1

Carbohydrates
Structure and Biological Function

Monosaccharides
Carbohydrates in Cyclic Structures
Reactions of Glucose and Other
Monosaccharides
Polysaccharides
Glycoproteins
2
Carbohydrates
Compounds containing C, H and O

General formula : C
x
(H
2
O)
y

All have C=O and -OH functional groups.

Classified based on
Size of base carbon chain
Number of sugar units
Location of C=O
Stereochemistry
3
Types of carbohydrates
Classifications based on number of sugar
units in total chain.
Monosaccharides - single sugar unit
Disaccharides - two sugar units
Oligosaccharides - 2 to 10 sugar units
Polysaccharides - more than 10 units
Chaining relies on bridging of oxygen
atoms
glycoside bonds
4
Monosaccharides
Based on location of C=O
H
|
C=O
|
H-C-OH
|
H-C-OH
|
H-C-OH
|
CH
2
OH
CH
2
OH
|
C=O
|
HO-C-H
|
H-C-OH
|
H-C-OH
|
CH
2
OH
Aldose Ketose
- aldehyde C=O - ketone C=O
5
Monosaccharide classifications
Number of carbon atoms in the chain
H
|
C=O
|
H-C-OH
|
H-C-OH
|
H-C-OH
|
CH
2
OH
H
|
C=O
|
H-C-OH
|
H-C-OH
|
H-C-OH
|
H-C-OH
|
CH
2
OH
H
|
C=O
|
H-C-OH
|
H-C-OH
|
CH
2
OH
H
|
C=O
|
H-C-OH
|
CH
2
OH
triose tetrose pentose hexose

Can be either aldose or ketose sugar.
6
Examples
H
|
C=O
|
H-C-OH
|
CH
2
OH
CH
2
OH
|
C=O
|
HO-C-H
|
H-C-OH
|
H-C-OH
|
CH
2
OH
D-glyceraldehyde D-fructose
triose hexose
aldose ketose
aldotriose sugar ketohexose sugar
7
Examples
H
|
C=O
|
H-C-OH
|
H-C-OH
|
H-C-OH
|
CH
2
OH
H
|
C=O
|
H-C-OH
|
H-C-OH
|
HO-C-H
|
HO-C-H
|
CH
2
OH
D-ribose L-mannose
pentose, aldose hexose, aldose
aldopentose sugar aldohexose sugar
8
Stereoisomers
Stereochemistry
Study of the spatial arrangement of molecules.

Stereoisomers have
the same order and types of bonds.
different spatial arrangements.
different properties.

Many biologically important chemicals, like
sugars, exist as stereoisomers. Your body can
tell the difference.
9
Enantiomers
Pairs of stereoisomers
Designated by D- or L- at the start of the name.
They are mirror images that cant be
overlapped.
If you dont believe it,
give it a try!
10
Enantiomers
11
L- and D- glyceraldehyde
CHO
HO
H
C
CH OH
2
CH OH
2
H
CHO
HO
CHO
H
C
CH OH
2
OH
CH OH
2
H
CHO
OH
12
Enantiomers
Chiral center.
Asymmetric carbon - 4 different things
are attached to it.
Cl
|
I - C - F
|
Br
You must have at least one asymmetric
carbon to have stereoisomers.
Chiral center
13
Examples
Is the red carbon chiral?
H
Cl
C=O
C-OH
H
H
3
C-
H
C-OH
CH
2
CH
3
H
3
C-
H
H
|
C=O
|
H-C-OH
|
CH
2
OH
C=C
Cl
Br
I
F
H
2
N-C-C-C-SH
H H H
H Cl Cl
14
Physical properties
Optical activity
ability to rotate plane polarized light.

dextrorotatory - rotate to right
- use + symbol
- usually D isomers

levorotatory - rotate to left
- use - symbol
- usually L isomers
15
Plane polarized light
Light is passed through a polarized filter.
A solution of an optical isomer will rotate the
light one direction.
16
Stereochemistry
Properly drawing enantiomers in 3-D is hard.
Use Fischer Projections
Specific type of formula that designates
the orientation of groups.
H
|
C=O
|
H-C-OH
|
H-C-OH
|
CH
2
OH
H
|
C=O
|
H-C-OH
|
CH
2
OH
17
With this system, a tetrahedral carbon atom is
represented by two crossed lines.





