Carbohydrates

Most abundant class of biological

molecules on Earth
Originally produced through CO2
fixation during photosynthesis

Roles of Carbohydrates
Energy storage (glycogen,starch)
Structural components
(cellulose,chitin)
Cellular recognition
Carbohydrate derivatives include
DNA, RNA, co-factors,
glycoproteins, glycolipids

Carbohydrates
Monosaccharides (simple sugars)
cannot be broken down into simpler
sugars under mild conditions
Oligosaccharides = "a few" - usually
2 to 10
Polysaccharides are polymers of the
simple sugars

Monosaccharides
Polyhydroxy ketones (ketoses)
and aldehydes (aldoses)
Aldoses and ketoses contain
aldehyde and ketone
functions, respectively
Triose, tetrose, etc. denotes
number of carbons
Empirical formula = (CH2O)n

H
C

CH2OH

C*

OH

HO

C*

C*

OH

CH2OH
D-ribose

HO

C*

C*

OH

CH2OH
D-ribulose

Monosaccharides
Monosaccharides are classified by their
number of carbon atoms.
Name

Formula

Triose
Tetrose
Pentose

C3 H6 O3
C4 H8 O4

Hexose

C6 H1 2 O6

Heptose
Octose

C5 H1 0 O5
C7 H1 4 O7
C8 H1 6 O8

Monosaccharides

There are only two trioses:

CHO

CH2 OH

CHOH

C=O

CH2 OH

CH2 OH

Glyceraldehyde
(an aldotriose)

Dihydroxyacetone
(a ketotriose)

Often aldo- and keto- are omitted and these compounds are
referred to simply as trioses.
Although triose does not tell the nature of the carbonyl group, it
at least tells the number of carbons.

Monosaccharides
Glyceraldehyde, the simplest aldose,
contains a stereocenter and exists as a pair
of enantiomers.
CHO

CHO
H

OH

CH2OH

HO

CH2OH

Monosaccharides

Fischer projection: a two dimensional representation for showing the

configuration of tetrahedral stereocenters.
Horizontal lines represent bonds projecting forward from the
stereocenter.
Vertical lines represent bonds projecting to the rear.
Only the stereocenter is in the plane.

CHO
H

OH

CH2OH

convert to
a Fischer
projection

CHO
H
OH
CH2 OH

D,L Monosaccharides
The most common D-tetroses and D-pentoses are:
CHO
CHO
CHO
CHO
H
OH
H
H
H
OH
HO H
H
OH
H
OH
H
OH
H OH
H
OH
H OH
CH2 OH
D-Erythrose

CH2 OH
D-Threose

CH2 OH

D-Ribose

CH2 OH

2-Deoxy-D-ribose

The three most common D-hexoses are:

CHO
H
OH
HO
H
H
OH
H
OH
CH2 OH
D-Glucose

CHO
H
OH
HO
H
HO H
H OH
CH2 OH
D-Galactose

CH2 OH
C=O
HO
H
H OH
H OH
CH2 OH
D-Fructose

Monosaccharides are chiral

Aldoses with 3C or more and
ketoses with 4C or more are
chiral
The number of chiral carbons
present in a ketose is always
one less than the number
found in the same length
aldose
Number of possible
steroisomers = 2n (n = the
number of chiral carbons)

H
C

CH2OH

C*

OH

HO

C*

C*

C*

HO

C*

OH

C*

OH

OH

C*

OH

CH2OH

CH2OH

D-glucose

D-fructose

Stereochemistry
Enantiomers
O

H
C

HO

C*

C*

OH

HO

C*

HO

C*

Epimers

Diastereomers
O

H
C

C*

OH

HO

C*

C*

OH

HO

C*

HO

C*

HO

C*

C*

OH

C*

OH

HO

C*

OH

C*

OH

CH2OH

L-glucose

D-glucose

H
C

CH2OH

H
C

C*

OH

HO

C*

HO

C*

HO

C*

C*

C*

OH

C*

OH

C*

OH

C*

OH

C*

OH

CH2OH

CH2OH

D-mannose

D-galactose

CH2OH
D-glucose

CH2OH
D-mannose

Enantiomers = mirror images

Pairs of isomers that have opposite configurations at
one or more chiral centers but are NOT mirror images
are diastereomers
Epimers = Two sugars that differ in configuration at
only one chiral center

Cyclization of aldose and ketoses

introduces additional chiral center
Aldose sugars (glucose) can cyclize to form a
H
cyclic hemiacetal H O ALDEHYDE
NEW CHIRAL
O
CARBON

