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lipid peroxidation

Saturday 4 February 2006


Definition: Peroxidase catalyzed oxidation of lipids using hydrogen peroxide as an electron acceptor. (MeSH)

Lipid peroxidation refers to the oxidative degradation of lipids. It is the process whereby free radicals "steal" electrons from the lipids in cell membranes, resulting in cell damage. This process proceeds by a free radical chain reaction mechanism.

Lipid peroxidation most often affects polyunsaturated fatty acids, because they contain multiple double bonds in between which lie methylene -CH2- groups that possess especially reactive hydrogens.

As with any radical reaction the reaction consists of three major steps: initiation, propagation and termination.

- Initiation is the step whereby a fatty acid radical is produced. The initiators in living cells are most notably reactive oxygen species (ROS), such as OH·, which combines with a hydrogen atom to make water and a fatty acid radical.

- The fatty acid radical is not a very stable molecule, so it reacts readily with molecular oxygen, thereby creating a peroxyl-fatty acid radical. This too is an unstable species that reacts with another free fatty acid producing a different fatty acid radical and a hydrogen peroxide or a cyclic peroxide if it had reacted with itself. This cycle continues as the new fatty acid radical reacts in the same way.

- When a radical reacts it always produces another radical, which is why the process is called a "chain reaction mechanism." The radical reaction stops when two radicals react and produce a non-radical species. This happens only when the concentration of radical species is high enough for there to be a high probability of two radicals actually colliding. Living organisms have evolved different molecules that speed up termination by catching free radicals and therefore protect the cell membrane. One important such antioxidant is alpha-tocopherol, also known as vitamin E. Other anti-oxidants made within the body include the enzymes superoxide dismutase, catalase, and peroxidase.

If not terminated fast enough, there will be damage to the cell membrane, which consists mainly of lipids. Phototherapy may case hemolysis by rupturing red blood cell cell membranes in this way.

In addition, end products of lipid peroxidation may be mutagenic and carcinogenic. For instance, the end product malondialdehyde reacts with deoxyadenosine and deoxyguanosine in DNA, forming DNA adducts to them, primarily M1G.

The onset of lipid peroxidation within cellular membranes is associated with changes in their physicochemical properties and with the impairment of protein functions located in the membrane environment.

Antioxidant effects of melatonin

Melatonin has effects on biological membranes, changes in fluidity, fatty acid composition and lipid-protein modifications during the lipid peroxidation process of photoreceptor membranes and modulation of gene expression by the hormone and its preventive effects on adriamycin-induced lipid peroxidation in rat liver.

Simple model systems have often been employed to measure the activity of antioxidants. Although such studies are important and essential to understand the mechanisms and kinetics of antioxidant action, it should be noted that the results of simple in vitro model experiments cannot be directly extrapolated to in vivo systems.

For example, the antioxidant capacity of melatonin, one of the important physiological lipophilic antioxidants, in solution of pure triglycerides enriched in omega-3 polyunsaturated fatty acids is considerably different from that in subcellular membranes.

See also

- cellular injury

  • membrane injury


- Catalá A.The ability of melatonin to counteract lipid peroxidation in biological membranes.Curr Mol Med. 2007 Nov;7(7):638-49. PMID: 18045142