In the present study, organophosphorus pesticides (OPs) (diazinon, methyl parathion, and parathion) were oxidized by bubbling ozone into a glass reactor. OP residues were detected using HPLC and ozonation intermediates were identified using GC-MS. The degradation of OPs followed pseudo-first-order kinetics through direct ozone oxidation and indirect hydroxyl radical oxidation. Diazinon, based on its relatively higher degradation constant, was easily degraded by ozonation. Increasing the pH of the solution accelerated diazinon degradation, but little effect was observed for methyl parathion or parathion. Diazoxon, methyl paraoxon and paraoxon were identified as ozonation intermediates of diazinon, methyl parathion and parathion, respectively. The ozonation of the PS group results in the formation of oxon intermediates, which suggests that OPs with this group would be degraded in a similar manner to that seen for the OPs tested in this study. Diazoxon was completely decomposed by ozonation in 30min, while trace methyl paraoxon and paraoxon accumulated to different amounts when the solution pH was varied. The presence of oxon intermediates should be noted in OP removal by ozonation.
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http://dx.doi.org/10.1016/j.chemosphere.2009.04.060 | DOI Listing |
JAMA Cardiol
December 2024
Department of Cardiology, Instituto do Coração, Hospital das Clínicas da Universidade de São Paulo, São Paulo, Brazil.
Importance: Over 10 000 people with Chagas disease experience sudden cardiac death (SCD) annually, mostly caused by ventricular fibrillation. Amiodarone hydrochloride and the implantable cardioverter-defibrillator (ICD) have been empirically used to prevent SCD in patients with chronic Chagas cardiomyopathy.
Objective: To test the hypothesis that ICD is more effective than amiodarone therapy for primary prevention of all-cause mortality in patients with chronic Chagas cardiomyopathy and moderate to high mortality risk, assessed by the Rassi score.
ACS Catal
August 2024
Department of Chemistry & Manchester Institute of Biotechnology, The University of Manchester, 131 Princess Street, Manchester M1 7DN, U.K.
The ability to introduce noncanonical amino acids as axial ligands in heme enzymes has provided a powerful experimental tool for studying the structure and reactivity of their Fe=O ("ferryl") intermediates. Here, we show that a similar approach can be used to perturb the conserved Fe coordination environment of 2-oxoglutarate (2OG) dependent oxygenases, a versatile class of enzymes that employ highly-reactive ferryl intermediates to mediate challenging C-H functionalizations. Replacement of one of the cis-disposed histidine ligands in the oxygenase VioC with a less electron donating -methyl-histidine (MeHis) preserves both catalytic function and reaction selectivity.
View Article and Find Full Text PDFInorg Chem
July 2024
Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford OX1 3QR, U.K.
Binary metal hydrides can act as low-temperature reducing agents for complex oxides in the solid state, facilitating the synthesis of anion-deficient oxide or oxyhydride phases. The reaction of LaSrCoRuO, with CaH in a sealed tube yields the face-centered cubic phase LaSrCoRuOH. The reaction with LiH under similar conditions converts LaSrCoRuO to a mixture of tetragonal LaSrCoRuOH and cubic LaSrCoRuOH.
View Article and Find Full Text PDFACS Catal
April 2024
Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, London WC1H 0AJ, United Kingdom.
CO hydrogenation over Rh catalysts comprises multiple reaction pathways, presenting a wide range of possible intermediates and end products, with selectivity toward either CO or methane being of particular interest. We investigate in detail the reaction mechanism of CO hydrogenation to the single-carbon (C1) products on the Rh(111) facet by performing periodic density functional theory (DFT) calculations and kinetic Monte Carlo (kMC) simulations, which account for the adsorbate interactions through a cluster expansion approach. We observe that Rh readily facilitates the dissociation of hydrogen, thus contributing to the subsequent hydrogenation processes.
View Article and Find Full Text PDFToxics
March 2024
Institute of Environmental Biotechnology and Functional Materials, School of Environmental Science and Engineering, Shandong University, Qingdao 266237, China.
Persulfate-based advanced oxidation process has been proven to be a promising method for the toxic pesticide chlorpyrifos (CPY) degradation in wastewater treatment. However, due to the limitation for the short-lived intermediates detection, a comprehensive understanding for the degradation pathway remains unclear. To address this issue, density functional theory was used to analyze the degradation mechanism of CPY at the M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G(d,p) level, and computational toxicology methods were employed to explore the toxicity of CPY and its degradation products.
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