Carbohydrates

Definitions and Classification

. The word carbohydrate arose because molecular formulas of

. We can now define carbohydrates more precisely in terms of their

. Carbohydrates are polyhydroxyaldehydes, polyhydroxyketones,

. The chemistry of carbohydrates is mainly the combined chemistry

these compounds can be expressed as hydrates of carbon.

organic structures.

or substances that give such compounds on hydrolysis.

of two functional groups: the hydroxyl group and the carbonyl

group.

Definitions and Classification

Monosaccharides (or simple sugars, as they are sometimes called) are

carbohydrates that cannot be hydrolyzed to simpler compounds.

Polysaccharides contain many monesaccharide units-sometimes

hundreds or even thousands. Usually, but not always, the units are

identical.

Two of the most important polysaccharides, starch and

cellulose, contain linked units of the same monosaccharide, glucose.

Oligosaccharides (from the Greek oligos, few) contain at least two and

generally no more than a few linked monosaccharide units. They may

be called disaccharides, trisaccharides, and so on, depending on the

number of units, which may be the same or different.

Monosaccharides

Monosaccharides are classified according to the number of carbon

atoms present (triose, tetrose, pentose, hexose, and so on) and

according to whether the carbonyl group is present as an aldehyde

(aldose) or as a ketone (ketose).

. There are only two trioses: glyceraldehyde and dihydroxyacetone.

. Each has two hydroxyl groups, attached to different carbon atoms, and

one carbonyl group.

Monosaccharides

. Glyceraldehyde is the simplest aldose, and dihydroxyacetone is the

simplest ketose

. Each is related to glycerol in that each has a carbonyl group in place of

one of the hydroxyl groups.

Other aldoses or ketoses can be derived from glyceraldehyde

or

dihydroxyacetone by adding carbon atoms, each with a

hydroxyl group.

In aldoses, the chain is numbered from the aldehyde carbon.

. In most ketoses, the carbonyl group is located at C-2.

Chirality in Monosaccharides;

Fischer Projection Formulas and D,L-Sugars

You will notice that glyceraldehyde, the simplest aldose, has one

stereogenic carbon atom (C-2) and hence can exist in two enantiomeric

forms.
Chirality in Monosaccharides;

Fischer Projection Formulas and D,L-Sugars

Emil Fischer used a small capital D to represent the

configuration of (+)-glyceraldehyde, with the hydroxyl group

on the right; its enantiomer, with the hydroxyl group on the

left, was designated L-(-)-glyceraldehyde.

The most oxidized carbon (CHO) was placed at the top.

Chirality in Monosaccharides;

Fischer Projection Formulas and D,L-Sugars

.Fischer extended his system to other monosaccharides in the

following way

. If the stereogenic carbon farthest from the aldehyde or ketone

group had the same configuration as D-glyceraldehyde (hydroxyl

on the right), the compound was called a D-sugar.

If the configuration at the remote carbon had the same

configuration as L-glyceraldehyde (hydroxyl on the left), the

compound was an L-sugar

Pyranose and Furanose Structures

. The six-membered cyclic form of most monosaccharides is the

preferred structure.
. These structures are called pyranose forms after the six-

membered oxygen heterocycle pyran.

Pyranose and Furanose Structures

Pyranoses are formed by reaction of the hydroxyl group at C-5,

with the carbonyl group. With some sugars, however, the hydroxyl

group at C-4 reacts instead.

In these cases, the cyclic hemiacetal that is formed

has a five-

membered ring.

This type of cyclic monosaccharide is called a

furanose, after the parent five-membered oxygen
heterocycle furan

Disaccharides

The most common oligosaccharides are disaccharides.

In a disaccharide, two monosaccharides are linked by a

glycosidic bond between the anomeric carbon of one

monosaccharide unit and a hydroxyl group on the other unit.

Disaccharides

Maltose

KilOMaltose is the disaccharide obtained by the partial hydrolysis of starch.

Further hydrolysis cf maltose gives only D-glucose.

Maltose must,
 therefore, consist of two linked glucose units

It turns out that the anomeric carbon of the left unit is linked to the C-

4 hydroxyl group of the unit at the right as an acetal (glycoside)

Disaccharides

Cellobiose

Cellobiose is the disaccharide obtained by the

partial hydrolysis of

cellulose.

Further hydrolysis of cellobiose gives only D-glucose. Cellobiose must

therefore be an isomer of maltose.

. In fact, cellobiose differs from maltose only in having the b

configuration at C-1 of the left glucose unit. Otherwise, all other

structural features are identical, including a link from C-1 of the left

unit to the hydroxyl group at C-4 in the right unit.

Disaccharides

Lactose

. Lactose is the major sugar in human and cow's milk (4% to 8%

lactose).

. Hydrolysis of lactose gives equimolar amounts of D-galactose and D-glucose.

. The anomeric carbon of the galactose unit has the b configuration at C-1 and is linked to the hydroxyl
groupat C-4 of the glucose unit.
Disaccharides

Lactose

Some human infants are born with a disease called

galactosemia.

They lack the enzyme that isomerizes galactose to glucose and

therefore cannot digest milk. If milk is excluded from suclh

infants' diets, the disease symptoms caused by accumulation of

galactose can be avoided.

Disaccharides

Sucrose

. The most importarit commercial disaccharide is sucrose, ordinary

table sugar.

More than 130 million tons are produced annually worldwide.

Sucrose occurs in all photosyntheticplants, where it functions as an

energy source.

. It is obtained commercially from sugar cane and sugar

beets, in

which it constitutes 14% to 20% of the plant juices.

