Some enzymes do not need any additional components to show full activity.

However, others require non-protein molecules called cofactors to be bound for activity

CoFactors
Apoenzyme + cofactor = holoenzyme
chemical teeth or helper molecules of enzymes.
Can either be metal ions or small organic molecules also known as Coenzymes.

Essential ions
Non-protein chemical compound.
Often classified as inorganic substances that are required for, or increase the rate of, catalysis.

Apoenzyme = inactive enzyme, without the cofactor = Without its respective coenzyme = The enzyme (protein) component of the holozyme

Holoenzyme = complete enzyme with cofactor = With the coenzyme

Precursors of coenzymes: B VITAMINS

thiamine (B1) riboflavin (B2) nicotinamide

(cofactors can be divided into two broad groups)

Classification:

Organic

Inorganic

 Such as flavin or heme often vitamins or are made from vitamins. Further divided into: > Coenzymes = loosely-bond cofactors > Prosthetic groups = tightly-bond cofactors
= non protein coenzyme component

Such as metal ions Mg, Cu, Mn or iron-sulfur clusters

Metal ion CoFactors

Usually transition metals that coordinate with enzyme-substrate complex. Usually TRACE elements : Cu2+, Fe2+, Zn2+etc.. Calcium, Chromium and Iodine are the only exceptions. Inorganic Metal-activated or Metalloenzymes activators

 Also known as the common COFACTORS

Iron (Fe3+), manganese (Mn2+), cobalt (Co2+), copper (Cu2+), zinc (Zn2+), selenium (Se2+), and molybdenum (Mo5+) The function of some enzymes cannot be carried out if a metal ion is not available

METAL IONS
Cupric

ENZYMES containing
Cytochromeoxidase

Ferrous or Feric

Magnesium Manganese

CatalaseCytochrome (via Heme) Nitrogenase Hydrogenase Glucose 6-phosphate Hexokinase Arginase Nitrate reductase
Urease Glutathioneperoxidase Alcohol dehydeogenase Carbonicanhydrase

Molybdenum
Nickel Selenium Zinc

Examples of some enzymes that require metal ions as cofactors:

cofactor
Zn++ Zn++

protein
carbonic anhydrase alcohol dehydrogenase

Fe+++ or Fe++ Fe+++ or Fe++ Cu++ or Cu+ K+ and Mg++

cytochromes, hemoglobin ferredoxin cytochrome oxidase pyruvate phosphokinase

Iron-Sulfur transfer
iron-sulfur clusters are complexes of iron and sulfur atoms held within proteins by cysteinyl residues. They play both structural and functional roles, including electron transfer, redox sensing, and as structural modules.

CoEnzymes
Highly organic molecules They must be regenerated : In order to complete the catalytic cycle, the
coenzyme must return to its original state.

Can either be Prosthetic or loosely bound Co substrates. Water-soluble vitamins are precursors of coenzymes. Mostly derived from vitamins.

VITAMIN source Thiamin (vitamin B1)

COENZYME

REACTION MEDIATED 2-carbon groups, alpha cleavage, decarboxylation in krebs cycle Electrons ( oxidation-reduction) Amino/carboxyl groups

Thiamine pyrophosphate

Niacin (vitamin B3)

NAD+ and NADP+ (nicotinamide) Pyridoxal phosphate

Pyridoxine (vitamin B6)

Lipoic acid

lipoamide

Acyl group transfer/electrons

Acyl groups

Vitamin B12

Methylcobalamin

VITAMINS
Vitamin B12

COENZYME
Cobalamine

REACTION MEDIATED Hydrogen/ alkyl groups CO2carboxylase reactions.

Vitamin H

Biotin

Vitamin B5 (pantothenic acid)

Folic acid

Coenzyme A

Acetyl group/ other acyl groups

Methyl, formyl, methylene and formino groups. Carbonyl groups/ oxidation-reduction of electrons.

Tetrahydrofolic acid

Vitamin K

Menaquinone

VITAMINS

COENZYMES

REACTION MEDIATED Oxidation/reduction of electrons. Oxidation of substrates

Vitamin C

Ascorbic acid

Vitamin B2 (RIBOFLAVIN)

Flavin mononucleotide (FMN)

Vitamin B2 (RIBOFLAVIN)
Vitamin B2 (RIBOFLAVIN) Vitamin A1 Vitamin A2

Flavin adenine dinucleotide (FAD)

CoEnzyme F420

Oxidation of substrates
Oxidation/reduction

retinol, dehydroretinol

Oxidation/reduction. Transfer of light energy.

Ion
Cupric

Examples of enzymes containing this ion

Cytochrome oxidase Catalase Cytochrome (via Heme) Nitrogenase Hydrogenase Glucose 6-phosphatase Hexokinase Arginase Nitrate reductase

Ferrous or Ferric

Magnesium Manganese Molybdenum

Nickel
Selenium Zinc

Urease
Glutathione peroxidase Alcohol dehydrogenase Carbonic anhydrase DNA polymerase