CHEM 160

CARBOHYDRATES:
Structure and Properties
Objectives
• Give the chemical structure and classification of
simple and complex carbohydrates and their
derivatives
• Correlate the structure of carbohydrates with
their function and activity
Carbohydrates
• Polyhydroxylated aldehydes and ketones and
substances that yield such compounds upon
hydrolysis
• Functions:
1. As energy source
2. As part of the structural framework
3. As structural elements in cell walls
4. As part of nucleic acids and some lipids and
proteins
5. As units on cell surfaces for cell-to-cell
recognition processes
Major Classes
1. Monosaccharides (simple sugars)
• Single polyhydroxylated aldehyde or ketone
unit
2. Disaccharides
• Consist of two monosaccharides linked
together by a glycosidic bond
3. Oligosaccharide
• Made up of 3-10 monosaccharide units
4. Polysaccharides
• Long chains of monosaccharide units
Monosaccharides
• General formula: (CH2O)n
• Simplest would be those with n=3
Classifying Monosaccharides
• Based on carbonyl group present
1. Aldose
2. Ketose
• Based on the number of carbon atoms:
1. Triose
2. Tetrose
3. Pentose
4. Hexose
5. Heptose
Classifying Monosaccharides
Stereochemistry
• All monosaccharides (except dihyroxyacetone)
are optically active
Stereochemistry
• Configurations:
• D – when ―OH group is at the right of the
penultimate carbon
• L – when ―OH group is at the left of the
penultimate carbon
No. of Stereoisomers = 2 n

• n = no. of chiral centers

• For ALDOTRIOSE, n = 1 ∴ 21 = 2 stereoiseomers
• D-glyceraldehyde and L-glyceraldehyde
• For ALDOTETROSE, n = 2 ∴ 22 = 4 stereoiseomers
No. of Stereoisomers = 2 n

• For ALDOPENTOSE, n = 3 ∴ 23 = 8 stereoiseomers

No. of Stereoisomers = 2 n

• For ALDOHEXOSE, n = 4 ∴ 24 = 16 stereoiseomers

Ketoses
Epimers
• Sugars that differ in configuration in only one
carbon other than the penultimate carbon
Cyclic Structures
• Recall: Formation of hemiacetals/hemiketals
Haworth Structures
C
H
2O
H
O
HH
OH C
O
H
C O
O
H O
HO
H
O
H
H
OH
HO
H p yra n
HO
H
C
HO
H C
H
2O
H C
H
2O
H
2
O OOH
D
-
gl
uco
s
e
O
H O
H
O
H O
H O
H
OH O H
α-D-glucopyranose β-D-glucopyranose
Haworth Structures
HOH2C
OH CH2OH
CH2 OH HO C
O
O O
HO
HO H
H OH fu ra n
H OH
CH2OH HOH2C HOH2C
O OH CH2OH O OH OH
D-fructose
OH CH2OH
HO HO
α-D-fructofuranose β-D-fructofuranose
Chair Cyclic Structures

C
HOH C
HO
2H
2 O H
O O
H
O
H
O O
H H
O
O
H O
H
OH
β-D-glucopyranose α-D-glucopyranose
Anomers
C
HOH C
HO
2H
2 O H
O O
H
O
H
O O
H H
O
O
H O
H
OH
β -D-glucopyranose α -D-glucopyranose

• β -anomer: ―OH at anomeric C cis to ―CH2OH

• α -anomer: ―OH at anomeric C trans to ―CH2OH
Anomers
• Stereoisomers that differ in configuration at the
anomeric carbon O H
C
CH2OH H OH CH2OH
HO O HO O
HO H
HO HO OH
H OH
OH OH
OH H OH
CH2OH

• Conversion of anomers – MUTAROTATION

• All three structures are in equilibrium in
aqueous soln’s
Reducing Sugars
• Sugars that are able to undergo oxidation
coupled with a reduction of another substance
Ag(s)
Ag(NH3)2+
O H (Tollens Reagent) O O
C C
H OH Cu2O(s) H OH
HO H [Cu(citrate)2]2-, -OH HO H
H OH (Benedict's Reagent) H OH
H OH Cu2O(s) H OH
CH2OH CH2OH
[Cu(tartrate)2]2-, -OH
glucose (Fehling's Reagent) gluconate
(aldose) (aldonate)
Disaccharides
• The anomeric carbon can react with an ―OH of
an alcohol to give a acetal called glycoside

