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Chemistry
and
Functions
of
Carbohydrates
What are Carbohydrates?
 Carbohydrates are organic biomolecules abundantly
present in the nature.
 Found in the cells of plants and animals.
 The term “Carbohydrate” was coined by “Karl
Schmidt”.
Carbohydrates Biosynthesis
 Carbohydrates are predominantly biosynthesized
by plants through photosynthesis.
 Glucose is synthesized in plants from CO2, H2O,
and solar energy from the sun.
chlorophyll
6 CO2 + 6 H2O C6H12O6 + 6 O2
Sunlight Glucose
(Simple Carbohydrate)
(+)-Glucose Starch or Cellulose
(Complex Carbohydrates Of Plants)
Photosynthesis
 Animals and Human beings cannot
biosynthesize Carbohydrates predominantly.
 To fulfill metabolic and structural role in human
beings,
 It is essential to ingest carbohydrates through
food substances of plant and animal origin.
 Thus Carbohydrates are chief constituents of human
food.
 R.D.A for Dietary Carbohydrates=
400-600 gm/day.
 However in a critical condition when cells are
deprived of Glucose
 Human body biosynthesizes Glucose using the
non carbohydrate precursors present in body
via Gluconeogenesis.
Functions of Carbohydrates
 Carbohydrates serve as primary source of
energy/Fuel of body
( Metabolic role).
 Carbohydrate (Glucose) is oxidized in living cells of human
body to produce CO2, H2O, and energy(ATP).
 Carbohydrates provide skeletal framework to cells ,tissues,
and organs of body.(Structural role)
 Carbohydrates are associated to many other roles with human
beings.
Definition of Carbohydrates (Old)
 Empirical formula/General formula for simple
carbohydrates : Cn (H2O)n
 Where n = number of carbon atom present in
carbohydrate structure.
 Old Definition-
Carbohydrates are “Hydrates of Carbon”
Observe the following chemical structures of simple
Carbohydrates: Glucose and Fructose
Aldose
(e.g., Glucose) have an aldehyde group
at one end
Ketose
(e.g., Fructose) have a ketone
group, usually at C2.
C
C OH
H
C H
HO
C OH
H
C OH
H
CH2OH
D-glucose
O
H
C H
HO
C OH
H
C OH
H
CH2OH
CH2OH
C O
D-fructose
 Simple Carbohydrates has many Hydroxyl groups
(Polyhydroxy).
 Simple Carbohydrates has carbonyl/ functional
groups as Aldehyde or Ketone.
 Simple Carbohydrates(Glucose/Fructose) repeatedly
linked to form its condensed complex
carbohydrates for ex Starch, Inulin.
 The hydroxyl groups may be free or substituted by
any other groups.
 Simple Carbohydrates on chemical reactions
produces derivatives of Carbohydrates.
 Old definition is not valid since-
 Certain Carbohydrates –
Rhamnose did not fit in the empirical formula
of carbohydrates.
 Certain non Carbohydrates –
Lactate and Acetate fitted in the empirical
formulae.
New Definition of Carbohydrates
Carbohydrates are organic biomolecules,
abundantly present in the plant and animal
bodies, chemically composed of Polyhydroxy
Aldehyde or Polyhydroxy Ketone, their
condensed products or their derivatives.
Classification Of Carbohydrates
 Depending Upon Number of Saccharide Units
 Four Main Classes of Carbohydrates
 Monosaccharides
(1 Saccharide Unit)
 Disaccharides
(2 Saccharide Units)
 Oligosaccharides
( 3-10 Saccharide Units)
 Polysaccharides
( More than 10 Saccharide Units)
Monosaccharides Sub Classification
 Monosaccharides are sub classified on the basis of:
 Functional Group
 Number of Carbon atoms.
Number of
Carbon
Atoms
Aldoses
(Aldehyde-CHO)
Ketoses
(Ketone -C=O)
3
Triose
Aldo Triose
Glyceraldehyde
Keto Triose
Di HydroxyAcetone
4
Tetrose
Aldo Tetrose
Erythrose
Keto Tetrulose
Erythrulose
5
Pentose
Aldo Pentose
Ribose, Xylose,
Arabinose
Keto Pentulose
Ribulose, Xylulose
6
Hexose
Aldo Hexose
Glucose, Galactose
,Mannose
Keto Hexose
Fructose
7
Heptose
Aldo Heptose
SedoHeptose
Keto Heptulose
SedoHeptulose
Disaccharides
 Disaccharides has 2 Monosaccharide units linked
by glycosidic bond.
 Disaccharides may be reducing or non reducing
Reducing Disaccharides –
 Lactose (Glu-Gal)
 Maltose (Glu-Glu)
 Non reducing Disaccharides-
 Sucrose(Glu-Fru)
Type Of Disaccharides
Oligosaccharides Sub Classification
 Oligosaccharides has 3-10 Monosaccharide
units linked by glycosidic bonds.
