CARBOHYDRATE

CARBOHYDRATE
Carbohydrates are essential to all living organisms and are the most abundant class of biological molecules. The metabolic breakdown of monosaccharides provides most of the energy used to power biological processes. Chemically, they are polyhydroxyl aldehydes or ketones. Contain three elements - C, H, O, many according to the formula (CH2O)n; where n 3. Greek saccharon means sugar Carbohydrates function: Energy sources (glucose/glycogen) Structural elements:
cell wall (plants, bacteria) connective tissues adhesion between cells

Monosaccharides
Monosaccharide is another term for a simple sugar, which is not linked to any other sugars. Common monosaccharides include: glucose, mannose, fructose, ribose, and galactose Monosaccharides can be classified as trioses, tetroses, pentoses, hexoses, or heptoses, depending upon the number of carbon atoms.

Some Examples of Monosaccharides

Glucose It is commonly found in fruits. It is known as dextrose, a name that derives from the fact that the predominant natural form of the sugar is dextrorotatory. It is made by the hydrolysis of starch. It is only 75% as sweet as sucrose.
Fructose It is found in fruits and honey. It also referred to as levulose because it has an optical rotation that is strongly levorotary (- 920) It exists in two forms, pyranose (free state) or furanose (combined form) . It is the sweetest sugar.

Galactose
It is more commonly found in the disaccharide, lactose or milk sugar. It does not occur in nature in the uncombined state. It is formed by the hydrolysis of lactose. It is needed by the human body for the synthesis of lactose (in the mammary glands) is obtained by the conversion of Dglucose into D-galactose. It is an important constituent of the glycolipids that occur in the brain and the myelin sheath of nerve cells.

 Monosaccharides can be classified as as aldoses or ketoses, depending upon they have an aldehyde or ketone group. Example:

Glyceraldehyde and dihydroxyacetone have the same atomic composition, but differ only in the position of the hydrogens and double bonds.

Aldose-ketose intercoversion via an enediol intermediate

When the structures of molecules are related in those ways, the molecules are called tautomers.

Fischer Projection of Monosaccharide

The structure of monosaccharide can be drawn by the Fischer projection formula. The carbon chain was composed vertical and the aldehyde carbon at the top. If the position of hydroxyl group of the highest numbered stereogenic center was at:

Right D Left L

D- and L-isomerism of glyceraldehyde and glucose

L-sugars are much less abundant in nature.

OH

The OH group is on the left

The OH group is on the right

Haworth Projection of Monosaccharide

Haworth projection is a conventional planar representation of a cyclized monosaccharide molecule. It is useful to show whether the OH groups on the ring are cis or trans to each other. The OH groups that are represented on the right in a Fischer projection are down in a Haworth projection, and vice versa.

Epimers
Epimers are diastereomers that contain more than one chiral center but differ from each other in the absolute configuration at only one chiral center.

 For a carbon with 'm' chiral carbons, the number of possible stereoisomers is 2m. Example: An aldohexose (D-glucose) has 4 chiral carbons, thus it has 16 stereoisomers.

How many are the enantiomers of D-glucose? How many are the diastereoisomers of D-glucose?

 Naturally occuring ketoses have the ketone group in the 2position. A ketose has one fewer chiral carbon than does an aldose with the same number of carbon atom. Therefore, a ketose has only half as many stereoisomers as an aldose with the same number of carbon atoms.
Example: A ketohexose (D-fructose) has 3 chiral carbons, thus it has 8 stereoisomers.

How many are the enantiomers of D-fructose? How many are the diastereoisomers of D-fructose?

Monosaccharide Ring Structures

Alcohol groups can react with the aldehydes or ketones to form hemiacetals and hemiketals.

A new chiral center is born!

Formation of the two cyclic forms of D-glucose

Sugars with 5 C mostly exist in their cyclized form

(intramolecular hemiacetal formation)

Monosaccharide can form the cyclic form as: Furanose form => five-membered ring Pyranose form => six-membered ring

The Chair and Boat Conformation of Monosaccharide

Both conformations (chair and boat) exist, though the chair form is thermodynamically more stable .

Mutarotation
Mutarotation is a process whereby the configuration of an anomeric carbon converts from to and vice-versa (the gradual change of optical rotation), which continues until equilibrium is established.

Monosaccharide as reducing agents

The reducing end: the sugar with the free anomeric carbon that can be oxidized. Oxidation occurs only with the linear form. Maltose and lactose are reducing sugars, while sucrose is not.

Bond between two anomeric carbons

 Monosaccharides act as reducing agents, because the aldehyde group that is present can be oxidized by oxidizing agents such as Fe3+ or Cu2+ ions to form a carboxylic acid group, or in the presence of a base, a carboxylate ion group.

Disaccharides
Disaccharides are compounds consisting of two monosaccharide subunits linked together by an glycosidic linkage. Disaccharides are taken apart by hydrolysis and put together by condensation Common disaccharides include: Sucrose => glucose + fructose Maltose => glucose + glucose Lactose => glucose + galactose Cellobiose => glucose + glucose

Glycosidic Bonds Disaccharides arise through the formation of O-glycosidic bonds: condensation of anomeric carbon hydroxyl group with an alcohol

Glu(a14)Glu

Some Examples of Disaccharides

Sucrose

It is known as beet sugar, cane sugar, tablet sugar, or simply as sugar. It is incapable of mutarotation and said to be a nonreducing sugar. This is because of the presence of the 1,2-glycosidic linkage makes it impossible for it to exist in the - or - configuration or in the openchain form.

