Bacterial proton-translocating NADH:quinone oxidoreductase (NDH-1) consists of a peripheral and a membrane domain. The peripheral domain catalyzes the electron transfer from NADH to quinone through a chain of seven iron-sulfur (Fe/S) clusters. Subunit NuoI in the peripheral domain contains two [4Fe-4S] clusters (N6a and N6b) and plays a role in bridging the electron transfer from cluster N5 to the terminal cluster N2. We constructed mutants for eight individual Cys-coordinating Fe/S clusters. With the exception of C63S, all mutants had damaged architecture of NDH-1, suggesting that Cys-coordinating Fe/S clusters help maintain the NDH-1 structure. Studies of three mutants (C63S-coordinating N6a, P110A located near N6a, and P71A in the vicinity of N6b) were carried out using EPR measurement. These three mutations did not affect the EPR signals from [2Fe-2S] clusters and retained electron transfer activities. Signals at g(z) = 2.09 disappeared in C63S and P110A but not in P71A. Considering our data together with the available information, g(z,x) = 2.09, 1.88 signals are assigned to cluster N6a. It is of interest that, in terms of g(z,x) values, cluster N6a is similar to cluster N4. In addition, we investigated the residues (Ile-94 and Ile-100) that are predicted to serve as electron wires between N6a and N6b and between N6b and N2, respectively. Replacement of Ile-100 and Ile-94 with Ala/Gly did not affect the electron transfer activity significantly. It is concluded that conserved Ile-100 and Ile-94 are not essential for the electron transfer.
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http://dx.doi.org/10.1074/jbc.M111.329649 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland.
Organic redox systems that can undergo oxidative and reductive (ambipolar) electron transfer are elusive yet attractive for applications across synthetic chemistry and energy science. Specifically, the use of ambipolar redox systems in proton-coupled electron transfer (PCET) reactions is largely unexplored but could enable "switchable" reactivity wherein the uptake and release of hydrogen atoms are controlled using a redox stimulus. Here, we describe the synthesis and characterization of an ambipolar functionalized terthiophene (TTH) bearing methyl thioether and phosphine oxide groups that exhibits switchable PCET reactivity.
View Article and Find Full Text PDFChemphyschem
January 2025
Southern Methodist University, Chemistry, 3251 Daniel Ave, 75275, Dallas, UNITED STATES.
We analyzed the intrinsic strength of distal and proximal FeN bonds and the stiffness of the axial NFeN bond angle in a series of cytochrome b5 proteins isolated from various species, including bacteria, animals, and humans. Ferric and ferrous oxidation states were considered. As assess- ment tool, we employed local vibrational stretching force constants ka(FeN) and bending force constants ka(NFeN) derived from our local mode theory.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Department of Applied Chemistry, Chuo University, Tokyo 112-8551, Japan.
We employed machine learning (ML) techniques combined with potential-dependent photoelectrochemical impedance spectroscopy (pot-PEIS) to gain deeper insights into the charge transport mechanisms of hematite (α-FeO) photoanodes. By the Shapley Additive exPlanations (SHAP) analysis from the ML model constructed from a small data set (dozens of samples) of electrical parameters obtained from pot-PEIS and the PEC performance, we identified the dominant factors influencing the electron transport to the back contact in the bulk and hole transfer to a solution at the hematite/electrolyte interface. The results revealed that shallow defect states significantly enhance electron transport, while deep defect states impede it, and also one of the surface states enhances the hole transfer to the electrolyte solution.
View Article and Find Full Text PDFChemistry
January 2025
Jadavpur University, Chemistry, 188 Raja S. C. Mallick Road, 700032, Kolkata, INDIA.
Two π-radical complexes containing bisazo-aromatic-centered radical anion (1•-) were synthesized through in-situ electron transfer from metal-to-ligand using [IrI] and 2-(2-Pyridylazo)azobenzene (1) in inert hydrocarbon solvent. These are characterized as diradical [IrIII(1•-)2]+[2]+ and monoradical [IrIII(1•-)Cl2(PPh3)] 3. In contrast, a rare metal-mediated hydrolytic cleavage of the C(sp2)-N bond occurred in protic solvent resulting in quaternary radical complex [IrIII(1•-)(1')(PPh3)]+(4)+.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Ritsumeikan University: Ritsumeikan Daigaku, Applied Chemistry, B805 Biolink, 1-1-1 Nojihigashi, 525-8577, Kusatsu, JAPAN.
Inorganic photochromic materials offer several advantages over organic compounds, including relatively inexpensive and higher thermal stability. However, tuning their color with the same component has remained a significant challenge. In this study, we demonstrate that the photochromic color of Cu-doped ZnS nanocrystals (NCs), which is initially pale yellow before light irradiation, can be tuned from gray to brown by adjusting the surface stoichiometry of Zn and S, which is controlled through the use of thiol and non-thiol ligands.
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