Sucrose

Sucrose is very water soluble (2 grams per mililiter at

room temperature)

because it is polar due to the presence of eight hydroxyl

groups on its

surface.
Hydrolysis of sucrose gives equimolar amounts of D-glucose and the

ketose D-fructose

Sucrose differs from the other disaccharides in that the anomeric

carbons of both units are involved in the glycosidic link, that is, C-1 of the

glucose unit is linked via oxygen to C-2 of the fructose unit.

An additional difference is that the fructose unit is in the furanose form.

Polysaccharides

. Polysaccharides contain many linked monosaccharides and vary

in chain length and molecular weight.

: Most polysaccharides give a single monosaccharide on

complete hydrolysis. The monosaccharide units may be linked

linearly, or the chains may be branched.

Polysaccharides

Starch and Glycogen

. Starch is the energy-storing carbohydrate of plants. It is a major

component of cereals, potatoes, corn, and rice.

It is the form in which glucose is stored by plants for later use.

Starch is made up of glucose units joined mainly by 1,4-a-glycosidic

bonds, although the chains may have a number of branches

attached through 1,6-a-glycosidicbonds.

Partial hydrolysis of starch gives maltose, and complete hydrolysis

gives only D-glucose.

 Starch and Glycogen

Starch can be separated

by various techniques
into two fractions:

amylose and amylopectin

. In amylose, which constitutes about 20% of starch, the glucose units (50

to 300) are in a continuous chain, with 1,4 linkages.

Amylopectin is highly branched. Although each molecule may contain

300 to 5000 glucose units, chains with consecutive 1,4 links average only

25 to 30 units in length. These chains are connected at branch points by

1,6 linkages.

Because of this highly branched structure, starch granules swell and

eventually form colloidal systems in water.

Polysaccharides
Starch and Glycogen

. Glycogen is the energy-storing carbohydrate of animals. Like starch, it is made of 1,4-and 1,6-linked
glucose units. Glycogen

has a higher molecular weight than starch (perhaps 100,000 glucose

units), and its structure is even more branched than that of

amylopectin, with a branch every 8 to 12 glucose units.

. Glycogen is produced from glucose that is absorbed from the

intestines into the blood; transported to the liver, muscles, and

elsewhere; and then polymerized enzymatically.

Polysaccharides

Starch and Glycogen

. Glycogen helps maintain the glucose balance in the body by

removing and storing excess glucose from ingested food and later

supplying it to the blood when various cells need it for energy.

Polysaccharides

Cellulose

Cellulose is an unbranched polymer of glucose joined by 1,4-b-glycosidic

bonds

. X-ray examination of cellulose shows that it consists of linear chains of

cellobiose units in which the ring oxygens alternate in "forward" and

"backward" positions.

.
 Polysaccharides

Cellulose

. These linear molecules, containing an average of 5000 glucose units,

aggregate to give fibrils bound together by hydrogen bonds between

hydroxyls on adjacent chains.

. Cellulose fibers having considerable physical strength are built up

from these fibrils, wound spirally in opposite directions around a

central axis.

. Wood, cotton, hemp, linen, straw, and corncobs are mainly

cellulose

Polysaccharides

Cellulose

. Although humans and other animals can digest starch and glycogen,

they cannot digest cellulose. This is a truly striking example of the

specificity of biochemical reactions.

. The only chemical difference between starch and cellulose is the

stereochemistry of the glucosidic link-more precisely, the

stereochemistry at C-1 of each glucose unit.

The human digestive system contains enzymes that can catalyze the

hydrolysis of a-glucosidic bonds, but it lacks the enzymes necessary

to hydrolyze b-glucosidicbonds.

Polysaccharides
Cellulose

. Many bacteria, however, do contain b-glucosidases and can

hydrolyze cellulose. Termites, for example, have such bacteria in

their intestines and thrive on wood (cellulose) as their main

food. Ruminants (cud-chewing animals such as cows) can digest

grasses and other forms of cellulose because they harbor the

necessary microorganisms in their rumen.

Polysaccharides

Other Polysaccharides

. Chitin is a nitrogen-containing polysaccharide that forms the

shells of crustaceans and the exoskeletons of insects.

. It is similar to cellulose, except that the hydroxyl group at C-2 of

each glucose unit is replaced by an acetylamino group.

Polysaccharides

Other Polysaccharides

. Chitin is a nitrogen-containing polysaccharide that forms the

shells of crustaceans and the exoskeletons of insects.

. It is similar to cellulose, except that the hydroxyl group at C-2 of

each glucose unit is replaced by an acetylamino group,

Polysaccharides

Other Polysaccharides

Numerous other polysaccharides are known, such as gum arabic

and other gums and mucilages, chondroitin sulfate (found in

cartilage), the blood anticoagulant heparin

(found in the liver

and heart), and the dextrans (used as blood

plasma

substitutes).
Sugar Phosphates

Phosphate esters of monosaccharides are found in all living

cellscells,
where they
are
intermediates
in
carbohydrate

metabolism.
Some common sugar phosphates are the

following:

Sugar Phosphates

Phosphates of the five-carbon sugar ribose and its 2-deoxy

analog are important in nucleic acid structures (DNA and RNA)

and in other key biological compounds.

Deoxy Sugars

. In deoxy sugars, one or more of the hydroxyl groups is replaced

by a hydrogen atom.

. The most important example is 2-deoxyribose, the sugar

component of DNA.

It lacks the hydroxyl group at C-2 and occurs in DNA in the

 furanose form.

Amino Sugars

. In amino sugars,
one of the sugar
hydroxyl groups is
replaced by an

amino group.

. Usually the-NH2
group is also
acetylated.

D-Glucosamine is one of the more abundant amino sugars.