Biological Molecules

Carbon skeletons

Carbon has four unpaired electrons which can participate in four covalent bonds.

The geometric arrangement of these bonds is tetrahedral.

Such a bond arrangement is ideal for the formation of chains - carbon is the ultimate LEGOŽ block.

All biological molecules are made of carbon chains.

Polymorphism of carbon chains

Carbon chains can take many forms depending on:

(i) which of the four possible carbon bonds are utilized for carbon-to-carbon linkages (geometry);

(ii) how many electron pairs are shared (bond multiplicity);

(iii) presence of functional groups and

(iv) functional group arrangement (isomerism).

Chain geometry

"Straight" chain

butane

We often abbreviate the above representation by dropping the symbols. It is implicit that the joint of two segments contains CH2, the joint of 3 segments has a CH group and each chain ends with a CH3.

butane

Branched chain

isobutane

Ring

cyclohexane

Multiple bonds

The presence of multiple bonds introduces further polymorphism. Two carbon atoms can share two or three electron pairs.

benzene

Functional groups

The carbon chains, in addition to basic units of carbon and hydrogen, contain various specialized groups. These substituents give chemical (acid, base) or physical character (polar) to an otherwise nonpolar carbon chain.

Amino: -NH2

Amino groups are proton acceptors making carbon chains weak bases and increasing their polarity (and thus solubility in water).

Amino groups are very ubiquitous, present in aminoacids, proteins, nucleic acids, sugars and lipids.

Carboxyl: -COOH

Carboxylic groups are weak acids, their significance and presence matches that of amino groups.

Phosphate: -O-P(OH)3

Phosphate groups are weak acids. They often are joined together via phospho-ester bonds (P-O-P) which stores a lot of energy. Phosphate derivatives are often energy intermediates e.g. ATP or phosphorylated enzymes.

Alcohol: >CH-OH

Alcohol groups are weakly polar and are present in sugars, aminoacids, lipids.

Aldehyde: -CH=O; Keto: >C=O

Aldehyde and keto groups are present in sugars, they give molecules more polar character.

Isomerism

The presence of functional groups introduces a further complexity: isomerism. The constituent atoms are the same, but they are connected together differently.

Structural isomerism

Functional groups are different although the constituent atoms are the same: e.g. C2H6O:
ethanol: CH3CH2OH (pleasantly drinkable - only for those over 21)
ether: CH3OCH3 (pleasantly flammable and explosive);

Geometric stereoisomers

Even when functional groups are identical they can be arranged differently.

In maleic acid, the alcohol groups are cis with respect to the double bond, in fumeric acid the alcohol groups are trans.

Optical stereoisomers

The tetrahedral bond arrangement of the carbon bonds defines carbon as a chiral center, when bonded to 4 different atoms. The same four substituents can be bonded to carbon in two different ways, each of them being a mirror image of the other.

Different spatial arrangement of functional groups will result in different structures and different affinities for binding other molecules.

One stereoisomer might bind to an enzyme with high affinity, the other might not bind at all, it is like trying to thread a left-handed screw into a right-handed nut.

P. Fajer Carbon Chemistry 4/4 Chem-5 12/30/95 11:31 PM 4