C
H
ALCOHOL

H
R1

C*
O

R2

O
H

R1

R2

HEMIACETAL

can
cyclize toH form NEW
a CHIRAL
Ketose sugars (fructose)
H
KETONE
O
O
CARBON
cyclic hemiketal
C
R
ALCOHOL

R
R1

R1

O
R2

O
H

C*

R2

HEMIKETAL

Haworth Projections
O

-OH up = beta
-OH down = alpha

C1
H

C2

OH

HO

C3

C4

OH

C5

OH

CH2OH

6
5
4

1
3

Anomeric carbon
(most oxidized)

For all non-anomeric carbons, -OH groups

point down in Haworth projections if
pointing right in Fischer projections

Monosaccharides can cyclize to

form Pyranose / Furanose forms
= 64%
= 36%

= 21.5%
= 58.5%

= 13.5%
= 6.5%

Conformation of Monosaccharides

Pyranose sugars not planar molecules, prefer to be in

either of the two chair conformations.

Reducing Sugars
When in the uncyclized
form, monosaccharides
act as reducing agents.
Free carbonyl group from
aldoses or ketoses can
reduce Cu2+ and Ag+ ions
to insoluble products

Derivatives of
Monosaccharides

Sugar Phosphates

Deoxy Acids

Amino Sugars

Sugar alcohols

Monosaccharide structures
you need to know

Glucose
Fructose
Ribulose
Glyceraldehyde
Dihydroxyacetone

Physical Properties

Monosaccharides are colorless crystalline solids, very soluble in water,

but only slightly soluble in ethanol

Sweetness relative to sucrose:

Sweetness
Relative to
Carbohydrate
Sucrose
fructose
1.74
sucrose (table sugar) 1.00
honey
0.97
glucose
0.74
maltose
0.33
galactose
0.32
lactose (milk sugar) 0.16

Sweetness
Relative to
Artificial
Sweetener
Sucrose
saccharin
450
acesulfame-K
200
aspartame
180

Reduction to Alditols
The carbonyl group of a monosaccharide can be reduced to
an hydroxyl group by a variety of reducing agents,
including NaBH4 and H2 in the presence of a transition
metal catalyst.
The reduction product is called an alditol.
HO
HO

CH2OH
O
OH

OH
-D-Glucopyranose

CHO
H OH
HO H
NaBH4
H OH
H OH
CH2 OH
D-Glucose

CH2 OH
H OH
HO H
H OH
H OH
CH2 OH
D-Glucitol
(D-Sorbitol)

Reduction to Alditols
Sorbitol is found in the plant world in many berries and in
cherries, plums, pears, apples, seaweed, and algae.
It is about 60 percent as sweet as sucrose (table sugar) and is used
in the manufacture of candies and as a sugar substitute for
diabetics.
These three alditols are also common in the biological world.

CH2 OH
H OH
H OH
CH2 OH
Erythritol

CH2 OH
HO
H
HO
H
H OH
H OH
CH2 OH
D-Mannitol

CH2 OH
H OH
HO
H
H
OH
CH2 OH
Xylitol

Oxidation to Aldonic Acids

The aldehyde group of an aldose is oxidized under
basic conditions to a carboxylate anion.
The oxidation product is called an aldonic acid.
acid
A carbohydrate that reacts with an oxidizing agent to
form an aldonic acid is classified as a reducing sugar (it
O Oreduces the oxidizing agent). O H
C

HO
HO

CH2 OH
O
OH

OH

- D-Glucopyranose
( -D-Glucose)

OH oxidizing
H OH
agent
H
HO H
OH
basic
H OH
OH solution
H OH
CH2 OH
CH2 OH
D-Glucose
D-Gluconate

H
HO
H
H

Oxidation to Uronic Acids

Enzyme-catalyzed oxidation of the primary alcohol at C-6
of a hexose yields a uronic acid.
acid
Enzyme-catalyzed oxidation of D-glucose, for example,
yields D-glucuronic acid.
CHO
enzymeH
OH
catalyzed
HO H
oxidation
H
OH
H
OH
CH2 OH
D-Glucose

CHO
H
OH
COOH
O
HO H
HO
H
OH
HO
OH
H
OH
COOH
D-Glucuronic acid
(a uronic acid)

OH

D-Glucuronic Acid
D-Glucuronic acid is widely distributed in the plant and
animal world.
In humans, it is an important component of the acidic
polysaccharides of connective tissues.
It is used by the body to detoxify foreign phenols and
alcohols; in the liver, these compounds are converted to
glycosides of glucuronic acid and excreted in the urine.

