PH-Induced Binding of the Axial Ligand in an Engineered CuA Site Favors the πu State

Marcos N. Morgada, Florencia Emiliani, Kelly N. Chacón, Damián Álvarez-Paggi, Daniel H. Murgida, Ninian J. Blackburn, Luciano A. Abriata, Alejandro J. Vila

Research output: Contribution to journalArticle

Abstract

CuA centers perform efficient long-range electron transfer. The electronic structure of native CuA sites can be described by a double-potential well with a dominant σu∗ ground state in fast equilibrium with a less populated πu ground state. Here, we report a CuA mutant in which a lysine was introduced in the axial position. This results in a highly unstable protein with a pH-dependent population of the two ground states. Deep analysis of the high-pH form of this variant shows the stabilization of the πu ground state due to direct binding of the Lys residue to the copper center that we attribute to deprotonation of this residue.

Original languageEnglish (US)
JournalInorganic Chemistry
DOIs
StateAccepted/In press - Jan 1 2019

Fingerprint

Ground state
Ligands
ligands
ground state
Deprotonation
lysine
Lysine
Electronic structure
Copper
electron transfer
Stabilization
stabilization
electronic structure
proteins
copper
Electrons
Proteins

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Morgada, M. N., Emiliani, F., Chacón, K. N., Álvarez-Paggi, D., Murgida, D. H., Blackburn, N. J., ... Vila, A. J. (Accepted/In press). PH-Induced Binding of the Axial Ligand in an Engineered CuA Site Favors the πu State. Inorganic Chemistry. https://doi.org/10.1021/acs.inorgchem.9b01868

PH-Induced Binding of the Axial Ligand in an Engineered CuA Site Favors the πu State. / Morgada, Marcos N.; Emiliani, Florencia; Chacón, Kelly N.; Álvarez-Paggi, Damián; Murgida, Daniel H.; Blackburn, Ninian J.; Abriata, Luciano A.; Vila, Alejandro J.

In: Inorganic Chemistry, 01.01.2019.

Research output: Contribution to journalArticle

Morgada, Marcos N. ; Emiliani, Florencia ; Chacón, Kelly N. ; Álvarez-Paggi, Damián ; Murgida, Daniel H. ; Blackburn, Ninian J. ; Abriata, Luciano A. ; Vila, Alejandro J. / PH-Induced Binding of the Axial Ligand in an Engineered CuA Site Favors the πu State. In: Inorganic Chemistry. 2019.
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AU - Morgada, Marcos N.

AU - Emiliani, Florencia

AU - Chacón, Kelly N.

AU - Álvarez-Paggi, Damián

AU - Murgida, Daniel H.

AU - Blackburn, Ninian J.

AU - Abriata, Luciano A.

AU - Vila, Alejandro J.

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AB - CuA centers perform efficient long-range electron transfer. The electronic structure of native CuA sites can be described by a double-potential well with a dominant σu∗ ground state in fast equilibrium with a less populated πu ground state. Here, we report a CuA mutant in which a lysine was introduced in the axial position. This results in a highly unstable protein with a pH-dependent population of the two ground states. Deep analysis of the high-pH form of this variant shows the stabilization of the πu ground state due to direct binding of the Lys residue to the copper center that we attribute to deprotonation of this residue.

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