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What are Carbohydrates?

CARBOHYDRATES

Carbohydrates are polyhydroxy aldehydes or ketones, or


substances that yield such compounds upon hydrolysis.
Carbohydrates are also known as saccharides
(sakcharon G = sugar or sweetness)

hydrates of carbon or could be represented by


the general formula, Cn(H20)n

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).

As a precursor for other


biomolecules (purine, pyrimide)

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

2.1 Monosach Properties& classification


Colorless, crystalline solids
Soluble in water but insoluble in nonpolar
solvents
One of the carbon atoms is double-bonded to an
oxygen atom to form a carbonyl group; each of
the other carbon atoms has a hydroxyl group.
Carbohydrates with an aldehyde (-CHO) functional
group are called aldoses e.g. glyceraldehyde (CH OH-CHOH-CHO)
Those with a keto group (-C=O) are ketoses
2

e.g.dihydroxyacetone (CH2OH-C=O-CH2OH)

Classified according to the number of carbon atoms


they contain

Monosacharides : Exp. aldoses & ketoses

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

Isomers different compounds with the same molecular formula.

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.

ENANTIOMER PROPERTIES (continued)


The enantiomer that rotates polarized light to the left is the
levorotatory or (-) enantiomer.
The enantiomer that rotates it to the right is the
dextrorotatory or (+) enantiomer.
The D and L designations do not represent dextrorotatory
and levorotatory.
The property of rotating the plane of polarized light is called
optical activity, and the molecules with this property are said
to be optically active.
Measurements of optical activity are useful for differentiating
between enantiomers.

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:

The maximum number of stereoisomers is 2n where n=


number of chiral carbon atoms.
Therefore, this compound with two chiral carbon atoms has
22 or 4 stereoisomers.
The compound on the previous slide with four chiral carbon
atoms has 24 or 16 stereoisomers.

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.

Copyright 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

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.

Copyright 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

35

Examples of D and L Isomers of


Monosaccharides
O

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

Most monosaccharides are aldoses.


Almost all natural monosaccharides belong to the D series.
The maximum number of possible stereoisomers is 2n,
where n = number of chiral carbon atoms.
Half of stereoisomers are D and the other other half are L.

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

then 1%of CHO exist in an open


chain form.
Predominantly found in ring form.
Six

membered ring structures are called


Pyranoses .
five membered ring structures are called
Furanoses .

Haworth Perspective Formula

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).

Cyclic Structure of Fructose


Fructose
Is a ketohexose.
Forms a cyclic structure.
Reacts the OH on C-5 with the C=O on C-2.
CH2OH
C O

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

Cyclization of aldose and ketoses


introduces additional chiral center
Aldose sugars (glucose) can cyclize to form a
cyclic hemiacetal
Ketose sugars (fructose) can cyclize to form a
cyclic hemiketal

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

Isomeric forms of monosaccharides that differ only in their


configuration about the hemiacetal or hemiketal carbon atom
are called anomers.

The alfa and beta anomers of D-glucose interconvert in


aqueous solution by a process called mutarotation.

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

SUMMARY OF SUGAR STRUCTURES

ISOMERS- compounds that have the same chemical formula e.g.


fructose, glucose, mannose, and galactose are isomers of each
other having formula C6H12O6.
EPIMERS- refer to sugars whose configuration differ around one
specific carbon atom e.g. glucose and galactose are C-4 epimers
and glucose and mannose are C-2 epimers.
ENANTIOMERS- a special type of isomerism found in pairs of
structures that are mirror images of each other. The mirror images
are termed as enantiomers and the two members are designated as
D- and L- sugar. The vast majority of sugars in humans are Dsugars.
Diastereomers Pairs of stereoisomers that are not mirror images of
each other are called
CYCLIZATION OF SUGARS- most monosaccharides with 5 or more
carbon atoms are predominately found in a ring form, where the
aldehyde or ketone group has reacted with an alcoholic group on
the same sugar group to form a hemiacetal or hemiketal ring.
Pyranose ring- if the ring has 5 carbons and 1 oxygen.
Furanose ring- if the ring is 5-membered (4 carbons and 1 oxygen

Monosaccharides
Chemical Properties of
Monosaccharides

Copyright 2007 by Pearson Education, Inc.


Publishing as Benjamin Cummings

50

2.4.IMPORTANT REACTIONS IN MONOSACCHARIDES


Monosaccharides undergo the following reactions :

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.

Benedict's test, principle

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.

Interconversion of glucose, mannose and fructose (Enolization)

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.

Reduction to Form Alcohols


When treated with reducing agents, such as sodium
amalgam, hydrogen can reduce sugars. Aldose yields
corresponding alcohol.
But ketose forms two alcohols, because of
appearance of a new asymmetric carbon atom in this
process

Reduction to Form Alcohols


Glucose is reduced to sorbitol; mannose to mannitol;
while fructose becomes sorbitol and mannitol.
Galactose is reduced to dulcitol and ribose to ribitol.

Reduction of sugar to alcohol

61

Reduction to Form Alcohols


Sorbitol, mannitol and dulcitol are used to identify
bacterial colonies.
Mannitol is also used to reduce intracranial tension
by forced diuresis.
The osmotic effect of sorbitol and dulcitol produces
changes in tissues when they accumulate in
abnormal amounts, e.g. cataract of lens.

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,

mucopolysaccharides and cell membrane antigens.

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

IMPORTANT REACTIONS IN MONOSACCHARIDES


Details
1. Mutarotation
2

Oxidation and reduction

in presence of oxidising agents, metal

ions (Cu2+) and enzymes, monosacchs undergo several oxidation


reactions e.g. Oxidation of aldehyde group (R-CHO) yields aldonic
acid; of terminal CH2OH (alcohol) yields uronic acid; and of both
the aldehyde and CH2OH gives aldaric acid. The carbonyl groups in
both aldonic and uronic can react with an OH group in the sam
3

REDUCTION
reduction of the aldehyde and ketone groups of monosacchs yield
sugar alcohols (alditols) Sugar alcohols

IMPORTANT REACTIONS (Cont)

4. ISOMERIZATION

Monosaccharides undergo several types of

isomerization e.g. D-glucose in alkaline solution for several hours


containn D-mannose and D-fructose. The conversion of glucose to
mannose is termed s epimerization.
5 ESTERIFICATION Free OH groups of carbohydrates react with acids
to form esters. This reaction an change the physical and chemical
propteries of sugar.
6. GLYCOSIDE

FORMATION- hemiacetal

or

hemiketal

form

of

monosaccharide reacts with alcohol, the new linkage is called


glycosidic linkage and the compound glycoside.

Some hexose derivatives important in biology.

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.