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Formation and Electronic Structure of an Atypical CuA Site.


ABSTRACT: PmoD, a recently discovered protein from methane-oxidizing bacteria, forms a homodimer with a dicopper CuA center at the dimer interface. Although the optical and electron paramagnetic resonance (EPR) spectroscopic signatures of the PmoD CuA bear similarities to those of canonical CuA sites, there are also some puzzling differences. Here we have characterized the rapid formation (seconds) and slow decay (hours) of this homodimeric CuA site to two mononuclear Cu2+ sites, as well as its electronic and geometric structure, using stopped-flow optical and advanced paramagnetic resonance spectroscopies. PmoD CuA formation occurs rapidly and involves a short-lived intermediate with a ?max of 360 nm. Unlike other CuA sites, the PmoD CuA is unstable, decaying to two type 2 Cu2+ centers. Surprisingly, NMR data indicate that the PmoD CuA has a pure ?u* ground state rather than the typical equilibrium between ?u* and ?u of all other CuA proteins. EPR, ENDOR, ESEEM, and HYSCORE data indicate the presence of two histidine and two cysteine ligands coordinating the CuA core in a highly symmetrical fashion. This report significantly expands the diversity and understanding of known CuA sites.

SUBMITTER: Ross MO 

PROVIDER: S-EPMC6953997 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Formation and Electronic Structure of an Atypical Cu<sub>A</sub> Site.

Ross Matthew O MO   Fisher Oriana S OS   Morgada Marcos N MN   Krzyaniak Matthew D MD   Wasielewski Michael R MR   Vila Alejandro J AJ   Hoffman Brian M BM   Rosenzweig Amy C AC  

Journal of the American Chemical Society 20190307 11


PmoD, a recently discovered protein from methane-oxidizing bacteria, forms a homodimer with a dicopper Cu<sub>A</sub> center at the dimer interface. Although the optical and electron paramagnetic resonance (EPR) spectroscopic signatures of the PmoD Cu<sub>A</sub> bear similarities to those of canonical Cu<sub>A</sub> sites, there are also some puzzling differences. Here we have characterized the rapid formation (seconds) and slow decay (hours) of this homodimeric Cu<sub>A</sub> site to two monon  ...[more]

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