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Monosaccharides
Disaccharides
Oligosaccharides
Polysaccharides
Monosaccharides:
Aldoses :
When the functional group in monosaccharides is an aldehyde ( CHO ),
they are referred to as aldoses. Ex : Glyceraldehyde, glucose.
Ketoses :
When the functional group in monosaccharides is an ketone ( C=0 ),
These terms are used along with functional groups, while naming
monosaccharides.
Ex : Glucose : Aldohexose
Fructose : Ketohexose.
Carbon atoms
Trioses (3C)
Tetroses (4C)
Pentoses (5C)
Hexoses (6C)
Heptoses (7C)
Aldoses
Ketoses
Glyceraldehyde
Dihydroxyacetone
Erythrose
Ribose, xylose,
Arabinose
Glucose, Galactose,
Mannose
Glucoheptose,
Galactoheptose
Erythrulose
Rbulose, Xylulose
Fructose
Sedoheptulose
H-C=O
H-C-OH
H-C-OH
H-C-OH
CH2OH
H-C=O
12 % HCl
C
3H2O
HC
HC
HC
Pentose Sugar
Furfural
H-C=O
H-C=O
H-C-OH
HO-C-H
HC
H-C-OH
O
HC
H-C-OH
CH2OH
CH2OH
D Glucose
furfuryl
Hydroxy Methyl
With strong mineral acids hexose sugars like glucose form hydroxy methyl
furfural and pentose sugars form furfural. This reaction forms the basis of
some colour tests ( Ex: Molisch test & bials orcinol test) for sugars as
aldehyde products of these reactions condense with certain organic phenols
to give characteristic coloured products.
Tetroses & trioses do not undergo this reaction, as they do not possess the
necessary 5 carbon atoms for furfural formation.
Mannose
R
H
H-C=O
H-C-OH
R
Glucose
H-C-OH
H-C-OH
C-OH
C=O
R
Enediol
R
Fructose
(Incomplete alcohol)
Carbohydrates on Oxidation
Strong oxidants
CHO
(CHOH)4
COOH
+
3 [o]
(CHOH)4
CH2OH
(HNO3)
Glucose
nitric acid
H2O
COOH
Glutaric acid
(or) Saccharic acid
CH2OH
COOH
COOH
CH2OH
C=O
(CHOH)2 +
+
COOH
(CHOH)3
COOH
Fructose
acid
glycolic acid
[O]
(CHOH)3
COOH
trihydroxy
Glutaric acid
tartaric
II)
CHO
COOH
(CHOH)4
CH2OH
Glucose
HOBr
bromine
water
(CHOH)4
HBr
CH2OH
Gluconic acid
With strong oxidants (like conc HNO3), both the aldehyde group (or ketone
group) and the primary alcohol group are oxidized to yield dicarboxylic
acids. With aldoses, acids with same number of carbon atoms are
obtained whereas ketoses react to produce acids with fewer number of
carbon atoms.
With mild oxidants (like HOBr), only the
aldehyde group is oxidized to produce monocarboxylic acids. Ketoses
however, do not respond to this reaction. Hence, this reaction can be used
to distinguish aldoses from ketoses.
III)
Metal hydroxides like Cu(OH)2, AgOH and Bi(OH)3 oxidize the free
aldehyde (or ketone) group of mutarotating mono and di saccharides and
at the same time reduce themselves to lower oxides or free metals.
Oxidized Sugar +
(blue)
Cupric ion (Cu++) is the most common oxidizing agent . It is the active
ingredient in fehlings, Benedicts and Barfoeds reagent.
Carbohydrates on reduction :
Sugars maybe reduced in various ways depending upon the type of
reducing agent used.
(a) With sodium amalgum: The monosaccharides are reduced to their
corresponding alcohols by treating thwm with reducing agents like Naamalgum. Thus glucose yields sorbitol (=glucitol), mannose yields
H2H
(Sodium Amulgum)
HOH-CH-
Glucose
+ 2H
(1)H-C=O
H-C=N-NH-C6H5
H-C-OH +
H2N.NH.C6H5
C-OH
R
R
HH2O
Aldohexose
Phenylhydrazone
(2) H-C=N-NH.C6H5
NH.C6H5
H-C-OH
+ C6H5.NH2+NH3
R
H-C=NH2N-NH-C6H5
C=O
R
Aniline
Phenyl hydrazone
aldohydrzone
(3) H-C-N-NH.C6H5
NH-C6H5
C=O
C=N-NH-C6H5 + H2O
R
H-C-NH2N-NH-C6H5
H2O
Aldohydrazene
Osazone
Asymmetric carbon :
A carbon is said to be asymmetric carbon when
it is attached to four different atoms or groups. The number of asymmetric
carbon atoms (n) determines the possible isomers of a given compound,
which is equal to 2n.
For example glucose contains 4 asymmetrical carbons and thus has 16
isomers.
C1HO
H-C2-OH
glucose)
HO-C3-H
H-C4-OH
H-C5-OH
C6H2OH
Glucose
D & L isomers :
The D and L isomers are mirror images of each other. The spatial
orientation of H and
-OH on the carbon atom ( C5 for glucose ) that is adjacent to the terminal
primary alcohol carbon determines, whether the sugar is D or L isomer.
