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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(52):16868-16871
Triplet dioxygen was reduced by TEMPO or trityl radicals in the presence of two molar equivalents of the strong B(p ‐C6F4X)3 (X: F or H) boron Lewis acids under mild conditions to give the bis(borane)superoxide systems 2 . The sensitive radical anion species were isolated and characterized by methods including X‐ray crystal structure analysis and EPR spectroscopy. 相似文献
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David G. Kwabi Vyacheslav S. Bryantsev Thomas P. Batcho Daniil M. Itkis Carl V. Thompson Yang Shao‐Horn 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(9):3181-3186
Understanding and controlling the kinetics of O2 reduction in the presence of Li+‐containing aprotic solvents, to either Li+‐O2− by one‐electron reduction or Li2O2 by two‐electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li‐O2 batteries. Standard potentials of O2/Li+‐O2− and O2/O2− were experimentally measured and computed using a mixed cluster‐continuum model of ion solvation. Increasing combined solvation of Li+ and O2− was found to lower the coupling of Li+‐O2− and the difference between O2/Li+‐O2− and O2/O2− potentials. The solvation energy of Li+ trended with donor number (DN), and varied greater than that of O2− ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li+‐O2− solubility and DN. These results highlight the importance of the interplay between ion–solvent and ion–ion interactions for manipulating the energetics of intermediate species produced in aprotic metal–oxygen batteries. 相似文献
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Mike Lange Kiwon Ok Geoffrey D. Shimberg Biljana Bursac Lajos Mark Ivana Ivanovi‐Burmazovi Sarah L. J. Michel Milos R. Filipovic 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8081-8085
H2S is a gaseous signaling molecule that modifies cysteine residues in proteins to form persulfides (P‐SSH). One family of proteins modified by H2S are zinc finger (ZF) proteins, which contain multiple zinc‐coordinating cysteine residues. Herein, we report the reactivity of H2S with a ZF protein called tristetraprolin (TTP). Rapid persulfidation leading to complete thiol oxidation of TTP mediated by H2S was observed by low‐temperature ESI‐MS and fluorescence spectroscopy. Persulfidation of TTP required O2 , which reacts with H2S to form superoxide, as detected by ESI‐MS, a hydroethidine fluorescence assay, and EPR spin trapping. H2S was observed to inhibit TTP function (binding to TNFα mRNA) by an in vitro fluorescence anisotropy assay and to modulate TNFα in vivo. H2S was unreactive towards TTP when the protein was bound to RNA, thus suggesting a protective effect of RNA. 相似文献
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