Lesson Learning Outcome

Upon completion of this lecture, students should

be able to:
recognize and differentiate carbohydrates
know the functions of carbohydrates
Sugars: Structure and Stereochemistry
Carbohydrates have the general formula CnH2nOn, where
n varies from 3 to 8
However only the simple sugars (monosaccharides) fit
this formula exactly
When a few monosaccharides are linked together, they
form oligosaccharides
When many monosaccharides are linked together, they
form polysaccharides
Rxns that adds monosaccharide units to a growing
carbohydrate molecule involve the loss of one H2O for
each new link formed
Monosaccharides
The most basic units of biologically important
carbohydrates
They are the simplest form of sugar and are usually
colorless, water soluble
Some monosaccharides have a sweet taste.
glucose (dextrose), fructose (levulose), galactose, 
Monosaccharides are the building blocks
of disaccharides such as sucrose
and polysaccharides (such as cellulose and starch).
Structure
Monosaccharides can either be polyhydroxy aldehyde
(aldose) or polyhydroxy ketone (ketose)
Structure
● Monosaccharides are classified by their number of
carbon atoms

Name Formula
triose C3 H6 O3
tetrose C4 H8 O4
pentose C5 H1 0 O5
hexose C6 H1 2 O6
heptose C7 H1 4 O7
octose C8 H1 6 O8
● There are only two trioses
CHO CH2 OH
CHOH C=O
CH2 OH CH2 OH
Glyceraldehyde Dihydroxyacetone
(an aldotriose) (a ketotriose)
 aldo- and keto- are often omitted and these compounds
are referred to simply as trioses; although this designation
does not tell the nature of the carbonyl group, it at least
tells the number of carbons
● Glyceraldehyde (aldose with three C) contains a
chiral carbon and exists as a pair of enantiomers
Fischer Projections
● Fischer projection: a two dimensional
representation for showing the configuration of
tetrahedral stereocenters
 horizontal lines represent bonds projecting forward
 vertical lines represent bonds projecting to the rear
 the carbon atom at the intersection of the horizontal
and vertical lines is not shown
convert to
CHO a Fischer CHO
projection
H C OH H OH

CH2 OH CH2 OH
D-Glyceraldehyde D-Glyceraldehyde
D,L Monosaccharides
● According to the conventions
proposed by Fischer
 D-monosaccharide: a
monosaccharide that, when
written as a Fischer projection,
has the -OH on the right of the
highest-numbered chiral carbon
 L-monosaccharide: a
monosaccharide that, when
written as a Fischer projection,
has the -OH on the left of the
highest-numbered chiral carbon
The four aldotetroses
● Enantiomers: stereoisomers that are mirror images
 example: D-erythrose and L-erythrose are
enantiomers
● Diastereomers: stereoisomers that are not mirror
images
 example: D-erythrose and D-threose are
diastereomers
Mirror Mirror
plane plane

CHO CHO CHO CHO

H OH HO H HO H H OH
H OH HO H H OH HO H
CH2 OH CH2 OH CH2 OH CH2 OH
D-Erythrose L-Erythrose D-Threose L-Threose
D,L Monosaccharides
● Following are the two most common D-aldotetroses
and the two most common D-aldopentoses

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 CH2 OH CH2 OH CH2 OH
D-Erythrose D-Threose D-Ribose 2-Deoxy-D-
ribose
What if sugar form cyclic
molecule?
Sugars especially with five or six carbon atoms
normally exist as cyclic molecule
This is due to interaction between the functional
groups on distant carbons
e.g. C-1 and C-5 to form hemiacetal
What if sugar form cyclic
molecule?
Cyclic sugar can take either of two different forms (α
or β) and are called anomers of each other
Free carbonyl (C=O) group can readily form either α-
or β-anomer
Anomers can be converted from one form to another
through the free carbonyl species
Fischer projection formulas do not give a realistic
picture of the bonding situation in the cyclic forms
Thus Haworth projection formulas are more useful
for this purpose.
five- and six-membered hemiacetals are represented
as planar pentagons or hexagons, as the case may
be, viewed through the edge
most commonly written with the anomeric carbon on
the right and the hemiacetal oxygen to the back right
Haworth Projections
CH=O CH2 OH
H OH H5 OH
HO H redraw O
H
H OH OH H C
5 HO H
H OH anomeric
CH2 OH H OH carbon
D-Glucose CH OH CH2 OH
2
H5 O OH() H5 O
H
H + H
OH H OH H
HO H HO OH()
H OH H OH
-D-Glucopyranose -D-Glucopyranose
(-D-Glucose) (-D-Glucose)
Haworth Projections
 a six-membered hemiacetal ring is shown by the infix
-pyran
 a five-membered hemiacetal ring is shown by the
infix -furan

