Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 677 - 690 (1989)
Update date:2022-08-30
Topics:
Johnson, G. R. Alastair
Nazhat, Najdat B.
Saadalla-Nazhat, Rajiha A.
Reactions of the hydroxyl radical (OH) in amino acid (glycine and α-alanine)-copper(II) aqueous systems have been investigated by measurement of the γ-radiation yields of the products: ammonia, formaldehyde and glyoxylic acid (from glycine), acetaldehyde and pyruvic acid (from alanine) and CuI.It is concluded that OH radical reacts with the amino acid, whether free or coordinated with CuII, to give a radical that is oxidised by CuII, forming ligand decomposition products and CuI.Under conditions where the complex CuII (amino acid)2 is the main OH radical scavenger, the reaction results in ligand decomposition for only ca. 65percent of the OH radicals.The results are interpreted in terms of a mechanism that assumes that OH radical reacts with both the attached amino acid and at the metal centre.The latter reaction gives a CuIII species (possible OH radical bonded to CuII).The fate of the CuIII species depends on the prevailing CuI concentration.With an excess of CuI, CuIII is reduced to CuII by CuI, without ligand decomposition: the kinetics of the decay of CuIII, observed by pulse radiolysis, is consistent with this reaction, and gives a rate constant value k(CuIII+CuI)=(1.0+/-0.4)x109 dm3 mol-1 s-1.If CuI is absent, or complexed with DMP, CuIII can react to oxidise the amino-acid ligand.
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