Carbohydrate

• Carbohydrates are the most abundant biomolecules on Earth.

• Each year, photosynthesis converts more than 100 billion metric
tons of CO2 and H20 into cellulose and other plant products.
• Carbohydrates are polyhydroxy aldehydes and ketones, or
substances that yield such compounds on hydrolysis.
• Many, but not all have the empirical formula (CH2O)n, but some also
contain nitrogen, phosphorus, or sulfur.
• Carbohydrates occur in four main size classes: monosaccharides,
disaccharides, oligosaccharides, and polysaccharides.
• The most abundant monosaccharide in nature is D-glucose, which
is also known as dextrose.
• A common disaccharide, sucrose, consists of the six-carbon sugars
D-glucose and D-fructose.
• Common polysaccharides include cellulose and starches. Both of
these are homopolymers of D-glucose units, but with different
linkages between residues.
• More complex carbohydrate polymers attached to a protein or lipid
moiety (glycoconjugates) are also prevalent in nature. 2
 Carbohydrate
Compounds contain C, H, O with
general formula of Cm(H2O)n

All have C=O and -OH functional groups

Classified based on
Size of base carbon chain
Number of sugar unit
Location of C=O group
Stereochemistry
 Types of Carbohydrates
Classification based on the number of sugar units
in the total chain

Monosachcarides Single sugar unit

Disaccharides Two sugar units
Trisachcarides Three sugar units
Oligosaccharides up to 10/13/ sugar units
Polysaccharides > 13 sugar units

Chaining relies on the glycosidic bonds

• Monosaccharides are colorless, crystalline solids that are very
soluble in water, but insoluble in nonpolar solvents.
• Most have a sweet taste. The backbones of common
monosaccharides are unbranched carbon chains in which all the
carbons are linked by single bonds.
• In this open-chain form, one of the carbon atoms is double-bonded
to an oxygen atom to form a carbonyl group. Each of the other
carbons has a hydroxyl group.
• If the carbonyl group is at an end of the carbon chain (that is, in an
aldehyde group) the monosaccharide is called an aldose. If the
carbonyl group is at any other position (a ketone group) the
monosaccharide is a ketose.
• Monosaccharides with three, four, five, six, and seven carbons in
their backbones are called trioses, tetroses, pentoses, hexoses, and
heptoses. Many of the carbon atoms to which hydroxyl groups are
attached are chiral centers. This gives rise to the many
stereoisomers found in monosaccharides.
5
 D and L Notations
• By convention, the letter L is assigned to the
structure with the —OH on the left
• The letter D is assigned to the structure with —OH
on the right
 D and L Monosaccharides
• Stereochemistry determined by the asymmetric center
farthest from the carbonyl group
• Most monosaccharides found in living organisms are D

D
D L
Aldose
 Ketone Sugars
Ketones are not easy to oxidize except for ketoses
Enediol reaction -- All monosaccharides are reducing sugars

CHO OH OH
H OH OH O
HO H HO H HO H
H OH H OH H OH
H OH H OH H OH
CH2OH CH2OH CH2OH

Aldose cis-enediol Ketose

intermediate
 Ketose

Pure Fruits Sweetly Taste

 Disaccharides
A disaccharide (e.g., maltose) is
formed from two monosaccharides
(two D-glucose molecules for
maltose) when an -OH alcohol
group of the right D-glucose
condenses with the intramolecular
hemiacetal of the left D-glucose.
Water is eliminated, and a glycoside
with a glycosidic bond is formed.
The reversal of this reaction is
hydrolysis by attack of a water
molecule on this bond--a reaction
which is readily catalyzed using
dilute acid.
 COMPLICATION OF CARBOHYDRATE