O O
Furan Pyran
Conformational Formulas
 five-membered rings are so close to being planar that
Haworth projections are adequate to represent
furanoses
HOCH2 OH() HOCH2 H
O O
H H H H
H H H OH()
HO OH HO OH
-D-Ribofuranose -D-Ribofuranose
(-D-Ribose) (-D-Ribose)
Conformational Formulas
 for pyranoses, the six-membered ring is more
accurately represented as a strain-free chair
conformation

CH2 OH
HO O
HO
OH()
OH
-D-Glucopyranose
(chair conformation)
Conformational Formulas
 if you compare the orientations of groups on
carbons 1, 2, 3, 4, and 5 in the Haworth and chair
projections of -D-glucopyranose, you will see that
in each case they are up-down-up-down-up
respectively
CH2 OH
5
H O 4 CH2 OH
OH()
H HO 5 O
4 OH
H 1 HO
HO H 2 1 OH()
3 2 3
OH
H OH
-D-Glucopyranose -D-Glucopyranose
(Haworth projection) (chair conformation)
Ascorbic Acid (Vitamin C)
 L-Ascorbic acid (vitamin C) is synthesized both
biochemically and industrially from D-glucose

CHO
both biochemial
H OH CH2 OH
and industrial
HO H syntheses H OH O
H OH O
H OH H
HO OH
CH2 OH
L-Ascorbic acid
D-Glucose (Vitamin C)
Ascorbic Acid (Vitamin C)
 L-Ascorbic acid is very easily oxidized to L-
dehydroascorbic acid
 both are physiologically active and are found in
most body fluids

CH2 OH CH2 OH
H OH O H OH O
oxidation
O O
H reduction H
HO OH O O
L-Ascorbic acid L-Dehydroascorbic acid
(Vitamin C)
Reactions of monosaccharide
Oxidation and reduction reactions of sugars play an
important role in biochemistry
Oxidation of sugars  energy for organisms to carry
out life processes
Highest yeild of energy from complete oxidation of
sugar to CO2 and H2O in aerobic process
The reverse of this reaction takes place in
photosynthesis where sugar is formed as end product
 Oxidation
● Reducing sugar: one that reduces an oxidizing agent
 oxidation of a cyclic hemiacetal form gives a lactone
 when the oxidizing agent is Tollens’ solution, silver (Ag)
precipitates as a silver mirror

CH2 OH CH2 OH
H OH H O
H H
OH H + Ag(NH3 ) 2 + OH- OH H O + Ag
HO OH HO
H OH H OH
A cyclic A lactone
hemiacetal (a cyclic ester)
Disaccharides
● Sucrose
 table sugar; obtained from the juice of sugar cane
and sugar beet
 one unit of D-glucose and one unit of D-fructose
joined by an a-1,2-glycosidic bond

CH2 OH CH2 OH
D-Glucose O O
HO
OH 1 HO 1
HO OH
-1,2-glycosidic
OHO bond HOCH O
HOCH2 2 O
O
HO 2 HO 2

D-Fructose CH2 OH CH2 OH

1 1
OH OH
Disaccharides
● Lactose
 about 5% - 8% in human milk, 4% - 5% in cow’s milk
 one unit of D-galactose and one unit of D-glucose
joined by a b-1,4-glycosidic bond
D-glucose

