Redox cycling of iron complexes of N-(dithiocarboxy)sarcosine and N-methyl-d-glucamine dithiocarbamate |
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| Institution: | 1. Inorganic Institute, Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich, Switzerland;1. Department of Applied Chemistry and Biochemical Engineering, Graduate School of Engineering, Shizuoka University, 3-5-1 Johoku Naka-ku, Hamamatsu 432-8561, Japan;2. Research Institute of Green Science and Technology, Shizuoka University, 3-5-1 Johoku Naka-ku, Hamamatsu 432-8561, Japan;3. Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan;1. Université Paris-Est, Laboratoire Géomatériaux et Environnement (EA 4508), UPEM, 77454 Marne-la-Vallée, France;2. Lucia Beamline, Synchrotron SOLEIL, 91192 Gif-sur-Yvette, France;3. Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR-CNRS 7583, Université Paris Est Créteil, France;4. Laboratoire Interdisciplinaire des Environnements Continentaux, CNRS UMR7360, Université de Lorraine, 54501 Vandoeuvre-lès-Nancy, France;5. Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, Muséum National d’Histoire Naturelle, CNRS, UPMC, IRD, 75005 Paris, France;1. Department of Applied Chemistry, College of Chemistry & Molecular Engineering, Peking University, Beijing 100871, PR China;2. Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China;3. College of Chemical Engineering, Inner Mongolia University of Technology, Huhhot 010051, PR China |
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| Abstract: | Iron(II)–dithiocarbamate complexes are used to trap nitrogen monoxide in biological samples, and the resulting nitrosyliron(II)–dithiocarbamate is detected and quantified by ESR. As the chemical properties of these compounds have been little studied, we investigated whether iron dithiocarbamate complexes can redox cycle. The electrode potentials of iron complexes of N-(dithiocarboxy)sarcosine (dtcs) and N-methyl-d-glucamine dithiocarbamate (mgd) are 56 and ?25 mV at pH 7.4, respectively, as measured by cyclic voltammetry. The autoxidation and Fenton reaction of iron(II)–dtcs and iron(II)–mgd were studied by stopped-flow spectrophotometry with both iron(II) complexes and dioxygen or hydrogen peroxide in excess. In the case of excess iron(II)–dtcs and –mgd complexes, the rate constants of the autoxidation and the Fenton reaction are (1.6–3.2) × 104 and (0.7–1.1) × 105 M?1 s?1, respectively. In the presence of nitrogen monoxide, the oxidation of iron(II)–dtcs and iron(II)–mgd by hydrogen peroxide is significantly slower (ca. 10–15 M?1 s?1). The physiological reductants ascorbate, cysteine, and glutathione efficiently reduce iron(III)–dtcs and iron(III)–mgd. Therefore, iron bound to dtcs and mgd can redox cycle between iron(II) and iron(III). The ligands dtcs and mgd are slowly oxidized by hydrogen peroxide with rate constants of 5.0 and 3.8 M?1 s?1, respectively. |
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