Although water ice has been widely accepted to carry a positive charge via the transfer of excess protons through a hydrogen-bonded system, ice was recently found to be a negative charge conductor upon simultaneous exposure to electrons and ultraviolet photons at temperatures below 50 K. In this work, the mechanism of electron delivery was confirmed experimentally by both measuring currents through ice and monitoring photodissociated OH radicals on ice by using a novel method. The surface OH radicals significantly decrease upon the appearance of negative current flow, indicating that the electrons are delivered by proton-hole (OH) transfer in ice triggered by OH production on the surface. The mechanism of proton-hole transfer was rationalized by density functional theory calculations.
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http://dx.doi.org/10.1021/acs.jpclett.0c03345 | DOI Listing |
J Phys Chem Lett
November 2024
Institute of Low Temperature Science, Hokkaido University, Sapporo 060-0819, Japan.
Although proton transport in water ice is well understood, proton-hole transfer (PHT) involving proton abstraction by anions remains less explored. This study investigates PHT in HS and NH solids at low temperatures, aiming to determine whether these solids exhibit negative charge transport similar to that in ice. In HS and NH solids at 10 K, surface HS and NH anions in hydrogen-bonded systems trigger negative current flow, providing a clear signature of PHT.
View Article and Find Full Text PDFPhys Chem Chem Phys
March 2022
Department of Chemistry, Indian Institute of Technology, Palakkad-678557, Kerala, India.
N-terminal disulfide bond oxidoreductase-D (nDsbD), an essential redox enzyme in Gram-negative bacteria, consists of a single disulfide bond (Cys-Cys) in its active site. The enzymatic functions are believed to be regulated by an electron transfer mediated redox switching of the disulfide bond, which is vital in controlling bacterial virulence factors. In light of the disulfide bond's inclination towards nucleophilic cleavage, it is also plausible that an internal nucleophile could second the existing electron transfer mechanism in nDsbD.
View Article and Find Full Text PDFJ Phys Chem B
January 2022
Van 't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands.
Di-iron hydrogenases are a class of enzymes that are capable of reducing protons to form molecular hydrogen with high efficiency. In addition to the catalytic site, these enzymes have evolved dedicated pathways to transport protons and electrons to the reaction center. Here, we present a detailed study of the most likely proton transfer pathway in such an enzyme using QM/MM molecular dynamics simulations.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
September 2021
Institute of Physical Chemistry, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany;
Extensive classical and quantum mechanical/molecular mechanical (QM/MM) molecular dynamics simulations are used to establish the structural features of the O state in bacteriorhodopsin (bR) and its conversion back to the bR ground state. The computed free energy surface is consistent with available experimental data for the kinetics and thermodynamics of the O to bR transition. The simulation results highlight the importance of the proton release group (PRG, consisting of Glu194/204) and the conserved arginine 82 in modulating the hydration level of the protein cavity.
View Article and Find Full Text PDFAcc Chem Res
February 2021
Institute of Low Temperature Science, Hokkaido University, N19-W8, Kita-ku, Sapporo, Hokkaido 060-0819, Japan.
ConspectusBecause chemical reactions on/in cosmic ice dust grains covered by amorphous solid water (ASW) play important roles in generating a variety of molecules, many experimental and theoretical studies have focused on the chemical processes occurring on the ASW surface. In laboratory experiments, conventional spectroscopic and mass-spectrometric detection of stable products is generally employed to deduce reaction channels and mechanisms. However, despite their importance, the details of chemical reactions involving reactive species (i.
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