 Oligosaccharides are sub classified on the
basis of number of Saccharide units.
Number of
Monosacchari
de Units
Type Of Oligosaccharides
(3-10 Monosaccharide Units )
3 Trisaccharides
Maltotriose (Glu-Glu-Glu)
Raffinose (Glu-Fru-Gal)
4 Tetrasaccharides
Stachyose (Glu-Fru-2Gal)
5 Pentasaccharides
Verbascose (Glu-Fru-3Gal)
Polysaccharide Sub Classification
 Polysaccharides/ Glycans
contain more than 10, same/ different
Monosaccharide units linked by glycosidic
linkages.
 Homopolysaccharides/
Homoglycans-
Contains more than 10 same repeating units.
 Heteropolysaccharides / Heteroglycans-
Contains more than 10, different repeating units.
Types of Polysaccharides
POLYSACCHARIDES/ Glycans
( More than 10 Monosaccharide Units )
Homopolysaccharides/ Homoglycans
( > 10 Same Repeating Units )
Glucosans
(Repeating Unit of Glucose/Polymer
of Glucose)
Starch
Glycogen
Cellulose
Dextrin
Dextran
Fructosans
(Repeating Unit of
Fructose/Polymer of
Fructose)
Inulin
Hetero Polysaccharides
( More than 10 Different Repeating Units )
 Agar
 Pectin
 Lignin
 Gum
What are Sugars?
 Sugars are chemically simple Carbohydrates
Monosaccharides and Disaccharides.
 Sugars are Crystalline Solid substances.
 Soluble in water
 Sweet in taste
 Structure possess asymmetric /chiral carbon
atoms/stereogenic centers.
 The carbonyl/ functional groups of Carbohydrates
may be present as free or bound (involved in
glycosidic bonds).
Reducing Sugar
 Sugar structure possessing free or
potential(reactive) aldehyde or ketone group is
termed as reducing sugar.
 Reducing sugars show reducing property efficiently
in alkaline medium and reduces certain metallic
ions as- Cu++;Bi++;Fe+++
Types Of Sugars
 Reducing Sugars
 Non Reducing Sugars
 Reducing Sugars answer following tests positive
 Benedict’s Test
 Fehling’s test
 Nylander’s Test
 Form Osazones.
 Reducing Shows Mutarotation (Change in Optical
activity)
Examples Of Reducing Sugars
 All Monosaccharides are reducing sugars.
 Monosaccharides are strong reducing agents.
 Monosaccharides–
 Ribose, Glucose, Galactose, Fructose.
 Disaccharides are weak reducing agents.
 Reducing Disaccharides-
 Lactose, Maltose.
Non Reducing Sugars
 Sugar structure not possessing free or potential
aldehyde or ketone group in its structure is
termed as non reducing sugar.
 Non reducing sugar does not show reducing
property and do not reduce metallic ions.
Examples of Non reducing Sugars
 Non reducing Disaccharides.
 Sucrose (Biomedically Important)
 Trehalose (Glu-Glu linked with α(1-1)
glycosidic bond)
 Polysaccharides/Complex Carbohydrates are Non
reducing.
 Non reducing sugars give following reducing tests
negative.
 Benedict’s Test
 Fehling’s test
 Nylander’s Test
 Do not form Osazones
 Non Reducing sugars do not exhibit Mutarotation
(Change in Optical activity)
Sugar/Sugar Derivatives Percent
Sweetness
Glucose 75
Fructose
(Sweetest Sugar)
175
(Highest)
Galactose 30
Sucrose 100
Lactose 20
Maltose 30
Xylitol 250
Carbohydrates are Optically Active and Show
Stereoisomerism
 All Carbohydrates except Di Hydroxy
Acetone(DHA) possess asymmetric carbon atoms
in their structure.
 Presence of Asymmetric carbon atoms confer two
properties:
 Optical Activity
 Stereoisomerism.
Optical Activity
 Optically active solutions when placed in the tube
of Polarimeter.
 If moves the plane of polarized light toward right
are dextro rotatory (d/+).
 If moves the plane of polarized light toward left
are laevo rotatory (l/-).
 Stereoisomers are type of isomers
 Which have same chemical and molecular
formula,
 The structure slightly differs in the spatial
orientation of groups around the carbon atom.
 Stereoisomerism is due to presence of chiral carbon
atoms/stereogenic centers.
 Glyceraldehyde is a Monosaccharide
 Chemically –
Aldo Triose
C3H6O3
Erythrose
Erythrose is a Monosaccharide
 Erythrose is an Aldo Tetrose
 C4(H2O)4
 Occurrence/Sources :
 In Cytosol of cells
 Biomedical Importances :
 Erythrose -4-Phosphate is an intermediate of HMP shunt
.
