Author ORCID Identifier
https://orcid.org/0000-0002-2956-9781
Document Type
Article
Publication Date
2013
Publication Title
The Journal of Physical Chemistry
Volume
117
Issue
19
First Page
4057
Last Page
4065
Abstract
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)···ESH (ergothioneine) and ···OSH (ovothiol) has been assessed. For all functionals considered, convergence in the optimized structures and Cu(I)/(II)···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.
DOI
10.1021/jp402514w
Recommended Citation
De Luna, Phil; Bushnell, Eric Andre; and Gauld, James. (2013). A Density Functional Theory Investigation into the Binding of the Antioxidants Ergothioneine and Ovothiol to Copper.. The Journal of Physical Chemistry, 117 (19), 4057-4065.
https://scholar.uwindsor.ca/chemistrybiochemistrypub/118