BTY-213

PLANT BIOCHEMISTRY
CARBOHYDRATES-MONOSACCHRIDES
LECTURE 2

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
Ketose named for equivalent
aldose + ul inserted
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

Monosacchrides
Aldoses are monosacchrides with an aldehyde
group and many hydroxyl (-OH) groups.
Ketoses are monosacchrides with a ketone group
and many hydroxyl (-OH) groups.

Monosaccharides
Monosaccharides are composed of:
Carbon
Hydrogen
Oxygen
Basic Formula = (CH2O)n n = any integer 3 7

Many monosaccharides also contain

chemical modifications
Amino groups
Phosphate groups

Naming Monosaccharides
Named on the basis of
Functional groups
Ketone carbonyl = ketose
Aldehyde carbonyl = aldose

Number of carbon atoms

in the main skeleton
16.2 Monosaccharides

3 carbons = triose
4 carbons = tetrose
5 carbons = pentose
6 carbons = hexose

Stereoisomers and Stereochemistry

Prefixes D- and L- in a monosaccharide name identify
one of two isomeric forms
These isomers differ in the spatial arrangement of atoms
and are stereoisomers

Stereochemistry is the study of different spatial

arrangements of atoms
The stereoisomers D- and L- glyceraldehyde are nonsuperimposable mirror image molecules and are
called enantiomers (a subset of stereoisomers)

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

16.3 Stereoisomers and Stereochemistry

Enantiomers

Chirality

16.3 Stereoisomers and Stereochemistry

A carbon atom that has four different groups

bonded to it is called a chiral carbon atom
Any molecule containing a chiral carbon can
exist as a pair of enantiomers
Chirality in glyceraldehyde (the simplest
carbohydrate) is conveyed by a chiral carbon
Larger biological molecules often have more
than one chiral carbon

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

Chirality of Glyceraldehyde
Glyceraldehyde has a chiral carbon and thus, has
two enantiomers

16.3 Stereoisomers and Stereochemistry

The D isomer has the -OH on the stereocenter to the

right
The L isomer has the -OH on the stereocenter to the left
Chiral Carbon:
connected to
four
different atoms
or groups

Mirror
plane

O
C

H C OH
CH2OH
the D isomer

O
C

HO C H
CH2OH

the L isomer

16.3 Stereoisomers and Stereochemistry

Structural Formulas of D- and LGlyceraldehyde

16.3 Stereoisomers and Stereochemistry

Optical Activity
Enantiomers are also called optical
isomers
Enantiomers interact with plain polarized
light to rotate the plane of the light in
opposite directions
This interaction with polarized light is called
optical activity
Optical activity distinguishes the isomers
It is measured in a device called a polarimeter

Polarized Light
Normal light vibrates in an infinite number of
directions perpendicular to the direction of travel
16.3 Stereoisomers and Stereochemistry

When the light passes through a polarizing filter

(Polaroid sunglasses) only light vibrating in one plane
reaches the other side of the filter
A polarimeter allows the determination of the specific
rotation of a compound
Measures its ability to rotate plane-polarized light

16.3 Stereoisomers and Stereochemistry

Schematic Drawing of a Polarimeter

The Relationship Between Molecular

Structure and Optical Activity
When an enantiomer in a solution is placed in the
polarimeter, the plane of rotation of the polarized light is
rotated
16.3 Stereoisomers and Stereochemistry

One enantiomer always rotates light in a clockwise (+)

direction
This is the dextrorotatory isomer

The other isomer rotates the light in a counterclockwise (-)

direction
It is the levorotatory isomer

Under identical conditions, the enantiomers always rotate

light to exactly the same degree, but in opposite
directions

Fischer Projection Formulas

16.3 Stereoisomers and Stereochemistry

A Fischer projection uses lines crossing through a

chiral carbon to represent bonds
Projecting out of the page (horizontal lines)
Projecting into the page (vertical lines)

Compare the wedge to the Fischer diagrams

Fischer Projections of Monosaccharides

O
C

C H2O H

H
1
1
H2

O H3

16.3 Stereoisomers and Stereochemistry

C H2O H
4

D -e r y th r o s e
a n a ld o te tr o s e

HO

2
3C

4C

OH

OH

C H2O H
D -fr u c to s e
a k e to h e x o s e

16.3 Stereoisomers and Stereochemistry

Aldose or Ketose?