Ribose
 Ribose is a Monosaccharide.
 Ribose is an Aldo Pentose
 C5(H2O)5
 Biomedical Importances of Ribose :
 Ribose is an important component of Ribonucleotides
which forms RNA.
 Ribose is component of certain Nucleotide
Coenzymes-ATP, NAD
+
, NADP
+
,FAD
Deoxyribose is a Aldo Pentose
 Deoxyribose has one Oxygen atom less than Ribose at
C2.
 Deoxyribose has no –OH group at C2
 Instead has –H at C2.
7P1-38
Cyclic forms for sugars
Fischer projections for a D Glucose
C
C
C
OH
O
H
C OH
H
C
H
H
CH2OH
H
O
H
OH
C
C
C
OH
O
H
C OH
H
C
H
H
CH2OH
H
OH
H C
C
C
OH
O
H
C OH
H
C
H
H
CH2OH
H
O
H H
D-glucose a D-glucose
cyclic form
O
 D-glucose
cyclic form
O
C
C
C
OH
O
H
C OH
H
C
H
H
CH2OH
H
O
H
OH
C
C
C
OH
O
H
C OH
H
C
H
H
CH2OH
H
OH
H C
C
C
OH
O
H
C OH
H
C
H
H
CH2OH
H
O
H H
D-glucose a D-glucose
cyclic form
O
 D-glucose
cyclic form
O
Fischer’s and Haworth’s Projection
Fischer’s Projection
 Cyclization of Glucose to hemiacetal is
spontaneous to form stable ring structures.
Haworth’s Projection
 Gluco Furanose -5 membered ring with Oxygen
atom in it.
 Gluco Pyranose -6 membered ring with Oxygen
atom in it.
Monosaccharides can cyclize to
form Pyranose / Furanose forms
 =64%
a = 36%
 Specific rotation of Glucose optical activity:
 Pure α-D Glucose = specific rotation +112.2 º
 Pure β-D Glucose = specific rotation +18.7 º
 Enantiomers/ Mirror images of
each other/Left and Right Hand
 Non superimposible/Non
overlapping.
Enantiomers
 Physical and chemical properties of Enantiomers
are same, except optical rotation.
 Sugars present in human body are of ‘D’ series.
 To identify D and L Glucose
 In D Glucose -OH is at R.H.S.
 In L Glucose -OH is at L.H.S.
Anomers
α-Glucose and β-Glucose.
 Anomers has group variations at C1
Anomeric carbon atom of Glucose .
 Glucose anomers of Haworth’s projection shows
as follows.
 α-Glucose has -OH group below the plane.
 β-Glucose has OH group above the plane.
Epimers
 Epimers are stereoisomers which has variation in
the orientation of groups at C 2Epimers of
Glucose
 Mannose (C2 Epimer)
Mannose
Mutarotation
 Criteria for an optically active substance to
exhibit Mutarotaion:
 Anomerism:
 In aqueous solution the optically active substance
should exist in two or more stereoisomeric forms
by ready interconversions.
 Glucose in aqueous solution readily interconvert
from α Glucose to β Glucose and attain an
equilibrium mixture to exhibit mutarotation.
Mutarotation is a physico chemical property
Shown by certain optically active substances ,who in
aqueous solution has capacity to interconvert from
one stereoisomeric form to other and attain a
constant equilibrium mixture,
Mechanism of mutarotation
Chemical Properties
Glucose Sorbitol
(Sugar) (Sugar Alcohol)
Reduction Reaction
During reduction reaction the C1 carbonyl group
(-CHO) is reduced to primary alcohol group (-
CH2OH).
D-sorbitol D-xylitol
CH2OH
C
C
OH
OH
C H
O
H
C
H
H OH
CH2OH
H
C
H OH
CH2OH
CH2OH
C
C
OH
O
H H
H
Gluconic Acid
(Aldonic Acid)
(-CHO to -COOH)
Glucuronic Acid
(Uronic Acid)
(-CH2OH to -COOH)
Glucosaccharic Acid
(Dibasic Aldaric Acid)
(-CHO &-CH2OH to –COOH)
Glucose
Oxidation Reaction
Glucose Glucose -6-Phosphate
Phosphorylation Reaction (Robinson Ester)
OR
Glucose-1-Phosphtae
(Cori Ester)
Esteification
O
CH2OPO3
2-
H
H
O
H
H
OH
OH
H
H
OH
 D-glucose-6-phosphate
Biomedical Importance of Glucose
 Glucose is a reduced compound and has bond
energy in its structure.
 Glucose in body cells Oxidized/Catabolized to
liberate chemical form of energy-ATP.
