CARBOHYDRATE S

Carbohydrates are the most abundant biomolecule in nature.

Via photosynthesis, over 100 billion metric tons of CO2 and H2O are converted into cellulose and other plant products. The term carbohydrate refers primarily to carbon-containing compounds that contain hydroxyl, keto, or aldehydic functionalities.

Carbohydrates can range in sizes, from simple monosaccharides (sugars) to oligosaccharides and polysaccharides.

Nomenclature of Monosaccharides

In each structure, the majority of the carbons appear to be hydrated, This is where the name carbohydrate derives. These compounds are monosaccharides (simple sugars). Notice that there are two distinct types of monosaccharides, ketoses and aldoses. A ketose has a ketone functionality associated with it, while an aldose has an aldehyde functionality associated with it. The number of carbons is important in general nomenclature (triose = 3, pentose = 5, hexose =6)

Chirality in Monosaccharides
Most simple monosaccharides have at least one chiral center. As in the case of amino acids, sugars are given D or L designations based on their similarity with D or L glyceraldehyde (shown on left). Since some sugars contain many chiral centers, it is necessary to designate one chiral center that will act as the reference.

Sugars are frequently written as Fischer projections.

Stereochemistry

In Fischer projections: if the hydroxyl group on the reference carbon is on the right side, the sugar has a D configuration. if the hydroxyl group on the reference carbon is on the left side, the sugar has an L configuration. Most sugars as they occur in nature are in the D configuration. Some have naturally occuring L configurations, such as arabinose. The numbering of carbons in sugars begins at the end of the chain that is closer to the carbonyl functionality. How many stereoisomers are possible for any given sugar? In principle, a molecule with n chiral centers will have 2n stereoisomers.

D-Aldoses

D-Ketoses

E P I M E R S

Epimers are two sugars that differ only in the configuration around one carbon atom of their structures. D-Mannose differs from D-glucose only in its configuration around carbon 2. D-Galactose differs from D-glucose only in its configuration around carbon 4. D-Galactose and D-Mannose are not epimers.

Structures with which to be Familiar Glucose

Galactose Mannose Ribose Arabinose Xylose Fructose Glucose is the standard six-carbon sugar Galactose is an epimer of glucose Mannose is an epimer of glucose Ribose is the standard five-carbon sugar Arabinose is an epimer of ribose Xylose is an epimer of ribose Fructose is the ketose form of glucose

Hemiacetals and Hemiketals

When aldehydes are attacked by alcohols, hemiacetals are generated. When ketones are attacked by alcohols, hemiketals are generated.

Cyclization of Monosaccharides
The hydroxyl group can be on the same side (cis) of the ring as the CH2OH moiety (beta configuration), or it can be on the opposite side (trans) of the ring as the CH2OH moiety (alpha configuration).
Six-membered rings containing an oxygen heteroatom are called pyranoses. Notice the formal names for each of the two possible configurations.

Two Common Ring Structures

As shown in the previous slide, upon cyclization, two stereochemical outcomes are possible. These two stereochemical outcomes are called anomers. In principle, with a 6-carbon sugar (aldohexose), you could have a number of different ring sizes. If the hydroxyl group at C-2 attacked the aldehyde, you would build a 3-membered ring. If the hydroxyl group at C-3 attacked the aldehyde, you would build a 4-membered ring. These configurations are energetically unfavorable. Only 5-and 6-membered ring structures with respect to sugars occur to any significant extent in nature. They are energetically favorable. The fivemembered ring is called a furanose.

Two Common Ring Structures

Glucose exists primarily in the pyranose ring form, while fructose can exist to a substantial extent in both pyranose and furanose forms. When written in ring form, the anomeric carbon is usually drawn on the right side. Notice the two anomers of fructofuranose and the relevant nomenclature associated with each. The two forms of glucose or fructose rotate plane-polarized light in different directions. beta-D glucose rotates plane polarized light clockwise (dextrarotatory). This is why its name is dextrose. The two anomers of sugars can readily interconvert. This process is called mutarotation.

Pyranose Conformations

Pyranose ring structures are not planar, although frequently they are drawn like that on paper to denote simple structure. There are two well known conformations of pyranoses: the chair conformation and the boat conformation. The chair conformation is the most energetically favorable for sugars that have biological relevance.

Notice that there are two possible chair conformations.

Hexose Derivatives in Nature

The Glycosidic Bond

Two sugar molecules can be joined in tandem, when a hydroxyl (alcohol) group of one sugar displaces the hydroxyl group on the other sugars anomeric carbon.

The bond formed is called a glycosidic bond. In forming the glycosidic bond, an acetal is generated on one sugar (at carbon 1) in place of the hemiacetal.
Similarly to peptide bond formation, one mole of water is formed per glycosidic bond generated. The disaccharide formed upon condensation of two glucose molecules is called Maltose.

MALTOSE: glucose + glucose

-DISACCHARIDE RELEASED

DURING THE HYDROLYSIS OF STARCH (a polymer of glucose residues)

LACTOSE: galactose + glucose

-A MAJOR CARBOHYDRATE IN MILK

SUCROSE: fructose + glucose

-TABLE SUGAR; MOST ABUNDANT DISSACHARIDE FOUND IN NATURE AND IS SYNTHESIZED ONLY IN PLANTS

P O L Y S A C C H A R I D E S

In nature, carbohydrates are most often found as high molecular weight polymers of monosaccharides. These polysaccharides (sometimes called glycans) can be homopolysaccharides (if all of the repeating units are the same), or heteropolysaccharides (if the repeating units are not the same). Polysaccharides serve structural purposes (cellulose and chitin), or serve as fuel reserves (glycogen and starch).

Starch and Glycogen

Starch is the storage polysaccharide of plants, whereas glycogen is the storage polysaccharide of animals. Starch is made up of two types of glycose polymers: amylose and amylopectin. Amylose has long unbranched chains of glucose residues. Amylopectin. however, has 24 to 30 branched glucose residues.

For adjacent rigid chair structures, the most stable conformation of the sugars is one in which the polysaccharide chain is curved rather than linear. This causes amylose and amylopectin, and glycogen to form helical structures. It is these compact structures that produce the dense granules of stored starch or glycogen that can be seen in many cells.

Cellulose is the most common form of

polysaccharides found in nature. It is found in the cell walls of plants (stalks, stems, trunks, and all the woody portions of the plant body).
It is fibrous, tough, and water-insoluble.

However, it is composed of the same repeating units as starch and glycogen, which are not fibrous and tough.
What is it about the nature of the glucose linkages in cellulose that gives it distinctly different physical properties from those of starch and glycogen? The glucose linkages in cellulose are 1 4. The most stable conformation of 1 4 -linked glucose residues is such that each chair structure is oriented in trans with respect to its neighbor. The result is a linear (not helical) chain of greater tensile strength. Most animals cannot use cellulose as a fuel source because they lack the enzyme to hydrolyze 1 4 linkages.

END OF DISCUSSION