A mechanistic study of the gold-catalysed protodecarboxylation is described. Each reaction step has been investigated experimentally and computationally. More specifically, the activation parameters for the decarboxylation step have been determined through kinetic studies. Further experimental studies on the hydrolysis of the arylgold intermediate have revealed that the protodeauration can become competitive with the decarboxylation process at high conversions. This switch in rate-limiting step has been shown to be pKa -dependent. These studies have been supported by DFT calculations and permit a better understanding of which prevalent features of the reaction mechanism account for the decarboxylation process.
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http://dx.doi.org/10.1002/chem.201405716 | DOI Listing |
J Hazard Mater
January 2025
Department of Civil and Environmental Engineering, Seoul National University, Seoul 151-744, South Korea. Electronic address:
The presence of PFAS in water matrices has become a global environmental issue in the last half-century. Dielectric barrier discharge (DBD) and electrooxidation (EO) showed potential for PFAS degradation but have yet to find practical application due to relatively high energy consumption. In this study, a hybrid DBD-EO system for efficient degradation of PFAS was developed by involving more reactive oxygen, sulfate radicals (SO) and nitrogen species (RONS).
View Article and Find Full Text PDFNat Commun
January 2025
Modern Research Center for Traditional Chinese Medicine, Beijing Institute of Traditional Chinese Medicine, Beijing University of Chinese Medicine, 102488, Beijing, PR China.
Echinacoside (ECH), one of the most representative phenylethanoid glycosides (PhGs), has considerable neuroprotective effects and is an effective ingredient in numerous commercial drugs. Here, we elucidate the complete ECH biosynthetic pathway in the medicinal plant Cistanche tubulosa. In total, 14 related genes are cloned and functionally characterized.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
The simple and efficient conversion of carboxylic acids into structurally diverse organic molecules is highly desirable in chemical synthesis. This review covers recent developments in photocatalytic methodology for late-stage transformations of complex carboxylic acids and their derivatives enabled by radical decarboxylation and deoxygenation, highlighting some representative and significant contributions in this field. These advancements are categorized based on the reactivity patterns exhibited by the carboxylic acids.
View Article and Find Full Text PDFJ Hazard Mater
January 2025
School of Environmental Science and Engineering, Southwest Jiaotong University, Sichuan, Chengdu 611756, China. Electronic address:
The ultraviolet-activated peroxymosnofulate (UV/PMS) system, an effective advanced oxidation process for removing dissolved organic matter (DOM) from wastewater, is limited by high chloride ion (Cl) concentrations in landfill leachate. This study used Fourier transform ion cyclotron resonance mass spectrometry to explore the transformation of DOM in the UV/PMS system with a high Cl concentration. The results revealed that elevated Cl levels generate reactive chlorine species, including chlorine radicals, dichlorine radicals, and hypochlorous acid/hypochlorite, reducing the total organic carbon (TOC) removal efficiency of Suwannee River natural organic matter (SRNOM) from 78.
View Article and Find Full Text PDFSoft Matter
January 2025
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
The incorporation of a glassy material into a self-assembled nanoparticle (NP) film can produce highly loaded nanocomposites. Reduction of the NP diameter can lead to extreme nanoconfinement of the glass, significantly affecting the thermal and physical properties of the nanocomposite material. Here, we investigate the photostability and photodegradation mechanisms of molecular nanocomposite films (MNCFs) produced from the infiltration of indomethacin (IMC) molecules into self-assembled films of silica NPs (11-100 nm in diameter).
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