The CuATP react with methyl radicals to form methane and methanol, where CuATP reacts with CH in a process that is surprisingly slow. The low-rate constant of this process is attributed to the significant rearrangement of the chelating ligand required for the transient's formation. These results were corroborated by DFT calculations of the relevant compounds.
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http://dx.doi.org/10.1016/j.jinorgbio.2022.111883 | DOI Listing |
Biochemistry
January 2025
Department of Pharmaceutical Sciences, University of Shizuoka, Shizuoka 422-8526, Japan.
DtpC was isolated from the ditryptophenaline biosynthetic pathway found in filamentous fungi as a cytochrome P450 (P450) that catalyzes the dimerization of diketopiperazines. More recently, several similar P450s were discovered. While a vast majority of such P450s generate asymmetric diketopiperazine dimers, DtpC and other fungal P450s predominantly catalyze the formation of symmetric dimer products.
View Article and Find Full Text PDFEnviron Sci Process Impacts
January 2025
Univ. Lille, CNRS, UMR 8522, Physico-Chimie des Processus de Combustion et de l'Atmosphère - PC2A, 59000 Lille, France.
Fenpyrazamine (FPA) is a widely used fungicide in agriculture to control fungal diseases, but its environmental degradation by oxidants and the formation of potential degradation products remain unexplored. This study investigates the oxidation of FPA by hydroxyl radicals (HO˙) using density functional theory (DFT) calculations at the M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G(d,p) level of theory. Three standard oxidation mechanisms, including formal hydrogen transfer (FHT), radical adduct formation (RAF), and single electron transfer (SET), were evaluated in the aqueous phase, with reaction kinetics analyzed over a temperature range of 283-333 K.
View Article and Find Full Text PDFObjectives: We aim to determine the prognostic significance of DNA methylation () in two independent prostate cancer cohorts with long-term clinical follow-up data.
Subjects/patients And Methods: We first re-examined a published, in-house whole genome bisulphite sequencing (WGBS) prostate cancer dataset, derived from radical prostatectomy (RP) tissue ( = 15) with median follow-up 19.5 years, to confirm and visualise the association between and patient mortality.
J Am Chem Soc
December 2024
School of Chemistry, Xi'an Jiaotong University, Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education, Xi'an 710049, China.
Herein, SUMO-LUMO inversion (SLI) radicals - were designed by the combination of the tris(2,4,6-trichlorophenyl)methyl (TTM) radical and pyridinium derivatives (electron-withdrawing groups) for the first time. The energy of the LUMO lies below that of the SUMO, which deviated from the Aufbau principle as an alternative electronic configuration beyond the well-established SOMO-HOMO inversed system. Thus, for SLI radicals, the injection of one extra electron preferred to occupy the LUMO rather than the SUMO, giving diradicals, one of which had been fully confirmed by single crystal analysis, VT-NMR and VT-EPR experiments, as well as DFT calculations.
View Article and Find Full Text PDFACS Appl Energy Mater
December 2024
Department of Chemical and Environmental Process Engineering, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3, Budapest H-1111, Hungary.
Amphiphilic copolymers of comb-like poly(poly(ethylene glycol) methacrylate) (PPEGMA) with methyl methacrylate (MMA) synthesized by one-pot atom transfer radical polymerization were mixed with lithium bis (trifluoromethanesulfonyl) imide salt to formulate dry solid polymer electrolytes (DSPE) for semisolid-state Li-ion battery applications. The PEO-type side chain length (EO monomer's number) in the PEGMA macromonomer units was varied, and its influence on the mechanical and electrochemical characteristics was investigated. It was found that the copolymers, due to the presence of PMMA segments, possess viscoelastic behavior and less change in mechanical properties than a PEO homopolymer with 100 kDa molecular weight in the investigated temperature range.
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