BCH 4053 Biochemistry IFall 2001Dr.

Michael
Blaber

Lecture 12

Carbohydrates

Carbohydrate Nomenclature

Monosaccharides. "Simple sugars" with the

formula (C � H2O)n. The word carbohydrate
refers to the fact that this class of molecules
consists of hydrates of carbon.
Oligosaccharides. Polymeric molecule of sugar
comprising 2-10 covalently linked
monosaccharide units. Often found conjugated
to other classes of biomolecules including lipids
and proteins.
Polysaccharides. Larger polymers of simple
sugars. On the order of hundreds to thousands
of monosaccharide units as linear or branched
polymers.

Monosaccharides
Most taste sweet.
Contain 3-7 carbon atoms.
Are either an aldose or a ketose
Aldoses contain an aldehyde functional group
Ketoses contain a ketone functional group

The number of carbons, and the functional group,

are specified in the nomenclature for
monosaccharides. The letters "ul" are
sometimes inserted into the name (rather than
the word "keto") to indicate the monosaccharide
is a ketose.

Number of Carbons Aldose K

Functional Fu
(Generic monosaccharide name) Group

3 Ke
Aldotriose
(Triose) T

4 Ke
Aldotetrose
(Tetrose) T

5 Ket
Aldopentose
(Pentose) Pe

6 Aldohexose Ke
 (Hexose) H

Stereochemistry

In addition to the general name of the

monosaccharide, the stereochemistry about each
chiral center is important.

We need a way to specify both the chirality and the

particular carbon in the monosaccharide
molecule for each chiral center
We need a convenient way to represent such
stereochemical features when drawing
monosaccharides
The solution to these problems is the Fischer
projection method of drawing such molecules
Fischer Projection

The carbonyl group of the keto or aldose

functional group is considered to be closest to
the "start" of the carbon chain. The carbon
thus identified as the "first" carbon in the chain
is carbon #1. The remaining carbons are
numbered sequentially.
The "highest numbered" asymmetric carbon (i.e.
furthest from the "start" carbon) determines
whether the monosaccharide is the "D" or "L"
isomer. In Fischer Projections, the "D"
isomer will have the hydroxyl (-OH)
functional group located on the right-hand
side of the chiral C. Note that the D/L
nomenclature has nothing to do with optical
 rotation activity of the structure; this is indicated
by the use of (+) or (-).
The majority of saccharides in nature have the
"D" isomer

Common names are used to identify the chirality of

lower-numbered carbons in the structure.

In the above example of aldotetroses:

Carbon #1 is at the end closest to the aldehyde
carbonyl
Carbon #3 is the highest numbered carbon
that is chiral (carbon 4 is not chiral because
it contains two hydrogens)
The "D" or "L" nomenclature therefore refers to
the chirality of carabon #3. The "D" form
has the OH group on the right-hand side of
carbon #3; the "L" form has the OH group
on the left-hand side.
Carbon #2 is chiral, and the different isomers
of this aldotetrose (at locations other than
the highest chiral carbon) are indicated by
different common names
Here are some examples of Fischer projections for
some ketopentoses:

Carbon #1 is the end closest to the keto group

Carbon #4 is the highest chiral carbon and
determines the "L" or "D" isomer nomenclature
for the saccharide
Carbon #3 is also chiral, and its chirality determines
 the common name
Carbon #2 is not chiral, neither is carbon 1, or
carbon 5. For ketoses, the smallest chain
length that would include a chiral center is
four carbons (a ketotetrose, or tetrulose).

Stereochemistry terms:

If isomers are mirror images, then they are

enantiomers
If isomers contain more than one chiral center and
are not mirror images, then they are
diastereomers
If carbohydrate isomers differ at only a single
chiral center, then they are epimers.
(epimers are a special category of
diastereomers)

Cyclic Structures and Anomeric Forms

Alcohols react readily with aldehydes to form

hemiacetals:

This reaction is promoted in the presence of either

acid or base
One of the subtleties of this reaction involves the
stereochemistry of the aldehyde and keto
carbon - it goes from being achiral to chiral.
Likewise, alcohols react with ketones to produce
hemiketals:
Since aldoses and ketoses contain alcohol groups, in
addition to their aldehyde or ketone groups, they
have the potential to react to form cyclic forms.