1. Number of Carbon Atoms

2. The Location of Carbonyl Group
3. The Configuration of Sugar (D or L)
4. The Size of Ring (5, 6 or 7)
5. The Configuration at Position 1 (a or b)
6. The Connectivity between Sugar Units
7. Derivatives (oxidation, reduction, deoxy, various group)
CARBOHYDRATE ISOMERS
Combination of Number of
Individual Units Carbohydrates
Two identical units, 11
A-A dimer
Three identical units, 176
A-A-A trimer
Three different units, 1,056
A-B-C trimer
Five different units, 2,144,640
A-B-C-D-E
pentamer
 Intro. to Polysaccharides
Most carbohydrates found in nature occur
as polysaccharides, polymers of medium
to high molecular weight (Mr >20,000).
Polysaccharides, also called glycans, differ
from each other in the identity of their
recurring monosaccharide units, in the
lengths of their chains, in the types of
bonds linking the monosaccharide units,
and in the degree of branching.
Homopolysaccharides contain only a
single monomeric species, whereas
heteropolysaccharides contain two or
more different kinds.
Unlike proteins, polysaccharides generally
do not have defined molecular weights.
This is because polysaccharides are not
synthesized from a template. Instead,
there is no specific stopping point for the
enzymes involved in their biosynthesis.
 Starches (I)
Starch is a storage homopolysaccharide of D glucose residues that is
found in the cytoplasm of plant cells. Starch (and glycogen) is extensively
hydrated because it has many exposed hydroxyl groups available to
hydrogen-bond with water.
Starches consist of two types of polymers called amylose and amylopectin.
Amylose is a linear polymer of D glucose residues that all are connected
via (14) linkages (as in maltose). The molecular weights of amylose
chains vary from a few thousand to more than a million. Amylopectin is a
branched polymer of D glucose residues that can weigh up to 200 million
Da. The glycosidic linkages between D glucose residues in amylopectin
chains are also (14); the branch point linkages between D glucose units,
however, are (16) linkages. Branch points occur about every 24 to 30
residues.
 Starches (II)
A cluster of amylose and amylopectin molecules, like that believed to be
present in the starch granules in plant cells. Strands of amylopectin
(black) form double-helical structures with each other or with amylose
strands (blue). Amylopectin has (16) branch points (red). Glucose
resides at the nonreducing ends of the outer branches are removed
enzymatically during the mobilization of starch for energy production.
Glycogen has a structure that is similar to amylopectin, but is more highly
branched and more compact.
 Glycogen
Glycogen is the main storage polysaccharide occurring in animal cells.
Its structure is very similar to amylopectin, in that main chain linkages
between D glucose units are (14) and the linkages at branch points are
(16).
Branch points occur more frequently in glycogen (about every 8 to 12
residues) than in amylopectin.
Glycogen is especially abundant in hepatocytes of the liver where it may
constitute as much as 7% of the wet weight of the tissue. Slightly less
glycogen (about 2% by wet weight) is stored in skeletal muscle cells.
Glycogen molecules occur in large granules that can be observed in the
cytoplasm of cells by electron microscopy.
A single glycogen molecule can weigh several million Da. Like amylopectin,
glycogen molecules have many nonreducing ends at the ends of the
branches, but only one reducing end.
The enzymes of glycogen metabolism build up and break down glycogen to
glucose units at the nonreducing ends of the molecule. Simultaneous
reactions at the many nonreducing ends speed up the metabolism of the
polysaccharide.
 Cellulose
Cellulose is a linear homopolysaccharide composed exclusively of D
glucose units held together in (ß14) linkages. A single chain of cellulose
can contain 10-to-15,000 residues. Due to the presence of ß linkages,
cellulose chains fold quite differently than chains of D glucose in the
starches and glycogen (see below).
Cellulose molecules are insoluble in water and form tough fibers. Cellulose
is found in the cell walls of plants, particularly in stalks, stems, trunks, and
all the woody portions of the plant body. Cellulose constitutes much of the
mass of wood, and cotton is almost pure cellulose.
Vertebrate animals lack the hydrolytic enzymes (cellulases) that can
cleave the (ß14) linkages between glucose units in cellulose. These
enzymes are produced by many cellulolytic microorganisms. These
microorganisms, such as Trichonympha, a symbiotic protist that resides in
the termite gut, allow the host to derive energy from the glucose units
stored in cellulose. Similarly, cellulases produced by microorganisms living
in the rumens of cattle, sheep, and goats allow these animals to obtain
energy from cellulose present in soft grasses in the diet.
 Chitin
Chitin is a linear homopolysaccharide composed of N-acetylglucosamine
residues in (ß14) linkage.
The only chemical difference from cellulose is the replacement of the
hydroxyl group at C-2 with an acetylated amino group.
Chitin also forms extended fibers similar to those of cellulose. Like
cellulose, chitin cannot be digested by enzymes found in vertebrates.
Chitin is the principal component of the hard exoskeletons of nearly a
million species of arthropods--insects, lobsters, and crabs, for example--
and is probably the second most abundant polysaccharide in nature.