A horizontal bond to an asymmetric carbon
designates bonds in the front plane of the page.
Vertical bonds are behind the plane of the page.
Fischer projections
H
|
C=O
|
H-C-OH
|
H-C-OH
|
CH
2
OH
H

O

H OH

H OH

CH
2
OH
18
Some important monosaccharides
D-glyceraldehyde Simplest sugar
D-glucose Most important in diet
D-fructose Sweetest of all sugars
D-galactose Part of milk sugar
D-ribose Used in RNA


note that each is a D- enantiomer
19
D-glyceraldehyde
Three carbon sugar
Aldose sugar
Triose sugar

aldotriose




H
|
C=O
|
H-C-OH
|
CH
2
OH
20
D-glucose
Glucose is an aldohexose sugar.

Common names include
dextrose, grape sugar, blood
sugar.

Most important sugar in our diet.

Most abundant organic
compound found in nature.

Level in blood can be as high as
0.1%
C
C
C
C
C
CH
2
OH
OH
OH
H
OH H
HO
H
H
O
H
21
D-fructose


Another common sugar.

It is a ketohexose.

Sweetest of all sugars.


CH
2
OH
|
C=O
|
HO-C-H
|
H-C-OH
|
H-C-OH
|
CH
2
OH
22
Carbohydrates in cyclic structures
If optical isomers werent enough, sugars also
form rings. For many sugars, its the most
common form.

hemiacetal - forms from alcohol and aldehyde

hemiketal - forms from alcohol and ketone
R OR
\ |
C=O + ROH R - C - OH
/ |
R R
23
Intramolecular cyclization
Cyclization.
Remember - chains can bend and rotate.
C
C
C
CH
2
OH
C
C
OH
O
H
C
C
C
CH
2
OH
C
C
O
OH
24
Intramolecular cyclization
The -OH group that forms can be above or
below the ring resulting in two forms -
anomers

and are used to identify the two forms.
- OH group is down compared to CH
2
OH
(trans).
- OH group is up compared to CH
2
OH
(cis).
25
Intramolecular cyclization
The and forms are in equilibrium so one
form can convert to the other -
mutarotation.
Haworth projections can be used to help
see and orientations.
O
O
26
Cyclization of D-glucose
-D - glucose
- D - glucose
H
OH
O
H
OH
H
OH
H
OH
CH
2
OH
H
C
C
C
C
C
CH
2
OH
OH
OH
H
OH H
HO
H
H
O
H
O
H
OH
OH
H
H
H
OH
CH
2
OH
H
OH
27
Fischer vs. Haworth projections
H
OH
O
H
OH
H
OH
H
OH
CH
2
OH
H
-D-glucose
C
C
C
C
C
OH
H
OH H
HO
H
HO-CH
2
H OH
H
O
28
Cyclization of D-fructose
This can also happen
to ketose sugars.
CH
2
OH
O
OH
CH
2
OH
H
OH
H
H OH
OH
CH
2
OH
O
CH
2
OH
OH
H
H
H OH
CH
2
OH
C
C
C
C
CH
2
OH
O
H
OH
OH
H
H
HO


29
D-galactose
Not found in many biological systems
Common part of lactose - disaccharide
O
OH
H
H
OH
H
OH H
OH
CH
2
OH
H
C
C
C
C
C
CH
2
OH
OH
H
H
OH H
HO
HO
H
O
H
O
OH
H
OH
H
H
H
OH
CH
2
OH
H
OH
30
D-glucose vs. D-galactose
C
C
C
C
C
CH
2
OH
OH
OH
H
OH H
HO
H
H
O
H
O
C
C
C
C
C
CH
2
OH
OH
H
H
OH H
HO
HO
H
H
D-glucose D-galactose
Can you find a difference? Your body can!
You cant digest galactose - it must be
converted to glucose first.
31
D-ribose
An important sugar used
in genetic material.