 1 Glucose molecule on complete oxidation
produces 32 ATPs.
 Glucose serve as primary source of energy to all body
cells.
 Glucose is an universal fuel of fetus.
 Brain, Erythrocytes ,lens cells, spinal cord, peripheral
nerves are completely dependent on Glucose for its
energy.
Fructose
 Fructose is a Monosaccharide
 Fructose is Sweetest Sugar.
 Laevulose (Laevorotatory)
Occurrence/Sources Of Fructose
 In Fruits, Honey
 Body cells, Semen.
 Fructose is component of Sucrose.
 Fructose is more stable in
βD Fructofuranose form.
 Selivanoff ‘s test is characteristic test for Fructose.
(positive result-Cherry red color).
 Fructose on reduction forms Sorbitol and Mannitol.
Biomedically Important
Disaccharides
 Disaccharides are class of Carbohydrates, chemically
composed of two, same or different Monosaccharide
units, linked by glycosidic bond.
General Formula of Disaccharides Cn(H2O)n-1
 Glycosidic bonds are Acetal/ Ketal bonds involving the
anomeric carbon of Monosaccharides.
 Glycosidic bonds are formed with α/β configuration.
 Reducing Disaccharides
 Lactose (Milk Sugar)
 Maltose
(Malt Sugar, Product of Starch digestion))
 Isomaltose (product of Starch digestion)
 Lactulose (Laxative)
 Cellobiose ( Product of Cellulose)
Types of Disaccharides
Components and Linkage of Lactose
Lactose is a Reducing Disaccharide
β (1-4 ) glycosidic bond
β D Galactose β D Glucose
Components and Linkage Of Sucrose
 α D Glucose- β D Fructose
 α 1- β 2 glycosidic bond.
Maltose
Maltose also known as maltobiose or malt sugar, is
a disaccharide formed from two units of glucose joined
with an α(1→4) bond. In the isomer isomaltose, the two
glucose molecules are joined with an α(1→6) bond.
Inversion process
 A non reducing and dextrorotatory Sucrose, on acid
hydrolysis/by action of enzyme Invertase ,
 Produces a hydrolytic mixture of free, Glucose(+52.50)
and Fructose(-930) which is reducing and
laevorotatory(- 20.40).
 Invert Sugar is Reducing.
 Invert sugar is laevorotatory.
(since Fructose has high magnitude of optical
rotation -930)
 Invert Sugar is sweeter than Sucrose
(since it contains free Fructose,a sweetest sugar)
Inter conversions of sugars (ascending and
descending of sugar series, conversion of
aldoses to ketoses
Lobry de Bruyn-van Ekenstein rearrangement
Lobry de Bruyn–Alberda van Ekenstein transformation is
the base or acid catalyzed transformation of an aldose into
the ketose isomer or vice versa, with a tautomeric enediol
as reaction intermediate. The enediol is also an
intermediate for the epimerization of an aldose or ketose
It proceeds via synthesis and hydrolysis of a cyanohydrin,
thus elongating the carbon chain of an aldose by one
carbon atom while preserving stereochemistry on all the
previously present chiral carbons
The Wohl degradation in carbohydrate chemistry is a chain
contraction method for aldoses. The classic example is the
conversion of glucose to arabinose as shown below. The reaction is
named after the German chemist Alfred Wohl
 Polysaccharides are complex class of Carbohydrates,
 Chemically composed of more than ten, same or
different Monosaccharide units or their derivatives
 Repeatedly linked by glycosidic linkages.
 Iodine test is based on Physical property of adsorption.
 Iodine get adsorbed on complex structure of
Polysaccharides to give characteristic color.
 General Formula of Polysaccharides (C6H10O5 )n
 Iodine test is a characteristic test for Polysaccharides
Homopolysaccharides
 Homopolysaccharides are type of Polysaccharides
composed of more than 10, same type of
Monosaccharide units repeatedly linked by glycosidic
bonds.
 Type of Homopolysaccharide
 Repeating unit of Glucosan is Glucose
 Glucosan is a Polymer of Glucose.
Examples Of Glucosans
Starch, Glycogen, Cellulose, Dextrin, Dextran
Fructosan
 Type of Homopolysaccharide
 Repeating unit in Fructosan is Fructose.
 Fructosan is a Polymer of Fructose.
Chemistry Of Starch
 Starch is Glucosan
 Repeating Unit -
α D Glucose (approx 7000)
 Components of Starch-
 Amylose and Amylopectin
Starch is a 1-4 linkage of α glucose monomers and Cellulose is
formed by 1-4 linkage of β glucose monomers.
Source/Occurrence Of Starch
 Plants- Seeds, Tubers, Roots, Raw fruits.
Dietary Sources of Starch.
 Grains- Rice ,Wheat, Jawar, Bajra
 Potatoes
 Beetroot.