HO

Propofol

HO
HO

COO-

OH

A urine-soluble glucuronide

CH2OH

Glycosidic
Linkage

CH2OH
hemiacetal

OH

OH
OH

OH

OH
OH

alcohol

OH

Hydrolysis
H2O

H2O

Condensation

CH2OH
O

CH2OH
acetal

OH

OH

OH
O

OH
OH

OH
glycosidic linkage

OH

CH2OH
H

CH2OH

O H
OH

Disaccharides

O
OH

OH

maltose

H
H

OH

CH2OH
OH
O

sucrose

OH
OH

CH2OH
O
H
OH

CH2OH
OH

CH2OH
H

O OH
OH

O
H

H
H

OH

OH

lactose

OH
H

-D-glucosyl-(1->4)--D-glucopyranose)

O H
OH

OH
H

OH

CH2OH
H

O
OH

-D-glucosyl-(1->4)--D-glucopyranose)

O OH
OH

OH

CH2OH

cellobiose

CH2OH

OH

OH

-D-galactosyl-(1->4)--D-glucopyranose)

-D-glucosyl-(1->2)--D-fructofuranose)

Higher Oligosaccharides

Oligosaccharide groups are incorporated

in to many drug structures

Polysaccharides

Amylose and Amylopectin

Iodine binding to starch

 Alpha amylase- breaks alpha 1,4- linkage

B- amylase- found in plants attacks from
the non-reducing end to yield successive
units of maltose
Limit dextrin- near branch points alpha 1,4
and alpha 1,6 not hydrolysed
Debranching enzyme or alpha 1,6
glucosidase hydrolyzes bonds at branch
points

glycogen

Dextrans
A small but significant difference from starch
and glycogen
If you change the main linkages between
glucose from alpha(1,4) to alpha(1,6), you
get a new family of polysaccharides dextrans
Branches can be (1,2), (1,3), or (1,4)

Dextrans

Cellulose

Cellulose vs Amylose
amylose

cellulose

Glucose units rotated 180o relative to next residue

Chitin

Chitin vs Cellulose

Glycoproteins

O-linked Glycoproteins

Blood ABO Antigens

Structure of the ABO blood group

carbohydrates,
R represents the linkage to protein
in the secreted forms, sphingolipid
in the cell-surface bound form
open square = GlcNAc, open diamond
= galactose, filled square = fucose,
filled diamond = GalNAc, filled
diamond = sialic acid (NANA)

Other Structural Polysaccharides

Alginates - Ca-binding polymers in algae

Agarose and agaropectin - galactose polymers
Glycosaminoglycans - repeating disaccharides with amino sugars and negative
charges
Pectins- contain arabinose, galactose and galacturonic acid- found in plant cell
wall

Reactions of Monosaccharides
1. Monosaccharides exhibit mutarotation
2. When these sugars act as reducing
agents, they are in turn oxidized
Glucose
A. mild OAs aldonic acids
B. strong OAs HNO3- aldaric acids
C. enzyme- uronic acids

 3. The aldehyde and ketone functions may be

reduced to sugar alcohols, e.g.
Glucose----H2, Pt or NaBH4 sorbitol-
Fermentation-sorbose - ascorbic acid
4. They form glycosides
5. Characteristic reactions: formation of
furfuraldehyde and
hydroxymethylfurfuraldehyde

Tests to dehydrate sugars

Test

Reagents/procedures

Product responsible
for the color

Positive result

Molisch test

Alpha naphthol, then

heat with conc.
H2SO4, general test
for carbohydrates

Furfural and
Violet ring
hydroxymethyl furfural

Bials Orcino test

, orcinol, 30% HCl

FeCl3 soln
Presence of pentoses
and nucleotides with
pentoses

Formation of
furfural(pentoses) and
hydroxymethylfurfural
(hexoses) which yields
blue green compound
in the presence of Fe3+

Heptoses- blue or
green products
Hexoses- yellow
brown

Seliwanoffs test

HCl + resorcinol
differentiates
aldohexoses from
ketohexoses

Dehydrated ketoses
react faster to give
colored condensation
products

Bright cherry red with

ketohexose,
aldohexose give pale
pink color

Test to oxidize sugars

Tests

Reagents/Procedures Product responsible Positive result

for color

Benedicts test

CuSO4, Na2CO3,
sodium citrate

Fehlings test

CuSO4, sodium citrate Cu2O

Brick red ppt

Barfoeds test

Copper acetate in dil

HCl, can distinguish
bet. Reducing monoand disaccharides

Cu2O

Brick red ppt

Tollens tes

AgNO3, NH3

Ag mirror

Ag

Phenylhydrazine

Phenylhydrazine +
heat

Phenyl hydrazone

Yellow-orange ppt

Cu2O

Brick red