This sugar is not used as
an energy source but is a part
of the backbone of RNA.

When the C-2 OH is removed,
the sugar becomes
deoxyribose which is used
in the backbone of DNA.
H
|
C=O
|
H-C-OH
|
H-C-OH
|
H-C-OH
|
CH
2
OH
32
Reactions of glucose
and other monosaccharides
Oxidation-Reduction. Required for their
complete metabolic breakdown.

Esterification. Production of phosphate
esters.

Amino derivatives. Used to produce
structural components and glycoprotein.

Glycoside formation. Linkage of
monosaccharides to form polysaccharides.
33
Aldehyde sugars (reducing sugars) are readily
oxidized and will react with Benedicts reagent.






This provides a good test for presence of glucose in
urine - forms a red precipitate.

Other tests - Tollens or Fehlings solutions.
Oxidation-Reduction.
H
|
C=O
| + 2 Cu
2+
+ 5 OH
-

H-C-OH
|
CH
2
OH
O
-

|
C=O
| + 2 Cu
2
O + 3H
2
O
H-C-OH
|
CH
2
OH
34
Benedicts reagent
B e n e d i c t ' s
R e a g e n t
0 . 5 % 2 %
g l u c o s e
35
Ketones are not easy to oxidize except ketoses.
Enediol reaction.






So all monosaccharides are reducing sugars.
Ketone sugars
C
C
C
C
C
CH
2
OH
OH
OH
H
OH H
HO
H
H
O
H
C
C
C
C
C
CH
2
OH
OH
OH
H
OH
HO
H
H
C
C
C
C
CH
2
OH
CH
2
OH
OH
OH
H
O H
HO
H
H
OH H
36
Esterification
Esters are formed by reaction of hydroxyl
groups (alcohols) with acids.





The hydroxyl groups of carbohydrates react
similarly to alcohols.
R OH
C R'
O
HO
R O C
O
R' + H
2
O
+
37
Esterification
The most important biological esters of
carbohydrates are phosphate esters.



Example. Phosphoryl group from ATP forms an
ester with D-glucose, catalyzed by kinases.

D-glucose + ATP D-glucose-6-phosphate + ADP
kinase
R OH
P OH
O
OH
+ H
2
O
+
HO
P OH
O
O - R
HO
38
Amino derivatives
The replacement of a hydroxyl group on a
carbohydrate results in an amino sugar.
H
O
OH
OH
H
H
OH H
OH
CH
2
OH
H
H
O
OH
OH
H
H
NH
2
H
OH
CH
2
OH
H
-D-glucose -D-2-aminoglucose
(glucosamine)
39
Amino derivatives
Uses for amino sugars.
Structural components of bacterial cell
walls.
As a component of chitin, a polymer found
in the exoskeleton of insects and
crustaceans.
A major structural unit of chondroitin
sulfate - a component of cartilage.
Component of glycoprotein and glycolipids.
40
Glycoside formation
or -OH group of cyclic monosaccharide
can form link with another one (or more).

glycosidic bond

sugar -O- sugar

oxygen bridge
O
H
OH
OH
H
H
H
OH
CH
2
OH
H
O
H
OH
H
OH
H
OH H
OH
CH
2
OH
H
OH
O
H
OH
H
H
H
OH
CH
2
OH
H
O
H
OH
H
H
OH H
OH
CH
2
OH
H
OH
o
+ H
2
O
41
Glycosidic bonds
O
O
Type is based on the position of the C-1 OH

glycosidic bond
- linkage between a C-1 OH and a C-4 OH

glycosidic bond
- linkage between a C-1 OH and a C-4 OH

bonds bonds
O
O
C-4 end can be either up or down depending
on the orientation of the monosaccharide.
42
Glycosidic bonds
O
O
O
O
bonds bonds
43
Glycosidic bonds
General format used to describe bond.