If the OH group is on the right side, it belongs to D series, and if on left,
it belongs to L series.
Epimers :
H-C=O
H-C-OH
H-C-OH
HO-C-H
HO-C-H
HO-C-H
H-C-OH
H-C=O
HO-C-H
HO-C-H
H-C-OH
H-C-OH
H-C-OH
H-C-OH
CH2OH
CH2OH
D-galactose
D-glucose
CH2OH
D-Mannose
Glucose and mannose are
C2 isomers
Hemiacetal :
The hydroxyl group of monosaccharides can react with its own aldehyde
functional group to form hemiacetal.
H
OR2
R1-C
R2-OH
R1 C-H
OH
Aldehyde
Alcohol
Hemiacetal
OH
C
H-C-OH
HO
H
C
H-C-OH
HO-C-H
HO-C-H
H-C-OH
H-C-OH
H-C
H-C
CH2OH
CH2OH
-D-Glucose
-D-Glucose
Anomers :
The & cyclic forms of D-glucose are known as anomers. They differ from
each other in the configuration only around C1 known as anomeric carbon
(Hemi acetal carbon).
anomer OH group held by anomeric carbon is on the the opposite side of
group CH2OH of sugar ring and vice versa.
Note : Anomers differ in certain physical and chemical properties.
Mutarotation :
It is defined as change in specicfic optical representing the interconversion of
and forms of D-glucose to an equilibrium mixture. It is explained by the
& form of glucose which requires the presence of asymmetric carbon C1 . In
mutarotation, hemi acetal ring is opened and reformed with change of
position of H and OH.
For example when D-glucose is dissolved in water its specicfic rotation is
112.2o, when ammonia is passed, the value is 52.5. If it is recrystallized from
boiling pyridine, the rotation is 18.7 and finally 52.5o.
D glucose
+ 112.2o
Disaccharides :
Equilibrium
mixture +52.7o
D glucose
+18.7o
Glucose
Glucose
Galactose
glucose
It doesnt exist in the body but occurs in the sugar cane, pine apple,
carrot roots, sweet potato and honey.
It is hydrolysed to glucose and fructose by the enzyme invertase in the
alimentary canal. The product of hyrolysis are observed.
It has no free aldehyde group or keto group because the inkage is
between the aldehyde group of glucose and keto group of fructose.
Hence it is non reducing sugar.
It doesnt exhibit mutarotation and cannot exist in or forms.
Since it is a non-reducing sugar, it doesnt reduce fehlings solution and
benedicts solution.
It cannot reduce barfoeds solution.
It cannot form osazone with phenyl hydrazene.
The specific rotation of sucrose is +66.5o.During hydrolysis this solution
changes to -19.5o.
Glucose
Fructose
Oligosaccharides :
In Greek : oligo few.
Oligosaccharides contain 2-10 monosaccharide molecules which are
liberated on hydrolysis.
Based on the no. of monosaccharide units present, oligosaccharides are
further sub divided to disaccharides, trisaccharides etc.
Ex : of Trisaccharides : raffinose ( Galactose + glucose+ fructose)
Tetrasaccharides : stachyose (2galactose+glucose+fructose)
Pentasaccharides : verbascose (3galactose+glucose+fructose)
PolysacchaRides :
Homopolysaccharides :
Starch :
Amylose
Amylopectin
Dextrins :
Inulin :
Glycogen :
-D-Glucose
-D-Glucose
-D-Glucose
Chitin :
Heteropolysaccharides :
When the polysaccharides are composed of different types of sugars or
their derivates, they are referred to as heteropolysaccharides or
heteroglycans.
Mucopolysaccharides :
These are heteroglycans made up of repeating units of sugar derivates,
namely amino sugars and uronic acids.
Hyaluronic acid :
Chondroitin Sulfate :
Heparin :
Heparin is an anticoagulant (prevents blood clotting) that occurs in
blood, lung, liver, kidney, spleen etc.
Heparin helps in the release of the enzyme lipoprotein lipase which
causes clearing the turbidity of lipenic plasma.
Composed of alternating units of N-sulfo D glucosamine 6 sulfate &
glucuronate 2 sulfate.
D glucuronate
2 sulfate
N sulfoglucosamine
6 sulfate
I)
Sangers method :
N(CH3)2
R1 O
+
R2 O
R3 O
O=S=O
OH -
5 methyl amino-1
Naphthalene sulfonyl
HCL
N(CH3)2
SO2 R1 O
R2 O
R3 O
NH-CH-C-NH-CH-C-NH-CH-C-OH
H 2O
H+
Dansyl polypeptide
N(CH3)2
R2
+ H 3N-CH-COOH
SO2
NH-CH-C-OH
Edmans method :
R3
+ H3N-CH-COOH (Free amino acids)
Phenyl Isothiocyanate (PITC) also known as edmans reagent reacts with Nterminal amino group of a polypeptide under mildly alkaline conditions to
form a phenylthiocarbonyl (PTC) adduct. This product is treated with
anhydrous trifluoro acetic acid which cleaves the N-terminal residue as a
thiazolinone derivative but doesnt hydrolyze other peptide bonds
Edmans reaction therefore releases the N-terminal amino acid residue but
leaves the rest of the poly peptide chain.
Carboxypeptidase Method :
This method identifies the C terminal of the polypeptide and sequences it.