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CARBOHYDRATES
Carbohydrates
Carbohydrates
Are produced by photosynthesis
in plants.
Such as glucose are synthesized
in plants from CO2, H2O, and
energy from the sun.
Are oxidized in living cells
(respiration) to produce CO2,
H2O, and energy.
Copyright 2007 by Pearson Education, Inc
Publishing as Benjamin Cummings
ROLE OF CARBOHYDRATES
As a major energy source for
living organisms (glucose is a principal energy
source in animal and plants)
As a means of transporting
energy ( exp: sucrose in plant tissues)
As a structural material
(cellulose in plants, chitin in insects, building blocks of
nucleotides).
SIGNIFICANCE OF CARBOHYDRATES
Carbohydrates are the most abundant
biomolecules in nature, having a direct link
between solar energy and the chemical bond
energy in living organisms.
Source of rapid energy production
Structural building blocks of cells
Components of several metabolic pathways
Recognition of cellular phenomena, such as cell
recognition and binding (e.g., by other cells,
hormones, and viruses)
CLASSIFICATION OF CARBOHYDRATES
Carbohydrates are classified according to size:
Monosaccharide a single polyhydroxy aldehyde or
ketone unit
Disaccharide composed of two monosaccharide units
Polysaccharide very long chains of linked
monosaccharide units
Monosaccharides
Monosaccharides, the simplest carbohydrates.
Monosaccharides consist of
3 to 6 carbon atoms, typically.
A carbonyl group (aldehyde or ketone).
Several hydroxyl groups.
Aldoses
Aldoses are monosaccharides
With an aldehyde group.
With many hydroxyl (OH)
groups.
aldotriose (3 C atoms)
tetrose (4 C atoms)
pentose (5 C atoms)
hexose (6 C atoms)
CH aldose
H COH
H COH
CH2OH
Erythose, an aldotetrose
10
Ketoses
Ketoses are monosaccharides
With a ketone group.
With many hydroxyl (OH)
groups.
triose (3 C atoms)
tetrose (4 C atoms)
pentose (5 C atoms)
hexose (6 C atoms)
CH2OH
C=O
ketose
H COH
H COH
HCOH
CH2OH
Fructose, a ketohexose
11
e.g.dihydroxyacetone (CH2OH-C=O-CH2OH)
Aldotriose
Ketotriose
Aldotetrose
Ketotetrose
Aldopentoses
Ketopentose
Aldohexose
Ketohexose
MONOSACCHARIDE CLASSIFICATION
(continued)
MONOSACCHARIDE CLASSIFICATION
(continued)
Learning Check
Identify each as aldo- or ketoO
CH2OH
C H
C O
H C OH
HO C H
H C OH
H C OH
H C OH
CH2OH
H C OH
CH2OH
A
B
16
Solution
A. aldohexose
B. ketopentose
17
Carbohydrates
Structural properties of
Monosaccharides
18
Stereochemistry
Stereochemistry, a subdiscipline of
chemistry, involves the study of the relative
spatial arrangement of atomsthat form the
structure
ofmoleculesand
their
manipulation.
An important branch of stereochemistry is
the study ofchiralmolecules.
Stereochemistry is also known as3D
chemistry because the prefix "stereo-"
means "three-dimensionality".
19
II-Stereoisomers:
These are compounds whose atoms are
connected in the same order but with
different geometry or arrangements.
Types of Stereoisomers are:
A- Optical isomers (e.g. enantiomers &
configurational diastereomers)
B- Geometric isomers or Cis &trans isomers or
cis &trans stereomers (both in alkenes and
cycloalkanes)
Geometrical isomers
Geometrical or cis-trans (cis = same side; trans = across) isomers arise
from peculiar geometry of compounds having a double bond within the
carbon chain.
It may be illustrated by cis-trans pair, maleic and fumaric acids.
23
enantiomers
Optical isomers (= enantiomers) differ from each other in the disposition
of the various atoms or groups of atoms in space around the asymmetric
carbon atom.
These are, in fact, the mirror image of each other.
24
ENANTIOMER PROPERTIES
The physical properties of D and L enantiomers are
generally the same.
D and L enantiomers rotate polarized light in equal, but
opposite directions.