OH type carbon# of carbon# of
( or ) first sugar second sugar

As we work through the next few examples
this will become clear.

For disaccharides - the sugar is either or
based on form of the
remaining C-1 OH.
( )
44
-Maltose
Malt sugar. Not common in nature except in
germinating grains.
-D-glucose -D-glucose
O
H
OH
H
H
H
OH
CH
2
OH
H
OH
O
H
OH
H
H
H
OH
CH
2
OH
H
OH
O
-D-glucose and -D-glucose, (1 4) linkage.
45
-Maltose
It is referred to as -maltose because the
unreacted C-1 on -D-glucose is in the
position.
O
H
OH
H
H
H
OH
CH
2
OH
H
OH
O
H
OH
H
H
H
OH
CH
2
OH
H
OH
O
46
-Maltose
Uses for -maltose
Ingredient in infant formulas.
Production of beer.
Flavoring - fresh baked aroma.

It is hydrolyzed the in body by:

maltose + H
2
O 2 glucose
maltase
47
Cellobiose
Like maltose, it is composed of two molecules of
D-glucose - but with a (1 4) linkage.
H
O
OH
H
OH H
OH
CH
2
OH
H
H
O
H
O
H
OH H
OH
CH
2
OH
H
H
OH
48
Cellobiose
O
H
OH
H
H
H
OH
CH
2
OH
H
OH
O
H
OH
H
H
H
OH
CH
2
OH
H
OH
O
H
O
OH
H
OH H
OH
CH
2
OH
H
H
O
H
O
H
OH H
OH
CH
2
OH
H
H
OH
The difference in
the linkage results
in cellobiose
being unusable

We lack an enzyme
that can hydrolyze
cellobiose.
cellobiose
(1 4)
maltose, (1 4)
49
Lactose
Milk sugar - dimer of -D-galactose and
either the or - D-glucose.

-Lactose
O
OH
H
H
H
H
OH
CH
2
OH
H
OH
O
H
OH
H
H
H
OH
CH
2
OH
H
OH
O
-D-galactose -D-glucose
(1 4) linkage, disaccharide.
50
Lactose
We cant directly use galactose. It must be
converted to a form of glucose.

Galactosemia - absence of needed enzymes
needed for conversion.

Build up of galactose or a metabolite like
dulcitol (galactitol) causes toxic effects.

Can lead to retardation, cataracts, death.
51
Lactose
Lactase
Enzyme required to hydrolyze lactose.

Lactose intolerance
Lack or insufficient amount of the
enzyme.

If lactase enters lower
GI, it can cause gas
and cramps.
52
Sucrose
Table sugar - most
common sugar in all
plants.
Sugar cane and beet,
are up to 20% by
mass sucrose.
Disaccharide of
-glucose and
-fructose.
(1 2) linkage
CH
2
OH
O
CH
2
OH
H
OH
H
H
OH
H
O
OH
H
H
OH H
OH
CH
2
OH
H
O
53
Sucrose
glucose
fructose
54
How sweet it is!
Sweetness relative
Sugar to sucrose
lactose 0.16
galactose 0.32
maltose 0.33
sucrose 1.00
fructose 1.73
aspartame 180
saccharin 450
55
Polysaccharides
Carbohydrate polymers
Storage Polysaccharides
Energy storage - starch and glycogen
Structural Polysaccharides
Used to provide protective walls or
lubricative coating to cells - cellulose
and mucopolysaccharides.
Structural Peptidoglycans
Bacterial cell walls
56
Starch
Energy storage used by plants

