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

作者：De Luna Phil; Bushnell Eric A C; Gauld James W^*

来源：Journal of Physical Chemistry A, 2013, 117(19): 4057-4065.

DOI：10.1021/jp402514w

The ability of hybrid, nonhybrid and metaGGA density functional theory (DFT) based methods (B3LYP, BP86, M06 and M06L) to provide reliable structures and thermochemical properties of biochemically important Cu(I)/(II)center dot center dot center dot ESH (ergothioneine) and center dot center dot center dot OSH (ovothiol) has been assessed. For all functionals considered, convergence in the optimized structures and Cu(I)/(II)center dot center dot center dot 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.

• 出版日期2013-5-16