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Analysis of resonance Raman data on the blue copper site in pseudoazurin: excited state π and σ charge transfer distortions and their relation to ground state reorganization energy

Hadt, Ryan G. and Xie, Xiangjin and Pauleta, Sofia R. and Moura, Isabel and Solomon, Edward I. (2012) Analysis of resonance Raman data on the blue copper site in pseudoazurin: excited state π and σ charge transfer distortions and their relation to ground state reorganization energy. Journal of Inorganic Biochemistry, 115 . pp. 155-162. ISSN 0162-0134. https://resolver.caltech.edu/CaltechAUTHORS:20180612-150514757

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Abstract

The short Cu^(2+)-S(Met) bond in pseudoazurin (PAz) results in the presence of two relatively intense S_p(π) and S_p(σ) charge transfer (CT) transitions. This has enabled resonance Raman (rR) data to be obtained for each excited state. The rR data show very different intensity distribution patterns for the vibrations in the 300-500 cm^(-1) region. Time-dependent density functional theory (TDDFT) calculations have been used to determine that the change in intensity distribution between the S_p(π) and S_p(σ) excited states reflects the differential enhancement of S(Cys) backbone modes with Cu-S(Cys)-C_β out-of-plane (oop) and in-plane (ip) bend character in their respective potential energy distributions (PEDs). The rR excited state distortions have been related to ground state reorganization energies (λ s) and predict that, in addition to M-L stretches, the Cu-S(Cys)-C_β oop bend needs to be considered. DFT calculations predict a large distortion in the Cu-S(Cys)-C_β oop bending coordinate upon reduction of a blue copper (BC) site; however, this distortion is not present in the X-ray crystal structures of reduced BC sites. The lack of Cu-S(Cys)-C_β oop distortion upon reduction corresponds to a previously unconsidered constraint on the thiolate ligand orientation in the reduced state of BC proteins and can be considered as a contribution to the entatic/rack nature of BC sites.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1016/j.jinorgbio.2012.03.006DOIArticle
ORCID:
AuthorORCID
Hadt, Ryan G.0000-0001-6026-1358
Solomon, Edward I.0000-0003-0291-3199
Additional Information:© 2012 Elsevier. Received 29 January 2012, Revised 18 March 2012, Accepted 21 March 2012, Available online 30 March 2012. This work was supported by NSFCHE-0948211 (E.I.S.). R.G.H. acknowledges a Gerhard Casper Stanford Graduate Fellowship. X. X. is grateful for a William S. Johnson Fellowship. S.R.P. thanks the financial support of Fundação para a Ciência e Tecnologia, Portugal (PTDC/BIA-PRO/098882/2008).
Funders:
Funding AgencyGrant Number
NSFCHE-0948211
Stanford UniversityUNSPECIFIED
Fundação para a Ciência e Tecnologia (FCT)PTDC/BIA-PRO/098882/2008
Subject Keywords:Blue copper; Entatic/rack state; Electronic absorption; Resonance Raman; Excited state distortion; DFT
Record Number:CaltechAUTHORS:20180612-150514757
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180612-150514757
Official Citation:Ryan G. Hadt, Xiangjin Xie, Sofia R. Pauleta, Isabel Moura, Edward I. Solomon, Analysis of resonance Raman data on the blue copper site in pseudoazurin: Excited state π and σ charge transfer distortions and their relation to ground state reorganization energy, Journal of Inorganic Biochemistry, Volume 115, 2012, Pages 155-162, ISSN 0162-0134, https://doi.org/10.1016/j.jinorgbio.2012.03.006. (http://www.sciencedirect.com/science/article/pii/S0162013412000931)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87030
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Jun 2018 22:17
Last Modified:03 Oct 2019 19:51

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