Investigating the Tyrosine-Histidine Linkage in the Copper B Site of Cytochrome C Oxidase: Model Studies Utilizing a Zinc Imidazole-Phenol Containing Complex

A chelating ligand (BPAIP) was synthesized incorporating an ortho substituted imidazole-phenol moiety. The resultant Zn(II) complex, [Zn(BPAIP)(Br)]+, was found to exhibit a decreased pK A (8.24) and increased oxidation potential relative to the unbound BPAIP. In addition, the stability of [Zn(BPAIP)(Br)]+ in buffered D2O was found to be pH dependent. The increased stability of [Zn(BPAIP)(Br)] + in buffered D2O at basic pH coincides with the experimentally determined pKA of the phenolic proton of BPAIP. This implies changes in the donating ability of the imidazole to Zn(II) as a result of the protonation state of the cross-linked phenol. Thus, the linkage could serve to make the imidazole a stronger ligand to Zn(II).

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Pesavento, Russell P.

Contributors dc:contributor

• van der Donk, Wilfred A.

• Chemistry, Inorganic

Language dc:language

eng

Identifier

(MiAaPQ)AAI3153398

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84161