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involves an initial hydrogen-atom transfer within the copper-alkoxide/azo
complex generating the carbonyl-bound hydrazino-copper species. Then the
binding of dissociates the product aldehyde or ketone and forms a
binuclear copper(II) peroxide species which undergoes homolytic cleavage
followed by hydrogen-atom abstraction from the coordinated hydrazine
giving a Cu(I)-hydroxy complex. The Cu(I)-hydroxy complex binds to
another molecule of the alcohol and releases water to regenerate the copper-
alkoxide/azo complex. However, Cu(I) hydroxy complexes are unknown in
the literature. Therefore, the exact nature of the catalytic cycle is unclear.
5.
COPPER-PHENANTHROLINE DNA OXIDATION
Due to the toxicity and carcinogenicity of metal ions and metal
complexes there is considerable interest in understanding metal-mediated
oxidation of biopolymers. i.e., nucleic acids and proteins. Copper, in
particular is highly regulated in the cell to prevent the deleterious reactions
that can result from its interaction with dioxygen or reactive oxygen species
such as superoxide or hydrogen peroxide. 121 The reactive nature of copper
complexes, make them potential drug candidates and powerful tools for
studying the solution structure of biological substrates.
The chemistry of copper with DNA results in both reaction at the
deoxyribose sugar and some base oxidation. Although, some compounds
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