CH2OH CH2OH
HO O HO O
CH3OH
HO OH HO OCH3
HCl
OH OH
ß-D-glucopyranose methyl ß-D-glucopyranoside
+ a-anomer

• If the ―OH group is part of another

monosaccharide, then the resulting glycoside is
a disaccharide.
Disaccharides
C
HO
2H C
HO
2H
O
H OOH O
O
H OH
O
H OH
OH OH
ß
-
D-g
al
act
opy
r
an
os
e a
-
D-g
l
uco
py
r
an
os
e

C
HO
2H
OOHLACTOSE
C
HOH
2
O
OH - milk sugar
O
H O
O
H O
H - reducing
- β−1,4
O H
O-β-D-galactopyranosyl-(1→4)-α-D-glucopyranose
Disaccharides
CH2OH O CH2OH O
HO HO

HO HO
OH OH
OH OH
a-D-glucopyranose a-D-glucopyranose

CH2OH O
MALTOSE
HO
- sugar used in
HO
OH CH2OH brewing beer
O
O - α−1,4
HO - reducing
OH
OH
O-α-D-glucopyranosyl-(1→4)-α-D-glucopyranose
Disaccharides
CH2OH O CH2OH OH
HO O
HO
HO CH2OH
OH HO
OH
a-D-glucopyranose ß-D-fructofuranose

HO
CH2OH O SUCROSE
- common table
HO
OH sugar
CH2OH O
O
- α―1,β―2
HO
- non-reducing
CH2OH
HO
O-α-D-glucopyranosyl-(1→2)-β-D-fructofuranoside
Exercise
Consider the open chain structure of D-idose
O H
C
H O H
H O H
H O H
H O H
C H 2O H

1. Using Haworth structure, draw the β- and

α−anomer of D-idose.
2. Draw a disaccharide made up of two α−anomers
of D-idose linked through α−1,6 glycosidic bond
Polysaccharides
• Consist of ten to thousands of monosaccharide
units
• Can be:
• homopolymers – only one type of
monosaccharide as repeating unit
• heteropolymers – more than one type of
monosaccharide are linked together
Polysaccharides
Cellulose
• Major component of plant cell wall
C H 2O H
O O C H 2O H
O C H 2O H
H O O O
O C H 2O H
O H H O O
O H H O O
O H H O O
O H

β−1,4
Polysaccharides
Starch
• Major storage form of carbohydrates in plants

CH2OH
O O

HO
OH CH2OH
O Amylose
O
HO
OH CH2OH
O
O
HO
α−1,4 OH CH2OH
O
O
HO O
OH
Polysaccharides
Starch
C H 2O H
O
O
Amylopectin
HO
OH C H 2O H
O
C H 2O H O
O O HO
OH C H 2O H
O
HO
OH C H 2O H
O
O α−1,6
HO
O OH
HO
OH C H 2O H O
O
O
α−1,4 HO
OH CH2
O
O
HO O
OH
Polysaccharides
Glycogen
• Major storage form of carbohydrates in animals
and fungi
• Very similar with amylopectin in structure but
with a higher degree of branching
Polysaccharides
Chitin
• N-containing polysaccharide which is the major
component of exoskeletons of crustaceans
(shrimp, crab, lobsters etc.)

C H 2O H
O O C H 2O H
O C H 2O H
HO O O
O C H 2O H
NH HO O
NH HO O
C O NH O
C O HO
CH3 C O NH
CH3 C O
CH3
CH3
N-acetyl-D-glucosamine
Polysaccharides
Hyaluronic Acid
• Major component of neural, connective and
epithelial tissues that functions as shock
absorber
CH2OH
O O COOH CH2OH
O HO O
HO O
NH HO O O
C O OH NH

CH3 C O
D-gulonic acid CH3
N-acetyl-D-glucosamine
References
CHEM 160 lecture slide of Profs. BP Serrano, KMP Caldo and AC Reyes

Nelson and Cox. Lehninger’s Principles of Biochemistry, 4th ed.

Stryer, Berg and Tymoczko. Biochemistry 4th ed.

© jcksanpascual 2014