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FREE RADICALS

R. Mareeswaran (09BC011) II ² M.Sc., Biochemistry

FREE RADICALS

A free radical is a atom or group of atoms possessing one or more unpaired electrons in their outer shell

PROPERTIES
Don't survive in their original state for very long and quickly react with their surroundings. Trying to gain stability by capturing the needed electron When the "attacked" molecule loses its electron, it becomes a free radical itself, beginning a chain reaction Once the process is started, it can cascade, finally resulting in the disruption of a living cell

FRS IN HUMAN BODY
Superoxide anion (O2*) Hydroxyl radical (OH), Nitric oxide (NO*), Peroxynitrite (ONOO*), Hypochlorous acid (HOCl*), Hydrogen peroxide (H2O2)

SUPEROXIDE
Formed when oxygen reduced by the transfer of a single electron to its outer shells . Major source of superoxide in-vivo is electron leakage from ETC of the mitochondria.

Play a central role as other reactive intermediates are formed from it. Main significance - being a main source for the generation of hydrogen peroxide and as a reductant of transition metals, which are precursors to the formation of the lethal hydroxyl radical.

HYDROXYL RADICAL
An extremely reactive oxidising radical that will react to most biomolecules. Around 1933, Fritz Haber and Joseph Weiss first proposed that hydroxyl free radicals ( OH) were produced when superoxide and hydrogen peroxide react together .

O2* + H2O2 *------- O2 + OH* + OH*

This formula was coined the Haber-Weiss reaction.

About

100 years ago, Henry Fenton had observed that the reducing agent, ferrous iron (Fe2+), together with hydrogen peroxide could oxidize some organic compounds. H2O2 + Fe2+---------OH*+ OH* + Fe3+

This

is known as iron catalysed Haber weiss reactn or Fenton reaction.

HYDROGEN PEROXIDE
Not

a free radical but falls in the category of reactive oxygen species. Oxidising agent that is not particularly reactive. Main source of hydroxyl radicals in the presence of transition metal ions. Involved in the production of HOCl by neutrophils. .

Two

superoxide molecules can react together to form hydrogen peroxide and oxygen: 2O2*+ 2H-------------------- H2O2 + O2

The

above reaction is called a dismutation reaction as the radical reactants produce non radical products.

SINGLET OXYGEN
Non radical (does not have an unpaired electron) reactive oxygen species often associated with oxygen free radicals that has strong oxidising activity . An electronically excited and mutagenic form of O2.

  

Generated by Input of energy, (radiation) Can also be generated enzymatically by the action of peroxidases or lipoxygenases Reaction of hydrogen peroxide with hypochlorite or peroxynitrite or during the respiratory burst of phagocyte

NITRIC OXIDE
Common

gaseous free radical. Vascular endothelium, neutrophils and macrophages produces nitric oxide from arginine using the enzyme Nitric oxide synthetase. It can be stimulated by cytokines, tumour necrosis factor, or interleukins . Inhibition - reduce microbicidal and tumouricidal activities of macrophages

PEROXYNITRITE
It is produced by the reaction of nitric oxide with superoxide. The result is a radical-radical reaction in which peroxynitrite (ONOO-) is formed:

O2* + NO* = ONOO-

HYPOCHLOROUS ACID

Activated polymorphonuclear cells produce HOCl as a major bactericidal agent. It is generated by the action of myeloperoxidase on chloride ions in the presence of H2O2. H2O2 + Cl ---- HOCl* + OH*

This reaction occurs in the neutrophils phagocytic vacuole after fusion with the myeloperoxidasecontaining lysosomal vesicles. Hypochlorous acid can cross cell membranes and, in the presence of transitional metal ions, generate hydroxyl radicals

POSITIVE EFFECTS OF FR
Immune system: neutrophils and macrophages use ROS to destroy engulfed microorganisms Can serve as second messengers modify oxidation-reduction (redox) states. Involved in some enzyme activation. Involved in drug detoxification.

NEGATIVE EFFECTS
lipid peroxidation protein modification DNA modification