molischs test
( characteristic test for carbohydrates)
6) Osazone formation
Phenylhydrazine in acetic acid, when
boiled with reducing sugars forms osazone
Glucosazone/ Fructosazone
Needle shaped
Lactosazone:
Puff ball shaped
Maltosazone:
Sunflower shaped
7) Formation of esters
Esterification of carbohydrate with
phosphoric acid is a common
reaction in metabolism
Eg; Glucose 6-phosphate and
Glucose 1-phosphate
8) Glycosides formation
Glycosides are formed when the hemiacetal
or hemiketal hydroxy group (of anomeric
carbon) of a carbohydrate reacts with hydroxy
group/ amino group of another carbohydrate
or non-carbohydrate
The bond formed is known as glycosidic bond
Are of two types:
A) O-glycosides
When hydroxyl group on anomeric
carbon of a sugar reacts with an alcohol
(sugar) O-glycoside is formed
) O-glycosidic linkage is present in
disaccharides, oligosaccharides and
polysaccharides. So, disaccharides,
oligosaccharides and polysaccharides are Oglycosides.
B) N-glycosides
N-Glycoside is formed when hydroxyl group
on anomeric carbon of sugar reacts with an
amine
N-glycosidic linkage is present in nucleotides,
RNA and DNA. So, nucleotides, RNA and DNA are
examples for N-glycosides.
9) Fermentation
Monosaccharides such as glucose,
fructose and mannose are readily
fermented by yeast.
The process of yeast fermentation is very
complex.
During this process, sugar phosphate and
sugar acid phosphate are formed.
Ordinarily, this process results in the formation
of alcohol and carbon dioxide.
Sugar Derivatives
1) Sugar acids
) Oxidation of aldo group of sugars produces aldonic
acids. Eg; oxidation of glucose produces gluconic and
) oxidation of terminal alcohol group (OH sixth carbon
atom) of glucose produces glucuronic acid or uronic
acid
) Uronic acids are components of mucopolysaccharides
and required for detoxification.
) Ketoses are not easily oxidized.
) Vitamin C or ascorbic acid is also sugar acid.
CHO
COOH
H
OH
HO
OH
OH
OH
OH
OH
HO
CH2OH
D-gluconic acid
COOH
D-glucuronic acid
2) Sugar alcohols
Reduction of aldose and keto groups of
sugar produces sugar alcohols or polyols
These polyols are intermediates of
metabolic reactions.
CH2OH
H
OH
OH
OH
CH2OH
D-ribitol
4) Deoxy sugars
Sugars in which oxygen of a hydroxyl
group is removed leaving hydrogen.
Deoxyribose is an example
It is present in nucleic acids.
Fucose is a deoxy sugar present in
blood group substances.
5) Sugar phosphates
Breakdown of sugar in animals
involves formation of sugar
phosphates. Eg; Glucose-6phosphate
6) Amino sugars
CH2OH
CH2OH
H
O
H
OH
H
OH
OH
H
NH2
-D-glucosamine
O
H
OH
H
O OH
OH
H
CH3
-D-N-acetylglucosamine
O
H3C
NH
R
H
COO
R=
OH
H
OH
HC
OH
HC
OH
CH2OH
N-acetylneuraminate
(sialic acid)
N-acetylneuraminate
(N-acetylneuraminic
acid,
also called sialic acid) is often found as a
terminal residue of oligosaccharide chains of
glycoproteins.
DISACCHARIDES
1) Maltose
Contains two glucose units.
Anomeric carbon atom of first glucose and
carbon atom 4 of the second glucose are
involved in glycosidic linkage.
Glycosidic linkage of maltose is symbolized as
(14)
2) Lactose
It contains one glucose and one galactose.
The anomeric carbon atom of galactose and
carbon atom 4 of glucose are involved in
glycosidic linkage. It is symbolized as (14)
The systematic name: O--D galactopyranosyl(14)--D-glucopyranose. Lactose is a reducing
sugar because anomeric carbon of glucose is
free.
Source: Lactose is synthesized in
mammary gland and hence it
occurs in milk
3) Sucrose
It contains glucose and fructose. The
anomeric carbon of glucose and anomeric
carbon of fructose are involved in glycosidic
linkage.
Further, glucose is in -form whereas fructose
is in -form in sucrose. Hence the glycosidic
linkage of sucrose is designated as , (12).
4) Isomaltose
It contains two glucose units.
Glycosidic linkage is (16)
Disaccharide unit present in glycogen,
amylopectin and dextran.
5)Cellobiose
Contains two glucose units but they are
joined in (14) linkage. It is formed from
cellulose.
6) Trehalose
It also contains two glucose units. The
glycosidic linkage is (11). So, it is a nonreducing
Disaccharide. It is a major sugar of insect
Invert sugar
Sucrose has specific optical rotation of
+66.5.
On hydrolysis, it changes to 19.8.
This change in optical rotation from dextro to
levo when sucrose is hydrolysed is called as
inversion.
The hydrolysis mixture containing glucose and
fructose is called as invert sugar.
The change in optical rotation on hydrolysis is
because of fructose which is more levo
rotatory than dextro rotatory glucose.
Polysaccharides
Polysaccharides (glycans)
consist of repeat units of
monosaccharides or their
derivatives held together
by glycosidic bonds.