EPIMERS
Any two sugars which differ from each other only in the
configuration around a single asymmetric carbon atom
other than the carbonyl carbon atom are called epimers.
Examples
Glucose, Fructose, Galactose, Mannose
Same chemical formula C6 H12 O6
Examples
of epimers :
D-glucose & D-galactose (epimeric at
C4)
D-glucose & D-mannose (epimeric at
C2)
D-idose & L-glucose (epimeric at C5)
STEREOCHEMISTRY
A chiral carbon is one that has four different groups
attached to it.
A chiral object cannot be superimposed on its mirror image.
STEREOCHEMISTRY (continued)
The presence of a single chiral carbon gives rise to
stereoisomerism.
If a carbon atom is attached to four different groups, it is
chiral.
If any two groups are identical, it is not chiral.
STEREOCHEMISTRY (continued)
Compounds can have more than one chiral carbon:
Fischer Projections
A Fischer projection
Is used to represent carbohydrates.
Places the most oxidized group at the top.
Shows chiral carbons as the intersection of vertical
and horizontal lines.
34
D and L Notations
In a Fischer projection, the OH group on the
Chiral carbon farthest from the carbonyl group
determines an L or D isomer.
Left is assigned the letter L for the L-isomer.
Right is assigned the letter D for the D-isomer.
35
O
C H
H
OH
HO
OH
OH
CH2OH
D-glucose
O
C H
H
OH
H
OH
H
OH
CH2OH
D-ribose
C H
HO
OH
OH
HO
H Referral
CH2OHcarbon
L-galactose
36
Learning Check
Identify each as the D or L isomer.
A.
B.
C.
CH2OH
O
C H
HO
HO
HO
HO
CH2OH
C H
HO
OH
OH
OH
CH2OH
CH2OH
38
Solution
Identify each as the D or L isomer.
A.
B.
C.
CH2OH
O
C H
HO
HO
HO
HO
CH2OH
L-ribose
C H
HO
OH
OH
OH
CH2OH
CH2OH
L-threose
D-fructose
39
Learning Check
Draw the structure and Fischer projection of D-fructose.
No of stereoisomers
40
Solution
CH2OH
C=O
1CH
2OH
C O
HO 3C
HO
H C OH
5
H C OH
6CH2OH
OH
OH
CH2OH
D-Fructose
Fischer projection
41
CYCLIZATION
Less
Formation of the
two cyclic forms of
D-glucose
In aqueous solution
monosaccharides with
five or more carbons
occur as cyclic structures.
Two stereoisomers are
produced and called
alpha (a) and beta (b).
CH2OH
HO C H
CH2OH
D-fructose
CH2OH
OH
H C OH
H C OH
CH2OH
OH
OH
OH
OH
-D-fructose
CH2OH
OH
-D-fructose
44
Mutarotation
O
H
C1
C2
OH
HO
C3
C4
OH
C5
OH
CH2OH
Anomeric
carbon
The hemiacetal (or carbonyl) carbon atom is
called the anomeric carbon.
5
Learning Check
Write the cyclic form of -D-galactose
O
C H
H C OH
HO C H
HO C H
H C OH
CH2OH
47
Solution
CH2OH
O
OH
OH
OH
OH
-D-galactose
48
Monosaccharides
Chemical Properties of
Monosaccharides
50
1.
2.
3.
4.
5.
6.
7.
Mutarotation
Oxidation
Reduction
Isomerization
Esterification
Glycoside formation
Formation of osazone with
phenylhydrazine
Oxidation of Sugars
Under mild oxidation conditions (hypobromous acid,
Br2/H2O), the aldehyde group is oxidized to carboxyl group
to produce aldonic acid. Thus, glucose is oxidized to
gluconic acid, mannose to mannonic acid and galactose
to galactonic acid.
Oxidation of D-Glucose
O
O
C
H C OH
HO C H
H C OH
C OH
Benedicts
reagent
+ Cu
2+
H C OH
[O]
HO C H
H C OH
H C OH
H C OH
CH2OH
CH2OH
D-glucose
Glucose is a reducing
sugar
Glucose is oxidized
to a carboxylic acid
+ Cu2O(s)
D-gluconic acid
53
Benedict's Reaction
Benedict's reagent contains sodium carbonate,
copper sulfate and sodium citrate.