 Sago (Tapioca)
 Vermicelli
 Suji.
 Raw Mangoes
Biomedical Importance Of Starch
 Starch is a storage form of Glucose and serves as
reservoir of energy in plants.
 To humans Starch is a predominant form of dietary
Carbohydrate ingested through foods which has high
dietary and calorific value.
THANKYOU

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Carbohydrates Chemistry Functions Guide

  • 2. What are Carbohydrates?  Carbohydrates are organic biomolecules abundantly present in the nature.  Found in the cells of plants and animals.  The term “Carbohydrate” was coined by “Karl Schmidt”. Carbohydrates Biosynthesis  Carbohydrates are predominantly biosynthesized by plants through photosynthesis.  Glucose is synthesized in plants from CO2, H2O, and solar energy from the sun.
  • 3. chlorophyll 6 CO2 + 6 H2O C6H12O6 + 6 O2 Sunlight Glucose (Simple Carbohydrate) (+)-Glucose Starch or Cellulose (Complex Carbohydrates Of Plants) Photosynthesis
  • 4.
  • 5.  Animals and Human beings cannot biosynthesize Carbohydrates predominantly.  To fulfill metabolic and structural role in human beings,  It is essential to ingest carbohydrates through food substances of plant and animal origin.  Thus Carbohydrates are chief constituents of human food.  R.D.A for Dietary Carbohydrates= 400-600 gm/day.
  • 6.  However in a critical condition when cells are deprived of Glucose  Human body biosynthesizes Glucose using the non carbohydrate precursors present in body via Gluconeogenesis.
  • 7. Functions of Carbohydrates  Carbohydrates serve as primary source of energy/Fuel of body ( Metabolic role).  Carbohydrate (Glucose) is oxidized in living cells of human body to produce CO2, H2O, and energy(ATP).  Carbohydrates provide skeletal framework to cells ,tissues, and organs of body.(Structural role)  Carbohydrates are associated to many other roles with human beings.
  • 8. Definition of Carbohydrates (Old)  Empirical formula/General formula for simple carbohydrates : Cn (H2O)n  Where n = number of carbon atom present in carbohydrate structure.  Old Definition- Carbohydrates are “Hydrates of Carbon”
  • 9. Observe the following chemical structures of simple Carbohydrates: Glucose and Fructose Aldose (e.g., Glucose) have an aldehyde group at one end Ketose (e.g., Fructose) have a ketone group, usually at C2. C C OH H C H HO C OH H C OH H CH2OH D-glucose O H C H HO C OH H C OH H CH2OH CH2OH C O D-fructose
  • 10.  Simple Carbohydrates has many Hydroxyl groups (Polyhydroxy).  Simple Carbohydrates has carbonyl/ functional groups as Aldehyde or Ketone.  Simple Carbohydrates(Glucose/Fructose) repeatedly linked to form its condensed complex carbohydrates for ex Starch, Inulin.  The hydroxyl groups may be free or substituted by any other groups.  Simple Carbohydrates on chemical reactions produces derivatives of Carbohydrates.
  • 11.  Old definition is not valid since-  Certain Carbohydrates – Rhamnose did not fit in the empirical formula of carbohydrates.  Certain non Carbohydrates – Lactate and Acetate fitted in the empirical formulae.
  • 12. New Definition of Carbohydrates Carbohydrates are organic biomolecules, abundantly present in the plant and animal bodies, chemically composed of Polyhydroxy Aldehyde or Polyhydroxy Ketone, their condensed products or their derivatives.
  • 14.  Depending Upon Number of Saccharide Units  Four Main Classes of Carbohydrates  Monosaccharides (1 Saccharide Unit)  Disaccharides (2 Saccharide Units)  Oligosaccharides ( 3-10 Saccharide Units)  Polysaccharides ( More than 10 Saccharide Units)
  • 15.
  • 16. Monosaccharides Sub Classification  Monosaccharides are sub classified on the basis of:  Functional Group  Number of Carbon atoms.
  • 17. Number of Carbon Atoms Aldoses (Aldehyde-CHO) Ketoses (Ketone -C=O) 3 Triose Aldo Triose Glyceraldehyde Keto Triose Di HydroxyAcetone 4 Tetrose Aldo Tetrose Erythrose Keto Tetrulose Erythrulose 5 Pentose Aldo Pentose Ribose, Xylose, Arabinose Keto Pentulose Ribulose, Xylulose 6 Hexose Aldo Hexose Glucose, Galactose ,Mannose Keto Hexose Fructose 7 Heptose Aldo Heptose SedoHeptose Keto Heptulose SedoHeptulose
  • 18. Disaccharides  Disaccharides has 2 Monosaccharide units linked by glycosidic bond.  Disaccharides may be reducing or non reducing Reducing Disaccharides –  Lactose (Glu-Gal)  Maltose (Glu-Glu)  Non reducing Disaccharides-  Sucrose(Glu-Fru) Type Of Disaccharides
  • 19. Oligosaccharides Sub Classification  Oligosaccharides has 3-10 Monosaccharide units linked by glycosidic bonds.  Oligosaccharides are sub classified on the basis of number of Saccharide units.