Maltose

It occurs in animals as the principal sugar formed by the enzymic (ptyalin) hydrolysis of starch. It is a reducing sugar, and it exhibits mutarotation. This is because of the presence of the 1,4-glycosidic linkage makes it possible for it to exist in the - or - configuration or in the open-chain form.

Cellobiose

It is a stereoisomers of maltose. It is also composed of two glucose units, but in this case the two sugar moieties are joined by -1,4glycosidic linkage. It is a reducing sugar, and it undergoes mutarotation. This is because of the presence of the 1,4-glycosidic linkage makes it possible for it to exist in the - or - configuration or in the open-chain form.

Lactose

It known as milk sugar because it occurs in the milk of humans, cows, and other mammals. It is a reducing sugar, and it exhibits mutarotation.

Polysaccharides
The polysaccharides are the most abundant of the carbohydrates found in nature. They serve as reserve food substances and as structural components of plant cell. They are high molar mass (25,000-15,000,000) polymers of monosaccharides joined together by glycosidic linkage.

 There are two types of polysaccharides: Homopolysaccharides: when all the monosaccharide units of a polysaccharide are the same. Storage: starch (storage in plants) and glycogen (storage in animals). Structural elements: cellulose (plants cell wall) and chitin (animal exoskeleton). Heteropolysaccharides: when the repeating monosaccharide units of the polysaccharide are different. ex: hyaluronic acid, keratan sulfate and agarase

Some Examples of Homopolysaccharides

Starch
It is a polymer of glucose used for energy storage in plants such as potatoes, rice, beans, and corn. Starch is a mixture of two polymers, amylose (10-30%) and amylopectin (70-90%).

Amylose and amylopectin, the polysaccharides of starch

Amylose is a straight-chain polysaccharide composed entirely of D-glucose units join by an -1,4-glycosidic linkage.

amylose

Amylopectin is a branchedchain polysaccharide composed of glucose units join by -1,4glycosidic linkage with -1,6glycosidic linkage.
amylopectin

occurs every 24 to 30 residues

Glycogen It is specially abundant in the liver, 4-8% (per weight of tissue), and in muscle cell, 0.5-1.0% It is quite similar to amylopectin, but it is more highly branched and its branches are shorter (8-12 glucose units in length).

A comparison of the amylose, amylopectin, and glycogen

Chitin It is the major structural component of the shells of crustaceans (e.g., lobsters, crabs, and shrimps) and the exoskeletons of insects. It is structurally similar to cellulose, but in that it has an Nacetylamino group instead of an OH group at the C-2 position.

Cellulose It is the major structural polysaccharide in woody and fibrous plants and is the most abundant single polymer in the biosphere. Many microorganisms and herbivorous animals can digest cellulose because their digestive tracts contain enzymes (cellulase) that can hydrolyze (14) linkage.

Cellulose breakdown by wood fungi

A comparison between starch and cellulose

starch

cellulose

Some Examples of Heteropolysaccharides

Hyaluronic Acid It is a type of polysaccharide called a glycosaminoglycan. Also known as hyaluronan or hyaluronate. It occurs naturally in the human body and is central to regulating cell growth and renewal. In fact, it is found extensively in connective, epithelial, and neural cells.

Keratan sulfate It is any of several sulfated glycosaminoglycans that have been found especially in the cornea, cartilage, and bone. It is also synthesized in the central nervous system where it participates both in development and in the glial scar formation following an injury.

Agarase It is an enzyme found in agarolytic bacteria and is the first enzyme in the agar catabolic pathway Agarases are classified as either -agarases or -agarases based upon whether they degrade or linkages in agarose, breaking them into oligosaccharide.

Derivatives of Monosaccharides
Monosaccharides can be chemically altered in several ways, in which a hydroxyl group in the parent compound is replaced with another substituent (NH-(C=O)-CH3, NH2, (C=O)H COO-, O-H O-PO32- ) or a carbon atom is oxidized to a carboxyl group to provide new classes of compounds.

Derivatives of monosaccharides include: Alditols, ex: erythritol, sorbitol, and D-mannitol Amino sugars, ex: -D-glucosamine, N-acetyl--Dglucosamine, muramic acid, and N-acetylmuramic acid

Some Examples of Derivatives of Monosaccharides

Alditols
They are made by reducing the carbonyl group of a sugar to a hydroxyl. They are used in chewable tablets as sweetening agents

to mask the unpleasant taste

of vitamins and minerals and to improve texture. These natural sweeteners are extracted and purified from plant sources, particularly from fruits.

Amino sugars
It is made by reducing a hydroxyl of sugar with an amine group.

Fiber
Fiber is often considered a carbohydrate. Found in food derived from plants. Includes polysaccharides such as cellulose, hemicellulose, pectins, gums and mucilages. Also includes non-polysaccharides such as lignin, cutins and tannins Its value to our digestive system is its ability to clean us out. It leaves water, vitamins and minerals in our body and scrubs our digestive tract on the way through. It is not a source of energy because human digestive enzymes cannot break down fibers.