In alkaline medium, sugars form enediol, cupric ions
are reduced, correspondingly sugar is oxidized.
Enediol Formation
In mild alkaline solutions, carbohydrates containing a free
sugar group (aldehyde or keto) will tautomerize to form
enediols, (ene =unsaturation ; ol = alcohol) where two
hydroxyl groups are attached to the double-bonded
carbon.
Enediol Formation
In mild alkaline conditions, glucose is converted into
fructose and mannose.
Enediol Formation
Since enediols are highly reactive, sugars are
powerful reducing agents in alkaline medium.
When oxidizing agents like cupric ions are present,
sugars form a mixture of carboxylic acids by breaking
at the double bonds.
Benedict's Reaction
Benedict's reagent is very commonly employed to
detect the presence of glucose in urine (glucosuria).
It is a standard laboratory test employed for follow-up
of diabetes mellitus.
Any sugar with free aldehyde/keto group will reduce
the Benedict's reagent.
61
Learning Check
Write the products of the oxidation and reduction of
D-mannose.
O
C H
HO
HO
OH
OH
CH2OH
D-mannose
63
Solution
Write the products of the oxidation and reduction of
D-mannose.
CH2OH
HO
HO
Reduction
C H
C OH
HO
HO
Oxidation
HO
HO
OH
OH
OH
OH
OH
OH
CH2OH
D-mannitol
CH2OH
CH2OH
D-mannose
D-mannonic acid
64
Formation of Esters
Hydroxyl groups of sugars can be esterified to form
acetates, propionates, benzoates, phosphates, etc.
Sugar phosphates are of great biological importance.
Amino Sugars
Amino groups may be substituted for hydroxyl groups
of sugars to give rise to amino sugars.
Generally, the amino group is added to the second
carbon atom of hexoses.
Glucosamine is seen in hyaluronic acid, heparin and
blood group substances.
Galactosamine is present in chondroitin of cartilage,
bone and tendons.
Mannosamine is a constituent of glycoproteins
Amino Sugars
The amino group in the
sugar may be further
acetylated to produce
N-acetylated sugars
such
as
N-acetyl-glucosamine
acetylgalactosamine
important
(GalNac),
constituents
of
(GluNac),
etc.
which
Nare
glycoproteins,
Osazone Formation
All reducing sugars will form osazones with excess of
phenylhydrazine when kept at boiling temperature.
Osazones are insoluble.
Each sugar will have characteristic crystal form of
osazones.
Osazones may be used to differentiate sugars
in biological fluids like urine.
Glycosidic Bonds
The anomeric hydroxyl and a hydroxyl of another sugar
or some other compound can join together, splitting out
water to form a glycosidic bond:
R-OH + HO-R' R-O-R' + H2O
E.g., methanol reacts with the anomeric OH on glucose
to form methyl glucoside (methyl-glucopyranose).
H OH
H OH
H2O
H O
HO
HO
H
H
OH
CH3-OH
HO
HO
H
H
OH
-D-glucopyranose
H O
methanol
H
OH
OCH3
methyl--D-glucopyranose
Glycosidic bond
REDUCTION
reduction of the aldehyde and ketone groups of monosacchs yield
sugar alcohols (alditols) Sugar alcohols
4. ISOMERIZATION
FORMATION- hemiacetal
or
hemiketal
form
of
Deoxy Sugars
Oxygen of the hydroxyl group may be removed to
form deoxy sugars.
L-fucose is present in blood group antigens and many
other glycoproteins.
Deoxy sugars
Pentoses
They are sugars containing 5 carbon atoms.
Ribose is a constituent of RNA. Ribose is also seen in
co-enzymes such as ATP and NAD. Deoxyribose is
seen in DNA.
Pentoses
Ribulose is an intermediate of HMP shunt pathway.
Arabinose is present in cherries and seen in
glycoproteins of the body. The name arabinose is
derived as it was originally isolated from gum arabic.
Xylose is seen in proteoglycans.
Xylulose is an intermediate of uronic acid pathway.