  • 20. Number of Monosacchari de Units Type Of Oligosaccharides (3-10 Monosaccharide Units ) 3 Trisaccharides Maltotriose (Glu-Glu-Glu) Raffinose (Glu-Fru-Gal) 4 Tetrasaccharides Stachyose (Glu-Fru-2Gal) 5 Pentasaccharides Verbascose (Glu-Fru-3Gal)
  • 21. Polysaccharide Sub Classification  Polysaccharides/ Glycans contain more than 10, same/ different Monosaccharide units linked by glycosidic linkages.  Homopolysaccharides/ Homoglycans- Contains more than 10 same repeating units.  Heteropolysaccharides / Heteroglycans- Contains more than 10, different repeating units. Types of Polysaccharides
  • 22. POLYSACCHARIDES/ Glycans ( More than 10 Monosaccharide Units ) Homopolysaccharides/ Homoglycans ( > 10 Same Repeating Units ) Glucosans (Repeating Unit of Glucose/Polymer of Glucose) Starch Glycogen Cellulose Dextrin Dextran Fructosans (Repeating Unit of Fructose/Polymer of Fructose) Inulin
  • 23. Hetero Polysaccharides ( More than 10 Different Repeating Units )  Agar  Pectin  Lignin  Gum
  • 24. What are Sugars?  Sugars are chemically simple Carbohydrates Monosaccharides and Disaccharides.  Sugars are Crystalline Solid substances.  Soluble in water  Sweet in taste  Structure possess asymmetric /chiral carbon atoms/stereogenic centers.
  • 25.  The carbonyl/ functional groups of Carbohydrates may be present as free or bound (involved in glycosidic bonds). Reducing Sugar  Sugar structure possessing free or potential(reactive) aldehyde or ketone group is termed as reducing sugar.  Reducing sugars show reducing property efficiently in alkaline medium and reduces certain metallic ions as- Cu++;Bi++;Fe+++
  • 26. Types Of Sugars  Reducing Sugars  Non Reducing Sugars  Reducing Sugars answer following tests positive  Benedict’s Test  Fehling’s test  Nylander’s Test  Form Osazones.  Reducing Shows Mutarotation (Change in Optical activity)
  • 27. Examples Of Reducing Sugars  All Monosaccharides are reducing sugars.  Monosaccharides are strong reducing agents.  Monosaccharides–  Ribose, Glucose, Galactose, Fructose.  Disaccharides are weak reducing agents.  Reducing Disaccharides-  Lactose, Maltose.
  • 28. Non Reducing Sugars  Sugar structure not possessing free or potential aldehyde or ketone group in its structure is termed as non reducing sugar.  Non reducing sugar does not show reducing property and do not reduce metallic ions. Examples of Non reducing Sugars  Non reducing Disaccharides.  Sucrose (Biomedically Important)  Trehalose (Glu-Glu linked with α(1-1) glycosidic bond)  Polysaccharides/Complex Carbohydrates are Non reducing.
  • 29.  Non reducing sugars give following reducing tests negative.  Benedict’s Test  Fehling’s test  Nylander’s Test  Do not form Osazones  Non Reducing sugars do not exhibit Mutarotation (Change in Optical activity)
  • 30. Sugar/Sugar Derivatives Percent Sweetness Glucose 75 Fructose (Sweetest Sugar) 175 (Highest) Galactose 30 Sucrose 100 Lactose 20 Maltose 30 Xylitol 250
  • 31. Carbohydrates are Optically Active and Show Stereoisomerism  All Carbohydrates except Di Hydroxy Acetone(DHA) possess asymmetric carbon atoms in their structure.  Presence of Asymmetric carbon atoms confer two properties:  Optical Activity  Stereoisomerism.
  • 32. Optical Activity  Optically active solutions when placed in the tube of Polarimeter.  If moves the plane of polarized light toward right are dextro rotatory (d/+).  If moves the plane of polarized light toward left are laevo rotatory (l/-).
  • 33.  Stereoisomers are type of isomers  Which have same chemical and molecular formula,  The structure slightly differs in the spatial orientation of groups around the carbon atom.  Stereoisomerism is due to presence of chiral carbon atoms/stereogenic centers.
