Biochemistry (1)

Biochemistry

The branch of science concerned with the chemical and physio-chemical processes and substances which occur within living organisms.

Carbohydrates The most abundant organic molecules in nature.

They have a wide range of functions:

providing a significant fraction of the dietary calories for most organisms.

acting as a storage form of energy in the body.

serving as cell membrane components that mediate some forms of intercellular communication.

also serve as a structural component of many organisms, including the cell walls of bacteria, the exoskeleton of many insects, and the fibrous cellulose of plants.

Classification and Structure of Carbohydrates

The empiric formula for many of the simpler carbohydrates is (CH2O)n or CnH2nOn.

Monosaccharides (simple sugars) can be classified according to thenumber of carbon atoms they contain.

Examples of some monosaccharides commonly found in humans arelisted below.

Carbohydrates with an aldehyde as their most oxidized functional group are called aldoses, whereas those with a keto as their most oxidized functional group are called ketoses.

Mono saccharides can be linked by glycosidic bonds to create larger structures. Monosaccharides can be joined to form disaccharides, oligosaccharides, and polysaccharides.

glycosidic bonds formed by enzymes known as glycosyltransferases.

Disaccharides include:

lactose (galactose + glucose).

sucrose (glucose + fructose).

maltose (glucose + glucose).

Polysaccharides include:

branched glycogen (from animal sources).

starch (plant sources) and unbranched cellulose (plant

sources); each is a polymer of glucose.

Naming glycosidic bonds:

Glycosidic bonds between sugars are named according to:

1- The numbers of the connected carbons.

2- The position of the anomeric hydroxyl group of the sugarinvolved in the bond.

If this anomeric hydroxyl is in the α-configuration, the linkageis an α-bond.

If it is in the β-configuration, the linkage is a β-bond.

For example Lactose, is synthesized by forming a glycosidicbond between carbon 1 of β-galactose and carbon 4 ofglucose. The linkage is, therefore, a β(1→4) glycosidic bond

Isomers and epimers Compounds that have the same chemical formula but have different

structures are called isomers.

For example, fructose, glucose, mannose, and galactose are allisomers of each other, having the same chemical formula, C6H12O6.

Carbohydrate isomers that differ in configuration around only one

specific carbon atom are defined as epimers of each other.

For example, glucose and galactose are C-4epimers—their structuresdiffer only in the position of the –OH group at carbon 4.

Glucose and mannose are C-2 epimers. However, galactose andmannose are NOT epimers—they differ in the position of –OH groups attwo carbons (2 and 4) and are, therefore, defined only as isomers.

Enantiomers

A special type of isomerism is found in the pairs of structures thatare mirror images of each other. These mirror images are calledenantiomers.

Two members of the pair are designated as a D- and an L-sugar. The vast majority of the sugars in humans are D-sugars.

In the D isomeric form, the –OH group on the asymmetriccarbon (a carbon linked to four different atoms or groups)farthest from the carbonyl carbon is on the right, whereasin the L-isomer it is on the left.

Enzymes known as racemases are able to interconvert D-and L-isomers.

Cyclization of monosaccharides

Less than 1% of each of the monosaccharides with five ormore carbons exists in the open-chain (acyclic) form.Rather, they are predominantly found in a ring (cyclic)form, in which the aldehyde (or keto) group has reactedwith an alcohol group on the same sugar, making thecarbonyl carbon (carbon 1 for an aldose or carbon 2 for aketose) asymmetric.

Reducing sugars:

If the hydroxyl group on the anomeric carbon of a cyclized sugaris not linked to another compound by a glycosidic bond, the ringcan open.

The sugar can act as a reducing agent, and is termed a reducingsugar. Such sugars can react with chromogenic agents (forexample, Benedict’s reagent or Fehling’s solution) causing thereagent to be reduced and colored, with the aldehyde group ofthe acyclic sugar becoming oxidized.

Complex carbohydrates Carbohydrates can be attached by glycosidic bonds to non-

carbohydrate structures, including purine and pyrimidinebases (found innucleic acids), aromatic rings (such asthose found in steroids and bilirubin), proteins (found inglycoproteins and proteoglycans), and lipids (found inglycolipids).

N- and O-glycosides:

If the group on the non-carbohydrate molecule to which the sugar is attached is an –NH2 group, the structure is an N-glycoside and the bond is called an N-glycosidic link. If the group is an –OH, the structure is an O-glycoside, and the bond is an O-glycosidic link.

Digestion of dietary carbohydrates

Abnormal degradation of disaccharides

Any defect in a specific disaccharidase activity of the intestinal mucosa

causes the passage of undigested carbohydrate into the large intestine.

As a consequence of the presence of this osmotically active material,

water is drawn from the mucosa into the large intestine, causing

osmotic diarrhea. This is reinforced by the bacterial fermentation of

the remaining carbohydrate to two- and three-carbon compounds

(which are also osmotically active) plus large volumes of CO2 and H2

gas, causing abdominal cramps, diarrhea, and flatulence.

Carbohydrate Metabolism

Glucose is the major form of sugar moiety present in blood and other bodyfluids.

The digestion of food carbohydrates, such as starch, sucrose, and lactoseproduces the monosaccharides glucose, fructose and galactose, which passinto the blood stream.

The study of synthesis (Anabolism) and degradation (Catabolism) ofbiomolecules is biochemically termed as metabolism.

Anabolism + Catabolism = Metabolism

(Synthesis) (Degradation)

Glucose is the most important carbohydrate existing in physiological amounts in the body

and is easily absorbed from the diet.

The monosaccharides galactose and fructose are converted to glucose in the liver.

All the monosaccharides are completely absorbed in the small intestine.

The glucose in the circulating blood and tissue fluids is drawn upon by all the cells of

the body and used for the production of energy.

Normally carbohydrate metabolism supplies more than half of the energy requirements

of the body.

In fact the brain largely depends upon carbohydrate metabolism as a source of energy

and quickly ceases to function properly when the blood glucose level falls much below

normal.

Carbohydrate as a source of energy

The major function of carbohydrate in metabolism is to serve as fuel and getoxidised to provide energy for other metabolic processes.

The metabolic intermediates are used for various biosynthetic reactions. For thispurpose, carbohydrate is utilized by the cells mainly in the form of glucose.

A major part of dietary glucose is converted to glycogen for storage in liver.

Glucose is degraded in the cell by way of a series of phosphorylated intermediatesmainly via two metabolic pathways.

1. Glycolysis

2. Tricarboxylic acid cycle