D-galactose CH2 OH -1,4-glycosidic bond

4
O OH HO CH OH
2
CH2 OH OH O CH2 OH
HO O O 4
HO 1 O O
OH 1
OH OH HO OH
OH
HO -1,4-glycosidic bond
Disaccharides
● Maltose
 two units of D-glucose joined by an a-1,4-glycosidic
bond

-1,4-glycosidic bond

1 4 CH2 OH CH2 OH
O
HOCH2 O O OH HO
O HO 1
OH OH 4 CH2 OH
OH O
HO O
HO HO OH
OH OH
 Disaccharide Unit 1 Unit 2 Bond

Sucrose (table
sugar, cane
sugar, beet Glucose Fructose α(1→2)β
sugar,
or saccharose)

Lactulose Galactose Fructose β(1→4)

Lactose (milk
Galactose Glucose β(1→4)
sugar)
Maltose Glucose Glucose α(1→4)
Trehalose Glucose Glucose α(1→1)α
Cellobiose Glucose Glucose β(1→4)
Structural and functions of
polysaccharides
Polysaccharides
● Cellulose: the major structural component of plants,
especially wood and plant fibers
 a linear polymer of approximately 2800 D-glucose units
per molecule joined by β-1,4-glycosidic bonds
 fully extended conformation with alternating 180° flips
of glucose units
 extensive intra- and intermolecular hydrogen bonding
between chains

HO-CH2 OH 1 HO-CH2
4 4
O HO O
O O
O 4 HO 1
HO 1 O
OH HO-CH2 OH
Polysaccharides
● Starch is used for energy storage in plants
 a polymers of a-D-glucose units
 amylose: continuous, unbranched chains of up to
4000 a-D-glucose units joined by α-1,4-glycosidic
bonds
 amylopectin: a highly branched polymer consisting
of 24-30 units of D-glucose joined by α-1,4-
glycosidic bonds and branches created by α-1,6-
glycosidic bonds
Polysaccharides
● Glycogen is a branced-chain polymer of α-D-
glucose like amylopectin
● It also consist of a chain of α-1,4-glycosidic
bonds and branches created by α-1,6-glycosidic
bonds
● The difference is that glycogen is more branched
than amylopectins
Polysaccharides
Polysaccharides
● Chitin: the major structural component of the
exoskeletons of invertebrates, such as insects
and crustaceans; also occurs in cell walls of
algae, fungi, and yeasts
 composed of units of N-acetyl-β-D-glucosamine
joined by β-1,4-glycosidic bonds
Polysaccharides
● Bacterial cell walls: prokaryotic cell walls
are constructed on the framework of the
repeating unit NAM-NAG joined by β-1,4-
glycosidic bonds
Plant Cell Walls
 consist largely of cellulose
 also contain pectin which
functions as an intercellular
cementing material
 pectin is a polymer of D-
galacturonic acid joined by
α-1,4-glycosidic bonds
 the major
nonpolysaccharide of cell
walls, especially in woody
plants, is lignin
Polysaccharides
● Glycosaminoglycans: polysaccharides based on a
repeating disaccharide where one of the
monomers is an amino sugar and the other has a
negative charge due to a sulfate or carboxylate
group
 heparin: natural anticoagulant
 hyaluronic acid: a component of the vitreous humor of the
eye and the lubricating fluid of joints
 chondroitin sulfate and keratan sulfate: components of
connective tissue
Glycoproteins
● Glycoproteins contain carbohydrate units
covalently bonded to a polypeptide chain
antibodies are glycoproteins
carbohydrates play a role as antigenic
determinants, the portions of the antigenic
molecule that antibodies recognize and to
which they bind
Blood Group Substances
● Membranes of animal plasma cells have large
numbers of relatively small carbohydrates
bound to them
these membrane-bound carbohydrates act as
antigenic determinants
among the first antigenic determinants
discovered were the blood group substances
in the ABO system, individuals are classified
according to four blood types: A, B, AB, and O
Read up Chapter 16