  • 34.  Glyceraldehyde is a Monosaccharide  Chemically – Aldo Triose C3H6O3
  • 35. Erythrose Erythrose is a Monosaccharide  Erythrose is an Aldo Tetrose  C4(H2O)4  Occurrence/Sources :  In Cytosol of cells  Biomedical Importances :  Erythrose -4-Phosphate is an intermediate of HMP shunt .
  • 36. Ribose  Ribose is a Monosaccharide.  Ribose is an Aldo Pentose  C5(H2O)5  Biomedical Importances of Ribose :  Ribose is an important component of Ribonucleotides which forms RNA.  Ribose is component of certain Nucleotide Coenzymes-ATP, NAD + , NADP + ,FAD
  • 37. Deoxyribose is a Aldo Pentose  Deoxyribose has one Oxygen atom less than Ribose at C2.  Deoxyribose has no –OH group at C2  Instead has –H at C2.
  • 38. 7P1-38 Cyclic forms for sugars Fischer projections for a D Glucose C C C OH O H C OH H C H H CH2OH H O H OH C C C OH O H C OH H C H H CH2OH H OH H C C C OH O H C OH H C H H CH2OH H O H H D-glucose a D-glucose cyclic form O  D-glucose cyclic form O C C C OH O H C OH H C H H CH2OH H O H OH C C C OH O H C OH H C H H CH2OH H OH H C C C OH O H C OH H C H H CH2OH H O H H D-glucose a D-glucose cyclic form O  D-glucose cyclic form O
  • 39. Fischer’s and Haworth’s Projection Fischer’s Projection  Cyclization of Glucose to hemiacetal is spontaneous to form stable ring structures. Haworth’s Projection  Gluco Furanose -5 membered ring with Oxygen atom in it.  Gluco Pyranose -6 membered ring with Oxygen atom in it.
  • 40. Monosaccharides can cyclize to form Pyranose / Furanose forms  =64% a = 36%
  • 41.  Specific rotation of Glucose optical activity:  Pure α-D Glucose = specific rotation +112.2 º  Pure β-D Glucose = specific rotation +18.7 º
  • 42.  Enantiomers/ Mirror images of each other/Left and Right Hand  Non superimposible/Non overlapping. Enantiomers  Physical and chemical properties of Enantiomers are same, except optical rotation.  Sugars present in human body are of ‘D’ series.
  • 43.  To identify D and L Glucose  In D Glucose -OH is at R.H.S.  In L Glucose -OH is at L.H.S. Anomers α-Glucose and β-Glucose.  Anomers has group variations at C1 Anomeric carbon atom of Glucose .
  • 44.  Glucose anomers of Haworth’s projection shows as follows.  α-Glucose has -OH group below the plane.  β-Glucose has OH group above the plane.
  • 45. Epimers  Epimers are stereoisomers which has variation in the orientation of groups at C 2Epimers of Glucose  Mannose (C2 Epimer) Mannose
  • 46. Mutarotation  Criteria for an optically active substance to exhibit Mutarotaion:  Anomerism:  In aqueous solution the optically active substance should exist in two or more stereoisomeric forms by ready interconversions.  Glucose in aqueous solution readily interconvert from α Glucose to β Glucose and attain an equilibrium mixture to exhibit mutarotation.
  • 47. Mutarotation is a physico chemical property Shown by certain optically active substances ,who in aqueous solution has capacity to interconvert from one stereoisomeric form to other and attain a constant equilibrium mixture,
  • 49. Chemical Properties Glucose Sorbitol (Sugar) (Sugar Alcohol) Reduction Reaction During reduction reaction the C1 carbonyl group (-CHO) is reduced to primary alcohol group (- CH2OH). D-sorbitol D-xylitol CH2OH C C OH OH C H O H C H H OH CH2OH H C H OH CH2OH CH2OH C C OH O H H H
  • 50. Gluconic Acid (Aldonic Acid) (-CHO to -COOH) Glucuronic Acid (Uronic Acid) (-CH2OH to -COOH) Glucosaccharic Acid (Dibasic Aldaric Acid) (-CHO &-CH2OH to –COOH) Glucose Oxidation Reaction
  • 51. Glucose Glucose -6-Phosphate Phosphorylation Reaction (Robinson Ester) OR Glucose-1-Phosphtae (Cori Ester) Esteification O CH2OPO3 2- H H O H H OH OH H H OH  D-glucose-6-phosphate
  • 52. Biomedical Importance of Glucose  Glucose is a reduced compound and has bond energy in its structure.  Glucose in body cells Oxidized/Catabolized to liberate chemical form of energy-ATP.  1 Glucose molecule on complete oxidation produces 32 ATPs.  Glucose serve as primary source of energy to all body cells.  Glucose is an universal fuel of fetus.  Brain, Erythrocytes ,lens cells, spinal cord, peripheral nerves are completely dependent on Glucose for its energy.
