A Density Functional Theory Investigation into the Binding of the Antioxidants Ergothioneine and Ovothiol to Copper.

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• 作者：Phil De Luna ; Eric A. C. Bushnell ; James W. Gauld
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：May 16, 2013
• 年：2013
• 卷：117
• 期：19
• 页码：4057-4065
• 全文大小：412K
• 年卷期：v.117,no.19(May 16, 2013)
• ISSN：1520-5215

文摘

The ability of hybrid, nonhybrid and meta-GGA density functional theory (DFT) based methods (B3LYP, BP86, M06 and M06L) to provide reliable structures and thermochemical properties of biochemically important Cu(I)/(II)路路路ESH (ergothioneine) and 路路路OSH (ovothiol) has been assessed. For all functionals considered, convergence in the optimized structures and Cu(I)/(II)路路路S/N bond lengths is only obtained using the 6-311+G(2df,p) basis set or larger, with the nonhybrid DFT method BP86 appearing, in general, to provide the most reliable structures. The reduction potentials associated with the reduction of Cu(II) to Cu(I) when complexed with either OSH and ESH were also determined. The implications for their ability to thus help protect against Cu-mediated oxidative damage are discussed. Importantly, the binding of OSH and ESH with Cu ions disfavors Cu(I)/Cu(II) recycling by increasing the reduction potential for the Cu(II) to Cu(I) reduction and as a result, inhibits the potential oxidative damage caused by such Cu ions.