The D- and L-System

16.3 Stereoisomers and Stereochemistry

Monosaccharides are drawn in Fischer projections

With the most oxidized carbon closest to the top
The carbons are numbered from the top
If the chiral carbon with the highest number has the OH to the
right, the sugar is D
If the OH is to the left, the sugar is L

Most common sugars are in the D form

CHO

CHO

H C OH H
CH2OH

OH
CH2OH

the Disomer

CHO

CHO

HO C H HO
CH2OH

H
CH2OH

the Lisomer

Biological Monosaccharides
Glucose is the most important sugar in the human body
Found in many foods
Several common names include: dextrose and blood sugar
Its concentration in the blood is regulated by insulin and
glucagon

Under physiological conditions, glucose exists in a cyclic

hemiacetal form where the C-5 hydroxyl reacts with the
C-1 aldehyde group
Two isomers are formed which differ in the location of the OH on the acetal carbon, C-1

An aldohexose with molecular formula C6H12O6

Cyclic Form of Glucose

The cyclic form of glucose is shown as a Haworth
projection

16.4 Biological Monosaccharides

arrows show
electron m ovem ent
C H 2 OH
O H
H
H
H
OH
H
O
HO
H

OH

C H 2 OH
O H form
H
H
(alpha)
OH
H
HO
OH
H
OH Pyranose
ring form

C H 2 OH
O OH
H
H
form
OH
H
(beta)
HO
H
H
OH

16.4 Biological Monosaccharides

Cyclization of Glucose

Fructose
Fructose is also called:
Fruit sugar

16.4 Biological Monosaccharides

Found in large amounts in:

Honey
Corn syrup
Fruits

The sweetest of all sugars

Ketohexose

C
H
O
H
2
2
C
O
3
H O 4C H
H 5C O H
H 6C O H
C H2O H
D -fru c to s e

C H2O H
C H2O H
O

OH
H
OH H
C H2O H
OH
O

H
OH H

C H2O H

Galactose
Galactose is the principal sugar found in mammalian milk
Aldohexose very similar to glucose
b-D-galactosamine is a component of the blood group
antigens
1

16.4 Biological Monosaccharides

CHO
2
H C OH
3
HO C H
4
HO C H
5
H C OH
6
CH2O H

C H2O H
HO
O H
H
OH H
OH
H
H
OH
- D -ga lac tose

Galactose Orientation

16.4 Biological Monosaccharides

Glucose and galactose differ only in

the orientation of one hydroxyl group

Ribose and Deoxyribose,

Five-Carbon Sugars

16.4 Biological Monosaccharides

CHO
H C OH
H C OH
H C OH
C H2O H

C H2O H H
O
H
H
OH
H
OH OH
-D -rib o se
Deoxyribose has
an -H here
replacing the -OH

Reducing Sugars

16.4 Biological Monosaccharides

The aldehyde groups of aldoses are oxidized by

Benedicts reagent, an alkaline copper(II) solution
The blue color of the reagent fades as reaction occurs
reducing Cu2+ to Cu+ with a red-orange precipitate
forming as Cu2O results
Test can measure glucose in urine

C
H C O H +2 C u 2+
CH2O H

C
H C OH
C H2O H

+ Cu2O (red-orange)

Reducing Sugars
All monosaccharides and the disaccharides
except sucrose are reducing sugars
Ketoses can isomerize to aldoses and react also

16.4 Biological Monosaccharides

CH2OH
CO
HO C H
H C OH
H C OH
CH2OH
D-fructose

HO CH
O CH
C OH
H C OH
HO C H
HO C H
H C OH
H C OH
H C OH
H C OH
CH2OH
CH2OH
enediol
D-glucose

A Reduced Sugar
The most important reduced sugar is deoxyribose

C
H C H
H C OH
H C OH
CH2OH
D-deoxyribose

CH2OH
O OH
H H
H
H
OH H
-D-2-deoxyribose

Derivatives of
Monosaccharides

Sugar Phosphates

Deoxy Acids

Amino Sugars

Sugar alcohols

THANKS