Long repeating chain of -D-glucose

Chains up to 4000 units

Amylose straight chain
major form of starch
Amylopectin branched structure

57
Amylose starch
Straight chain that forms coils (1 4)
linkage. Most common type of starch.
O
H
H
H
OH H
OH
CH
2
OH
H
O
H
H
H
OH H
OH
CH
2
OH
H
O
O
O
H
H
H
OH H
OH
CH
2
OH
H
O
H
H
H
OH H
OH
CH
2
OH
H
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
58
Amylose starch
Example showing coiled structure
- 12 glucose units
- hydrogens and side chains are omitted.
59
Amylopectin starch
Branched structure due to crosslinks.
(1 6) linkage
at crosslink
OH H OH H
OH H
O
H
H
H
OH
CH
2
OH
H
O
H
H
H OH
CH
2
OH
H
O
O
O
H
H
H
OH
CH
2
OH
H
O
H
H
H
OH H
OH
CH
2
OH
H
O
O
O
H
H
H
OH H
OH
CH
2
OH
H
O
H
H
H
OH H
OH
CH
2
OH
H
O
O
O
H
H
H
OH H
OH
CH
2
OH
H
O
H
H
H
OH H
OH
CH
2
H
O
O
60
c
Glycogen
Energy storage of animals.
Stored in liver and muscles as granules.
Similar to amylopectin.
(1 6) linkage
at crosslink
O
O
O
O
O
O
O
O
O
O
O
O
O
O
c
61
Cellulose
Most abundant polysaccharide.
(1 4) glycosidic linkages.
Result in long fibers - for plant structure.
O
H
H
H
OH H
OH
CH
2
OH
H
O
H
H
H
OH H
OH
CH
2
OH
H
O
O
O
H
H
H
OH H
OH
CH
2
OH
H
O
H
H
H
OH H
OH
CH
2
OH
H
O
O
O
H
H
H
OH H
OH
CH
2
OH
H
O
62
H
O
O
H
H
OH H
COO
-
HO
H
O
OH
O
H
H
NH
CH
2
OH
H
C O
CH
3
H
O
O
H
H
OH H
COO
-
HO
H
O
OH
H
H
NH
CH
2
OH
H
C O
CH
3
H
O
O
H
H
OH H
COO
-
HO
H
O
OH
O
H
H
NH
CH
2
OH
H
C O
CH
3
O
Mucopolysaccharides
These materials provide a thin, viscous, jelly-like
coating to cells.
The most abundant form is
hyaluronic acid.




Alternating units of
N-acetylglucosamine and
D-glucuronic acid.
(1 3)
(1 4)
63
Structural peptidoglycans
Bacterial cell walls are composed primarily of an
unbranched polymer of alternating units of N-
acetylglucosamine and N-acetylmuramic acid.
















Peptide crosslinks between the polymer
strands provide extra strength
- varies based on bacterium.
H
O
O
H
H
NH H
OH
CH
2
OH
H
C
CH
3
O
H
O
O
H
H
NH H
OR
CH
2
OH
H
C
CH
3
O
O
CH
3
CH
O L-Ala
D-Isoglu
L-Lys
D-Ala
(Gly)
5
(Gly)
5
R =
crosslink for
Staphylococcus
aureus
64
Glycoproteins
Proteins that carry covalently bound
carbohydrate units.

They have many biological functions.
immunological protection
cell-cell recognition
blood clotting
host-pathogen interaction
65
Glycoprotein structure
Carbohydrates only account for 1-30% of
the total weight of a glycoprotein.

The most common monosaccharides are
glucose mannose
galactose fucose
sialic acid
N-acetylgalactosamine
N-acetylglucosamine
66
Glycoprotein structure
Linking sugars to proteins.
O-glycosidic bonds using
hydroxyl groups of
serine and threonine


N-glycosidic bonds using
side chain amide
nitrogen of asparagine
residue
C
C
C
H
O
CH
3
C
H
2
C
O
H
N
O
O
H
H
H
NHCOCH
3
H
OH
CH
2
OH
H
H
O
O
H
H
NHCOCH
3
H
OH
CH
2
OH
H
p
o
l
y
p
e
p
t
i
d
e

c
h
a
i
n

threonine
asparagine