"Pyranose" is used to refer to the pyran ring

structure (6-membered ring with 5 carbons and
1 oxygen)
For five membered rings (four carbons and 1
oxygen) the structure is a furanose ring.
Cyclization is reversible
The resulting chirality of the aldehyde carbon (or
keto carbon in ketoses) in the cyclic structure
can be either the α - or β - form. This carbon is
termed the anomeric carbon, and the α - and
β - forms are anomers.
The ring structure representations are termed
"Haworth Projections"
Cyclic structures can also be represented using
Fischer diagrams

Alternative ring structures

Glucose has a variety of alcohol functional groups,

and is able to form alternative hemiacetal ring
structures
The 5C-OH can react with the aldehyde forming
the above pyranose ring
 The 4C-OH can react with the aldehyde forming
a five-membered furanose ring
Ring geometry

The carbon atoms in the ring are sp3 hybrid orbitals,

and tetrahedral geometry
The oxygen in the ring is also sp3, and tetrahedral
Thus, the ring structures cannot be planar (that
would require trigonal planar geometry, or sp2
hybrid orbitals, for the atoms in the ring)
What do the rings actually look like?

There is a "boat" and a "chair" structure. There are

two different orientations of the functional
groups bonded to the ring carbons:
If they point in the general plane of the ring,
they are said to be in the "equatorial"
position
If they point in an orientation perpendicular to
the general plane of the ring, they are side
to be in the "axial" position
Notice that the chair can have two different
conformations. The principle effect of
the alternative conformations is to
change the axial versus equatorial
orientations for the carbon functional
groups
Functional groups in the axial position are somewhat
crowded together, whereas, the same functional
groups in the equatorial position are separated from
each other.

The preferred chair conformation is the one

 that minimizes close contacts between large
functional groups - these will preferentially
occupy the equatorial position

If you look at various cyclic saccharide structures,

those with alternating hydroxyl groups will
minimize steric clashes of these groups when in
the axial configuration
Of all the D-aldohexoses, only β -D-
glucopyranose (β -D-glucose) is able to
adopt a chair conformation with bulky
groups in the axial orientation

Derivatives of Monosaccharides

Sugar acids. Sugars with a free aldehyde can

function as reducing agents by having the
aldehyde group oxidized to a carboxylic acid (as
in any redox reaction, for this to happen
something else must be reduced). Such sugars
are called reducing sugars.
Addition of alkaline copper sulfate will result in
a red precipitate of copper(I)oxide if
reducing sugars (sugars with free aldehydes
are present). This is a diagnostic test for
sugar in the blood of diabetic patients

Sugar alcohols. With an appropriate reducing

agent, the carbonyl group of aldoses and
ketoses can be reduced to an alcohol. Such
reduction prevents the cyclization of the
saccharide (which requires a keto group). The
 nomenclature to indicate sugar alcohols is the
-ol ending

Deoxy sugars. Monosaccharides with one or more

hydroxyl groups replaced by a hydrogen. 2-
deoxy-D-ribose is a key component of DNA
(deoxy-ribo-nucleic acids)
Sugar esters. Phosphate esters are high-energy
bonds that play an essential role in
thermodynamically coupled reactions. ATP
(adenosine triphophate) is a phosphate ester to
a ribose saccharide.

Amino sugars. Some saccharides have an amino (-

NH2) group instead of a hydroxyl group. Amino
sugars are found in bacterial cell walls, and the
exoskeletons of insects and crustaceans.
Acetals, Ketals and Glycosides. Hemiacetals and
hemiketals (found in cylic forms of saccharides)
can react with alcohols (under acidic conditions)
to form acetals and ketals. The alcohol can be
from another saccharide, and form a
glycosidic bond between two saccharides.
This is a condensation reaction (releases H2O)
similar to the formation of peptide bonds.

Oligosaccharides

The basic monomeric units that are used to build up

complex oligosaccharides are essentially limited to:

Hexoses. Glucose, mannose, galactose (all

 aldoses), and fructose (ketose)
Pentoses. Ribose, xylose (both aldoses)

Common disaccharides

Lactose. This disaccharide is a dimer comprised of

a galactose linked to glucose via a β -1-4
glycosidic bond. "Milk sugar" - it is the principle
carbohydrate of milk. Must be broken down into
galactose and glucose by the enzyme lactase.

Lactose

Sucrose. This disaccharide is glucose-α -1,2-

fructose. "Table sugar". No free anomeric
carbon, therefore, not a reducing sugar.

