Autocatalysis

A single chemical reaction is said to have undergone autocatalysis, or be autocatalytic, if the reaction product is itself the catalyst for that reaction.

A "set" of chemical reactions can be said to be "collectively autocatalytic" if a number of those reactions produce, as reaction products, catalysts for enough of the other reactions that the entire set of chemical reactions is self sustaining given an input of energy and food molecules (see autocatalytic set).

Rate law in autocatalytic reactions

The rate law for the second order autocatalytic reaction $A\; +\; B\; ightarrow\; ;2B$ is $v\; =\; k\; [A]\; [B]$.

The concentrations of A and B vary in time according to $[A]\; =frac\{\; [A]\; \_0+\; [B]\; \_0\}\{1+frac\{\; [B]\; \_0\}\{\; [A]\; \_0\}e^\{(\; [A]\; \_0+\; [B]\; \_0)kt$ and $[B]\; =frac\{\; [A]\; \_0+\; [B]\; \_0\}\{1+frac\{\; [A]\; \_0\}\{\; [B]\; \_0\}e^\{-(\; [A]\; \_0+\; [B]\; \_0)kt$.

The graph for these equations is a sigmoid curve, which is typical for autocatalytic reactions: these chemical reactions proceed slowly at the start because there is little catalyst present, the rate of reaction increases progressively as the reaction proceeds as the amount of catalyst increases and then it again slows down as the reactant concentration decreases. If the concentration of a reactant or product in an experiment follows a sigmoid curve, the reaction is likely to be autocatalytic.

Abiogenesis hypothesis

British ethologist Richard Dawkins wrote about autocatalysis as a potential explanation for abiogenesis in his 2004 book "The Ancestor's Tale". He cites experiments performed by Julius Rebek and his colleagues at the Scripps Research Institute in California in which they combined amino adenosine and pentafluorophenyl ester with the autocatalyst amino adenosine triacid ester (AATE). One system from the experiment contained variants of AATE which catalysed the synthesis of themselves. This experiment demonstrated the possibility that autocatalysts could exhibit competition within a population of entities with heredity, which could be interpreted as a rudimentary form of natural selection.

Examples of autocatalytic reactions

*Tin pest
* [http://jchemed.chem.wisc.edu/JCESoft/CCA/CCA3/MAIN/AUTOCAT/PAGE1.HTM Reaction of Permanganate with Oxalic Acid]
*The mechanism of the above reaction [cite journal | title = Revising the Mechanism of the Permanganate/Oxalate Reaction | author = Kovacs KA, Grof P, Burai L, Riedel M | journal = J. Phys. Chem. A | doi = 10.1021/jp047061u | year = 2004 | volume = 108 | pages = 11026]
*Vinegar syndrome
*Binding of oxygen by hemoglobin
*The spontaneous degradation of aspirin into salicylic acid and acetic acid, causing very old aspirin in sealed containers to smell mildly of vinegar.

Involvement in life processes

Two researchers, Robert Ulanowicz [Ecology, the Ascendant Prespective”, Robert Ulanowicz, Columbia Univ. Press 1997] and Stuart Kauffman. [Investigations, Stuart Kauffman, Oxford University Press] have suggested that autocatalytic reactions played a central role in the evolution of life, and continue to constitute a basic element in life architecture. See also Relational order theories

References

ee also

Autocatalytic reactions and order creation

External links

*http://www.eeng.dcu.ie/~alife/bmcm9901/html-multi/
*http://arxiv.org/pdf/adap-org/9809003