DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Spiers Memorial Lecture: activating metal sites for biological electron transfer

Journal Article · · Faraday Discussions
DOI: https://doi.org/10.1039/d2fd00001f · OSTI ID:1863413

Metal sites in biology often exhibit unique spectroscopic features that reflect novel geometric and electronic structures imposed by the protein that are key to reactivity. The blue copper active site involved in long range, rapid biological electron transfer is a classic example. This review presents an overview of both traditional and synchrotron based spectroscopic methods and their coupling to electronic structure calculations to understand the unique features of the blue copper active site, their contributions to function and the role of the protein in determining the geometric and electronic structure of the active site (called the “entatic state”). The relation of this active site to other biological electron transfer sites is further developed. Specifically, ultrafast XFEL spectroscopy is used to evaluate the methionine–S–Fe bond in cytochrome c, and its entatic control by the protein in determining function (electron transfer vs. apoptosis).

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1863413
Journal Information:
Faraday Discussions, Journal Name: Faraday Discussions Vol. 234; ISSN 1359-6640
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (36)

QM/MM calculations with DFT for taking into account protein effects on the EPR and optical spectra of metalloproteins. Plastocyanin as a case study journal January 2006
Axial ligand replacement in horse heart cytochromec by semisynthesis journal January 1989
Copper coordination in blue proteins journal October 2000
Electron transfers in chemistry and biology journal August 1985
QM/MM calculations of EPR hyperfine coupling constants in blue copper proteins journal August 2003
Amino acid sequence, haem-iron co-ordination geometry and functional properties of mitochondrial and bacterial c-type cytochromes journal May 1985
Electronic Structures of Metal Sites in Proteins and Models:  Contributions to Function in Blue Copper Proteins journal February 2004
Structural and Functional Aspects of Metal Sites in Biology journal January 1996
Spectroscopic and theoretical studies of the unusual EPR parameters of distorted tetrahedral cupric sites: correlations to x-ray spectral features of core levels journal April 1987
Spectroscopic Methods in Bioinorganic Chemistry:  Blue to Green to Red Copper Sites journal October 2006
Molecular g values of the planar tetrachlorocuprate(2-) ion journal June 1977
X-ray absorption spectroscopic studies of the blue copper site: metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin journal January 1993
Copper L-edge spectral studies: a direct experimental probe of the ground-state covalency in the blue copper site in plastocyanin journal April 1993
X-ray absorption edge spectroscopy of ligands bound to open-shell metal ions: chlorine K-edge studies of covalency in tetrachlorocuprate(2-) journal February 1990
Electronic structure of plastocyanin: excited state spectral features journal June 1988
Electronic structure and bonding of the blue copper site in plastocyanin journal July 1985
Detailed absorption, reflectance, and UV photoelectron spectroscopic and theoretical studies of the charge-transfer transitions of tetrachlorocuprate(2-) ion: correlation of the square-planar and the tetrahedral limits journal July 1983
Spectroscopic studies on plastocyanin single crystals: a detailed electronic structure determination of the blue copper active site journal July 1981
Preparation and characterization of [rac-5,7,7,12,14,14,-hexamethyl-1,4,8,11-tetraazocyclotetradecane]copper(II) o-mercaptobenzoate hydrate, [Cu(tet b)(o-SC6H4CO2)].H2O, a complex with a CuN4S (mercaptide) chromophore journal May 1979
Electron nuclear double resonance spectra of stellacyanin, a blue copper protein journal January 1980
L-edge X-ray Absorption Spectroscopy of Non-Heme Iron Sites:  Experimental Determination of Differential Orbital Covalency journal October 2003
Spectroscopic Studies of the Met182Thr Mutant of Nitrite Reductase:  Role of the Axial Ligand in the Geometric and Electronic Structure of Blue and Green Copper Sites journal November 2003
Spectroscopic and DFT Studies of Second-Sphere Variants of the Type 1 Copper Site in Azurin: Covalent and Nonlocal Electrostatic Contributions to Reduction Potentials journal October 2012
Metal–Ligand Covalency of Iron Complexes from High-Resolution Resonant Inelastic X-ray Scattering journal October 2013
Anisotropic Covalency Contributions to Superexchange Pathways in Type One Copper Active Sites journal October 2014
Resonant Inelastic X-ray Scattering on Ferrous and Ferric Bis-imidazole Porphyrin and Cytochrome c : Nature and Role of the Axial Methionine–Fe Bond journal December 2014
Methionine Ligand Lability of Type I Cytochromes c : Detection of Ligand Loss Using Protein Film Voltammetry journal May 2008
Spectroscopic and Geometric Variations in Perturbed Blue Copper Centers:  Electronic Structures of Stellacyanin and Cucumber Basic Protein journal September 1998
Effects of Ligation and Folding on Reduction Potentials of Heme Proteins journal December 1998
X-ray crystal structure analysis of plastocyanin at 2.7 Å resolution journal March 1978
Formulas and Numerical Tables for Overlap Integrals journal December 1949
Thermodynamic equilibrium between blue and green copper sites and the role of the protein in controlling function journal March 2009
Axial interactions in the mixed-valent Cu A active site and role of the axial methionine in electron transfer journal August 2013
Metalloenzymes: the entatic nature of their active sites. journal February 1968
The blue oxidases, ascorbate oxidase, laccase and ceruloplasmin Modelling and structural relationships journal January 1990
Metalloprotein entatic control of ligand-metal bonds quantified by ultrafast x-ray spectroscopy journal June 2017

Similar Records

Multicopper oxidases and oxygenases
Journal Article · 1996 · Chemical Reviews · OSTI ID:415591

O(2)And N(2)O Activation By Bi-, Tri-, And Tetranuclear Cu Clusters in Biology
Journal Article · 2009 · Accounts Chem. Res 40:581,2007 · OSTI ID:953888

Active-Site Environmental Factors Customize the Photophysics of Photoenzymatic Old Yellow Enzymes
Journal Article · 2020 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry · OSTI ID:1735629