Sucrose

Maltose. This disaccharide is glucose-α -1,4

glucose. "Grain sugar". Has a free anomeric
carbon and is therefore a reducing sugar.
Higher Oligosaccharides

Plants produce various higher oligosaccharides.

Humans may or may not have the enzymes
necessary to break them down into useful
monosaccharides (i.e. to break specific glycosidic
linkages). However, bacteria in our intestine may
have such enzymes. Therefore, if you eat some of
such complex carbohydrates, you are simply
nourishing the bacteria in your intestine. They will
thank you by producing more of their own waste
products - including certain gases.

Polysaccharides

The majority of carbohydrate material in nature

occurs in the form of polysaccharides (also known as
glycans). Other molecules that contain
polysaccharide structures are also referred to as
polysaccharides.

Homopolysaccharide. A polysaccharide whose

monosaccharide units are identical.
Heteropolysaccharide. A polysaccharide made up
of different monosaccharides
The most common constituent of polysaccharides is
D-Glucose
Homopolysaccharides composed of glucose are
called glucans; those composed of mannose are
called mannans; etc.

Glycosidic linkages involve only one anomeric

carbon (keto or aldehyde) per monosaccharide.
However, there are several potential hydroxyl
acceptor groups on a given monosaccharide. Thus,
polysaccharides can be branched as well as
linear.

The characterization of polysaccharides includes

their length, the type of monosaccharide units,
the linkages and branched nature
Starch is a glucan that has two polysaccharide
forms: one is a linear molecule with α -1-4
linkages called amylose. The other is a
 branched form of amylose, where the branches
have α -1-6 linkages, called amylopectin.
Polysaccharide Functions

Polysaccharides have historically been described as

having functions related to storage, structure and
protection. But, the full range of functions of
polysaccharides have not yet been fully determined.

Storage.

The most common storage polysaccharide in

plants is starch. One large polymer has a much
lower osmotic pressure than a bunch of
monomeric molecules. Glucose is therefore
stored as a polymer. Before use, the starch
(amylose, and amylopectin) must be broken
down into individual D-glucose units by starch
phosphorylase:

The major form of storage polysaccharide in

animals is glycogen (found in the liver and
skeletal muscle). It is highly branched with α -1-
6 branches. It is hydrolyzed by α - and β -
amylases to yield glucose and maltose (glucose-
α -1-4-glucose disaccharide). It can also be
hydrolyzed by glycogen phosphorylase (in liver
and muscle) to release glucose-1-phosphate.
Yeast and bacteria make dextran as a storage
polysaccharide. It is composed of α -1-6 linkages
of D-glucose, with branched chains (1-2, 1-3 or
1-4 linkages between glucose units). Important
component of dental plaque (from bacteria).
Structure.

Cellulose. The most abundant natural polymer

found in the world. Found in the cell wall of
almost all plants, it provides physical structure
and strength. Primary difference between
cellulose and starch is that cellulose glycosidic
linkages are β -1-4 linkages. The α -1-4
linkages in starch give the polysaccharide a
helical twist. The β -1-4 linkages in cellulose give
the polysaccharide an extended ribbon
conformation. Separate chains of cellulose can
hydrogen bond and this provides a network of
strong intermolecular interactions giving
cellulose its strength.
Cellulose is thus resistant to hydrolysis. A
special enzyme (cellulase) is needed to
hydrolyze the glycosidic bond. Some
bacteria make cellulase and can therefore
"eat" cellulose
Chitin. Similar to cellulose. Made in cell walls of
fungi and exoskeletons of crustaceans, insects
and spiders. Main difference is the hydroxyl at
the 2 position is replaced by -NHCOCH3.
Monomeric unit is therefore N-acetyl-D-
glucosamine.
Alginate. Made by marine brown algae. Binds
metal ions, and is necessary to form organized
polymeric structures that manifest as physical
"gels".
Agarose. Made by marine red algae. Forms edible
gel, not unlike gelatin.
 Glycosaminoglycans. Polysaccharide with amino
sugars and sulfate containing groups. Results in
negatively charged polymers. Natural
anticoagulant (inhibits blood clotting).
Chondroitins and keratin sulfates fall into this
group of polysaccharide and are in important
component of skin and tendons.

© 2001 Dr. Michael Blaber