  • 53. Fructose  Fructose is a Monosaccharide  Fructose is Sweetest Sugar.  Laevulose (Laevorotatory)
  • 54.
  • 55. Occurrence/Sources Of Fructose  In Fruits, Honey  Body cells, Semen.  Fructose is component of Sucrose.  Fructose is more stable in βD Fructofuranose form.  Selivanoff ‘s test is characteristic test for Fructose. (positive result-Cherry red color).  Fructose on reduction forms Sorbitol and Mannitol.
  • 57.  Disaccharides are class of Carbohydrates, chemically composed of two, same or different Monosaccharide units, linked by glycosidic bond. General Formula of Disaccharides Cn(H2O)n-1  Glycosidic bonds are Acetal/ Ketal bonds involving the anomeric carbon of Monosaccharides.  Glycosidic bonds are formed with α/β configuration.
  • 58.  Reducing Disaccharides  Lactose (Milk Sugar)  Maltose (Malt Sugar, Product of Starch digestion))  Isomaltose (product of Starch digestion)  Lactulose (Laxative)  Cellobiose ( Product of Cellulose) Types of Disaccharides
  • 59. Components and Linkage of Lactose Lactose is a Reducing Disaccharide β (1-4 ) glycosidic bond β D Galactose β D Glucose
  • 60. Components and Linkage Of Sucrose  α D Glucose- β D Fructose  α 1- β 2 glycosidic bond.
  • 61. Maltose Maltose also known as maltobiose or malt sugar, is a disaccharide formed from two units of glucose joined with an α(1→4) bond. In the isomer isomaltose, the two glucose molecules are joined with an α(1→6) bond.
  • 62. Inversion process  A non reducing and dextrorotatory Sucrose, on acid hydrolysis/by action of enzyme Invertase ,  Produces a hydrolytic mixture of free, Glucose(+52.50) and Fructose(-930) which is reducing and laevorotatory(- 20.40).  Invert Sugar is Reducing.  Invert sugar is laevorotatory. (since Fructose has high magnitude of optical rotation -930)  Invert Sugar is sweeter than Sucrose (since it contains free Fructose,a sweetest sugar)
  • 63. Inter conversions of sugars (ascending and descending of sugar series, conversion of aldoses to ketoses
  • 64. Lobry de Bruyn-van Ekenstein rearrangement Lobry de Bruyn–Alberda van Ekenstein transformation is the base or acid catalyzed transformation of an aldose into the ketose isomer or vice versa, with a tautomeric enediol as reaction intermediate. The enediol is also an intermediate for the epimerization of an aldose or ketose
  • 65.
  • 66. It proceeds via synthesis and hydrolysis of a cyanohydrin, thus elongating the carbon chain of an aldose by one carbon atom while preserving stereochemistry on all the previously present chiral carbons
  • 67.
  • 68. The Wohl degradation in carbohydrate chemistry is a chain contraction method for aldoses. The classic example is the conversion of glucose to arabinose as shown below. The reaction is named after the German chemist Alfred Wohl
  • 69.  Polysaccharides are complex class of Carbohydrates,  Chemically composed of more than ten, same or different Monosaccharide units or their derivatives  Repeatedly linked by glycosidic linkages.  Iodine test is based on Physical property of adsorption.  Iodine get adsorbed on complex structure of Polysaccharides to give characteristic color.  General Formula of Polysaccharides (C6H10O5 )n  Iodine test is a characteristic test for Polysaccharides
  • 70. Homopolysaccharides  Homopolysaccharides are type of Polysaccharides composed of more than 10, same type of Monosaccharide units repeatedly linked by glycosidic bonds.  Type of Homopolysaccharide  Repeating unit of Glucosan is Glucose  Glucosan is a Polymer of Glucose. Examples Of Glucosans Starch, Glycogen, Cellulose, Dextrin, Dextran
  • 71. Fructosan  Type of Homopolysaccharide  Repeating unit in Fructosan is Fructose.  Fructosan is a Polymer of Fructose.
  • 72. Chemistry Of Starch  Starch is Glucosan  Repeating Unit - α D Glucose (approx 7000)  Components of Starch-  Amylose and Amylopectin
  • 73. Starch is a 1-4 linkage of α glucose monomers and Cellulose is formed by 1-4 linkage of β glucose monomers.
  • 74. Source/Occurrence Of Starch  Plants- Seeds, Tubers, Roots, Raw fruits. Dietary Sources of Starch.  Grains- Rice ,Wheat, Jawar, Bajra  Potatoes  Beetroot.  Sago (Tapioca)  Vermicelli  Suji.  Raw Mangoes
  • 75. Biomedical Importance Of Starch  Starch is a storage form of Glucose and serves as reservoir of energy in plants.  To humans Starch is a predominant form of dietary Carbohydrate ingested through foods which has high dietary and calorific value.