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Molecular Mechanism of Unexpected Metal-Independent Hydroxyl Radical Production by Mercaptotriazole and HO.
Environ Sci Technol
January 2025
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, The Chinese Academy of Sciences, Beijing 100085, P. R. China.
It is well known that hydroxyl radical (OH) can be largely produced either through the classic iron-mediated inorganic-Fenton system or our recently discovered haloquinones/HO organic-Fenton-like system, but rarely produced via thiol compounds. Here, unexpectedly, we found that OH can be unequivocally generated by incubation of HO and mercaptotriazole (MTZ), a typical heterocyclic thiol which has been used as an environmentally friendly corrosion inhibitor for mild steel. By the complementary applications of HPLC-MS and oxygen-18 isotope-labeling method, MTZ-derived sulfenic (MTZ-SOH) and sulfinic acids were detected and identified as transient intermediates, and sulfonic acid as final products.
View Article and Find Full Text PDFMonitoring electrophilic intermediates in reactions of thiols in aqueous solution directly with F NMR.
Chem Sci
December 2024
Department of Chemistry and Biomolecular Sciences, University of Ottawa 10 Marie Curie Pvt Ottawa ON K1N6N5 Canada
Mechanistic studies of thiol reactivity can be challenging because electrophilic reaction intermediates, such as sulfenic acids (RSOH) and sulfenyl chlorides (RSCl), are generally too reactive to be observed directly. Herein we report the design and synthesis of a sterically-encumbered fluorinated triptycene thiol which enables direct observation of reaction intermediates in aqueous buffer by F NMR, as demonstrated in reactions with hydrogen peroxide and hypochlorous acid. Reactions with HO resulted in the formation of a persistent RSOH species, which was subsequently converted to a sulfinic acid (RSOH) and then a sulfonic acid (RSOH), while RSCl was found to be the intermediate in reactions with HOCl.
View Article and Find Full Text PDFDisulfide stress and its role in cardiovascular diseases.
Redox Biol
September 2024
Henan Key Laboratory of Medical Tissue Regeneration, Xinxiang Medical University, Xinxiang, China; Department of Human Anatomy and Histoembryology, Xinxiang Medical University, Xinxiang, China. Electronic address:
Cardiovascular disease (CVD) is one of the leading causes of mortality in humans, and oxidative stress plays a pivotal role in disease progression. This phenomenon typically arises from weakening of the cellular antioxidant system or excessive accumulation of peroxides. This review focuses on a specialized form of oxidative stress-disulfide stress-which is triggered by an imbalance in the glutaredoxin and thioredoxin antioxidant systems within the cell, leading to the accumulation of disulfide bonds.
View Article and Find Full Text PDF-Sulfenylation Driven Antigen Capture Boosted by Radiation for Enhanced Cancer Immunotherapy.
ACS Nano
July 2024
State Key Laboratory of Radiation Medicine and Protection, School of Radiation Medicine and Protection, and Collaborative Innovation Center of Radiological Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou 215123, People's Republic of China.
Radiotherapy (RT)-induced vaccination greatly promotes the development of personalized cancer vaccines owing to the massive release of antigens initiated by tumor-localized RT eliciting the tumor-specific immune response. However, its broad application in cancer treatment is seriously impeded by poor antigen cross-presentation, low response rate, and short duration of efficacy. Herein, the tumor-antigen-capturing nanosystem dAuNPs@CpG consisting of gold nanoparticles, 3,5-cyclohexanedione (CHD), and immunoadjuvant CpG were fabricated to enhance RT-induced vaccination.
View Article and Find Full Text PDFMechanisms underlying the formation of main volatile odor sulfur compounds in foods during thermal processing.
Compr Rev Food Sci Food Saf
July 2024
College of Tobacco Science, Henan Agricultural University, Zhengzhou, China.
Volatile sulfur compounds (VSCs) significantly influence food flavor and garner considerable attention in flavor research due to their low sensory thresholds, diverse odor attributes, and high reactivity. Extensive research studies have explored VSC formation through thermal processes such as the Maillard reaction, thermal pyrolysis, oxidation, and enzymatic reactions. However, understanding of the specific reaction mechanisms and processes remains limited.
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