CARBOHYDRATES-MONOSACCHRIDES

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
• Polyhydroxy ketones
O
(ketoses) and aldehydes H
(aldoses) C CH2OH

• Aldoses and ketoses contain H C* OH C O

aldehyde and ketone
HO C* H HO C* H
functions, respectively
H C* OH H C* OH
• Ketose named for “equivalent
aldose” + “ul” inserted CH2OH CH2OH
• Triose, tetrose, etc. denotes D-ribose D-ribulose

number of carbons
• Empirical formula = (CH2O)n
 Carbohydrates-
Classification
• 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
 Monosacchrides-classification
• Aldoses are
monosacchrides with an
aldehyde group and many
hydroxyl (-OH) groups.

• Ketoses are
monosacchrides with a
ketone group and many
hydroxyl (-OH) groups.
6
 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
– 3 carbons = triose
– 4 carbons = tetrose
16.2 Monosaccharides

– 5 carbons = pentose
– 6 carbons = hexose
 Chirality
• 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 single 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 O
H
ketose is always one less C CH2OH
than the number found in
H C* OH C O
the same length aldose
HO C* H
• Number of possible HO C* H

steroisomers = 2n (n = H C* OH H C* OH

the number of chiral H C* OH H C* OH

carbons) CH2OH CH2OH
D-glucose D-fructose
 Chirality of Glyceraldehyde
• Glyceraldehyde has a chiral carbon and thus, has two
enantiomers
– The D isomer has the -OH on the stereocenter to the right
– The L isomer has the -OH on the stereocenter to the left
16.3 Stereoisomers and Stereochemistry

Mirror
Chiral Carbon:
plane
connected to
four O H O H
different atoms C C
or groups
H C OH HO C H
CH2OH CH2OH
the D isomer the L isomer
 Structural Formulas of D- and L-
Glyceraldehyde
16.3 Stereoisomers and Stereochemistry
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 non-
superimposable mirror image molecules and are
called enantiomers (a subset of stereoisomers)
16.3 Stereoisomers and Stereochemistry Enantiomers
 The D- and L-System
• 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 CHO CHO

H C OH H OH HO C H HO H
CH2OH CH2OH CH2OH CH2OH
the D isomer the L isomer
 Stereochemistry
Enantiomers Diastereomers Epimers
O O O O O O
H H H H H H
C C C C C C

HO C* H H C* OH HO C* H H C* OH H C* OH HO C* H

H C* OH HO C* H HO C* H HO C* H HO C* H HO C* H

HO C* H H C* OH H C* OH HO C* H H C* OH H C* OH

HO C* H H C* OH H C* OH H C* OH H C* OH H C* OH

CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH

L-glucose D-glucose D-mannose D-galactose D-glucose 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
 Optical Activity
• Enantiomers are also called optical
isomers
• Enantiomers interact with plain polarized
light to rotate the plane of the light in
16.3 Stereoisomers and Stereochemistry

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
– 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
– 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
• 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
 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
CH2OH
arrows show H O H  form
electron movement H (alpha)
OH H
CH2OH HO OH
H O H
H H OH Pyranose
H ring form
OH H O CH2OH
HO
H O OH
H OH H  form
OH H (beta)
HO H
H OH
16.4 Biological Monosaccharides Cyclization of Glucose
 Fructose

• Fructose is also called:

– Fruit sugar
• Found in large amounts in:
– Honey
– Corn syrup
– Fruits
• The sweetest of all sugars
• Ketohexose
 CH2OH
1 CH2OH
2
CH2
OH O 

3
C O H OH
HO 4C H OH H
H 5C OH
H 6C OH CH2OH
CH2OH OH
O 
D-fructose
H CH2OH
OH H
 Galactose
 Galactose is the principal sugar found in mammalian milk
 Aldohexose very similar to glucose
 -D-galactosamine is a component of the blood group
antigens
1
CHO CH2OH
2
H C OH HO O H
3
HO C H H
4
HO C H OH H
5
H C OH H OH
6 H OH
CH2OH -D-galactose
 Galactose Orientation
Glucose and galactose differ only in
the orientation of one hydroxyl group
 Ribose and Deoxyribose,
Five-Carbon Sugars

CHO CH2OH H
H C OH O
H C OH H H
H C OH H OH
CH2OH OH OH
-D-ribose
Deoxyribose has
an -H here
replacing the -OH
 Reducing Sugars
• The aldehyde groups of aldoses are oxidized by
Benedict’s 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
16.4 Biological Monosaccharides

O H O O
C C
H C OH +2 Cu2+ H C OH
CH2OH CH2OH
+ Cu2O (red-orange)
 Reducing Sugars
• All monosaccharides and the disaccharides
except sucrose are reducing sugars
• Ketoses can isomerize to aldoses and react also

CH2OH HO CH O CH
CO C OH H C OH
HO C H HO C H HO C H
H C OH H C OH H C OH
H C OH H C OH H C OH
CH2OH CH2OH CH2OH
D-fructose enediol D-glucose
 A Reduced Sugar
• The most important reduced sugar is deoxyribose

O H CH2OH
C O OH
H C H
H C OH H H
H C OH
H H
CH2OH OH H
D-deoxyribose -D-2-deoxyribose
 Derivatives of
Monosaccharides
Sugar Phosphates
 Deoxy Acids

Complex
Plant
Nucleic acid DNA oligosaccharides of
Polysaccharide
Glycolipids and
glycoproteins
Amino Sugars
Sugar alcohols