This subproject is one of many research subprojects utilizing theresources provided by a Center grant funded by NIH/NCRR. The subproject andinvestigator (PI) may have received primary funding from another NIH source,and thus could be represented in other CRISP entries. The institution listed isfor the Center, which is not necessarily the institution for the investigator.The major emphasis of our research is to apply variable energy photoelectron spectroscopy (PES) combined with X-ray absorption edge spectroscopy (XAS) to define electronic structure contributions to electron transfer (ET) in biological systems. PES provides a direct method to study inorganic redox processes and the contribution of electronic relaxation to redox properties (E , HAB, lambda). The shake-up satellite structure present in core and valence PES data can be used in combination with a valence bond configuration interaction (VBCI) model to experimentally quantify electronic relaxation (i.e. the change in electronic structure of metal complexes upon oxidation) and its contributions to reduction potentials and kinetics of ET. Variable-energy PES experiments provide a mechanism to maximize the metal while minimizing the ligand contributions to the valence band region through cross section effects (delayed maximum and Cooper minimum) and resonance enhancement. Our synchrotron-based studies on simple model systems [FeX4]2-/1 (X=Cl-, -SR) have afforded experimental results that define electronic structure and its changes upon redox. Complemented by density functional theory (DFT) calculations, these studies provide insight into electronic relaxation and allow extension to the metalloprotein sites. Using the methodology developed in the studies on [FeX4]2-/1, we are now examining model heme complexes. The data on the heme models combined with DFT calculations should also allow extention to and define the superexchange pathways for ET in the cytochromes. We will also extend these PES/DFT studies to [Fe4S4(SR)4] systems modeling the 4Fe ferredoxins and HiPIPs (high potential iron proteins), which will provide insight into electronic relaxation and its contributions to the kinetics and pathways for ET in the ferredoxins and HiPIPS.

Agency
National Institute of Health (NIH)
Institute
National Center for Research Resources (NCRR)
Type
Biotechnology Resource Grants (P41)
Project #
5P41RR001209-28
Application #
7598122
Study Section
Special Emphasis Panel (ZRG1-BPC-E (40))
Project Start
2007-03-01
Project End
2008-02-29
Budget Start
2007-03-01
Budget End
2008-02-29
Support Year
28
Fiscal Year
2007
Total Cost
$16,266
Indirect Cost
Name
Stanford University
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
009214214
City
Stanford
State
CA
Country
United States
Zip Code
94305
Vickers, Chelsea; Liu, Feng; Abe, Kento et al. (2018) Endo-fucoidan hydrolases from glycoside hydrolase family 107 (GH107) display structural and mechanistic similarities to ?-l-fucosidases from GH29. J Biol Chem 293:18296-18308
Nguyen, Phong T; Lai, Jeffrey Y; Lee, Allen T et al. (2018) Noncanonical role for the binding protein in substrate uptake by the MetNI methionine ATP Binding Cassette (ABC) transporter. Proc Natl Acad Sci U S A 115:E10596-E10604
Aleman, Fernando; Tzarum, Netanel; Kong, Leopold et al. (2018) Immunogenetic and structural analysis of a class of HCV broadly neutralizing antibodies and their precursors. Proc Natl Acad Sci U S A 115:7569-7574
Herrera, Nadia; Maksaev, Grigory; Haswell, Elizabeth S et al. (2018) Elucidating a role for the cytoplasmic domain in the Mycobacterium tuberculosis mechanosensitive channel of large conductance. Sci Rep 8:14566
Lal, Neeraj K; Nagalakshmi, Ugrappa; Hurlburt, Nicholas K et al. (2018) The Receptor-like Cytoplasmic Kinase BIK1 Localizes to the Nucleus and Regulates Defense Hormone Expression during Plant Innate Immunity. Cell Host Microbe 23:485-497.e5
Pluvinage, Benjamin; Grondin, Julie M; Amundsen, Carolyn et al. (2018) Molecular basis of an agarose metabolic pathway acquired by a human intestinal symbiont. Nat Commun 9:1043
Beyerlein, Kenneth R; J├Ânsson, H Olof; Alonso-Mori, Roberto et al. (2018) Ultrafast nonthermal heating of water initiated by an X-ray Free-Electron Laser. Proc Natl Acad Sci U S A 115:5652-5657
Yoshizawa, Takuya; Ali, Rustam; Jiou, Jenny et al. (2018) Nuclear Import Receptor Inhibits Phase Separation of FUS through Binding to Multiple Sites. Cell 173:693-705.e22
Guillaume, Joren; Wang, Jing; Janssens, Jonas et al. (2017) Galactosylsphingamides: new ?-GalCer analogues to probe the F'-pocket of CD1d. Sci Rep 7:4276
Ishigami, Izumi; Zatsepin, Nadia A; Hikita, Masahide et al. (2017) Crystal structure of CO-bound cytochrome c oxidase determined by serial femtosecond X-ray crystallography at room temperature. Proc Natl Acad Sci U S A 114:8011-8016

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