Polysaccharides are linear
or branched polymers
Functions of polysaccharides
Serve as carbohydrate
Polysaccharide
omopolysaccharide
On hydrolysis,
yield only one
type
of
monosacchari
des. Eg;
Starch
Glycogen
Heteropolysaccharid
On hydrolysis,
give 2 or more
monsaccharides
or their
derivatives. Eg;
Hyaluronic acid
Chondroitin
sulfate
Starch
Carbohydrate reserve of pants
Most imp dietary source for higher
animals, including man
Consists of D-glucose units held by glycosidic bond (glucosan or glucan)
Consists of two polysaccharide units
Amylose and Amylopectin
Dextrins
Breakdown products of starch by enzyme
amylase or dilute acids
Starch is sequentially hydrolysed through
different dextrins and finally to maltose
and glucose
Various intermediates are identified by
iodine colouration;
Blue (starch)
Violet (amylodextrin)
Red (erythrodextrin)
Colourless (archodextrin)
Inulin
Glycogen
carbohydrate reserve of animals (animal
starch)
stored in liver, muscle, brain
found in plants that do not contain chlorophyll
(eg; yeast, fungi)
structure is similar to amylopectin with more
no. of branches
ie; Glucose with (1 6) glycosidic bonds at the
branching points and (1 4) bonds elsewhere
Glycogen: Glucose has (1 6) branches every
8- 12 residues whereas amylopectin has (1 6)
branches in every 12-30 residues
Cellulose
totally absent in animal body
occurs extensively in plants and is the most
abundant organic substance in plant kingdom
cannot be digested by mammals including
humans due to the lack of enzyme that breaks
glycosidic bonds. However, certain
hervivores contain microorganisms in the gut
which produce enzyme that cleave
glycosidic bonds
It is a major constituent of fiber, the non
digestible carbohydrate. So decrease the
absorption of glucose and cholesterol from the
Chitin
Composed of N-acetyl DGlucosamine units held together by
(1 4) glycosidic bonds
Structural polysaccharide found in
exoskeleton of some invertibrates
e.g; insects, crustaceans
Mucopolysaccharides
are heteroglycans made up of repeating units
of sugar derivatives namely amino sugars
and uronic acids
comonly known as
glycosaminoglycans (GAG)
acetylated amino groups, sulfate and
carboxyl groups are generally
present
presence of sulphate and carboxyl
groups contributes to acidity of the
molecules
Function
essential components of tissue structure
have the special ability to bind large amounts
of water, thereby producing the gel-like
matrix that forms the basis of the body's
ground substance
the extracellular spaces of tissue (esp.
connective tissue- cartilage, tendons, blood
vessels, skin) consist of collagen and elastin
fibres embedded in the matrix of ground
substance (predominantly composed of
Hyaluronic acid
Medical importance
1) As the age advances hyaluronic acid is
replaced by-dermatan sulfate in synovial
fluid. Dermatan sulfate is not a good
lubricant, hence age related pains develop in
old people.
2) In young people, vitreous is clear elastic gel
in which hyaluronic acid is associated with
collagen. As the age advances the elasticity
of vitreous is reduced due to decreased
association between collagen and hyaluronic
acid. As a result, vision is affected in older
people.
Chondroitin sulfates
chondroitin 4 sulphate is a major constituent of
various mammalian tissues (bone, cartilage,
tendons, heart valves, skin cornea etc)
structurally comparable to hyaluronic acid
consists of repeating disaccharide units
composed of D-glucoronic acid and N-acetyl Dglucosamine 4-sulfate
Heparin
composed of alternating units of N-sulfo Dglucosamine 6-sufate and glucoranate 2sulfate
acts as an anticoagulant
helps to release lipoprotein lipase which
helps in clearing the turbidity of lipemic
plasma
Dermatan sulfate
mostly occurs in skin
structurally related to chondroitin 4sulfate except for the inversion in the
configuration around C5 of Dglucuronic acid to form L-iduronic
acid
Keratan sulfate
Essentially consists of alternating
units of D-galactose and Nacetylglucosamine 6-sulfate
Proteoglycans
Some mucopolysaccharides are found in
combination with proteins to form
mucoproteins or mucoids or
proteoglycans.
Mucoprotein may contain upto 95%
carbohydrate and 5% protein
Glycoproteins
proteins covalently bound to carbohydrates
carbohydrate content of glycoprotein varies
from 1 to 90% by weight
They are found in mucous fluids, tissues, blood
and in cell membrane.
They are proteins containing short chains of
carbohydrates.
The carbohydrate chains are usually
oligosaccharides.
These oligosaccharide chains are attached to
proteins by O-glycosidic and N-glycosidic bonds
Major functions
Structure
Defence against infection
Lubrication
Hormone
Antigens
Blood clotting
Absorption of vit B12
Cell-cell adhesion and
recognition
Antifreeze glycoproteins
Antarctic fish are able to live below
-2 C, due to the presence of
antifreeze glycoproteins which lower
the freezing point of water and
interfere with the crystal formation of
ice
Sialic Acid
Sialic acids are acyl derivatives of neuraminic
acid.
Neuraminic acid is a 9 carbon sugar consisting
of mannosamine and pyruvate.
Usually amino group of mannosamine of
neuraminic acid is acetylated.
Hence, N-acetyl neuraminic acid (NANA) is an
example for sialic acid.
Functions
Oligosaccharides of some membrane
glycoproteins contains a terminal sialic acid.
Sialic acid is an important constituent of
glycolipids present in cell membrane and
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