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• W2052682112 abstract "AbstractOH-radicals were generated by pulse radiolysis of aqueous solutions of rabbit (Zn,Cd)-metallothionein (MT). They react with MT mainly by forming a thiyl radical with a rate constant of 1·7 × 1012 dm3 mol−1 s−1. The thiyl radical reacts rapidly but reversibly with a thiolate function to form RSSR.−: RS. + RS− RSSR.−. The kinetics of the formation and decay of this radical anion have been studied pulse radiolytically by monitoring the evolution of the optical absorption of RSSR.− at 450 nm. This process is mostly intermolecular, i.e. bimolecular in MT. In the absence of O2, RSSR.− decays bimolecularly: RSSR.− + RS. RSSR + RS−. In the presence of O2, RS. may be scavenged by O2 and thus the yield of RSSR.− decreases: RS. + O2 RSOO.. Under these conditions RSSR.− decays by first-order kinetics: RSSR.− + O2 RSSR + O.−2. The rate constants of these reactions have been determined at room temperature: k4 = 1·8 × 109 dm3 mol−1 s−1, k5 = 7 × 104 s−1, k10 = 9·2 × 108 dm3 mol−1 s−1, and k18 about 3 × 107 dm3 mol−1 s−1. From the dependence of the maximal absorbance at 450 nm on the thiolate concentration in the absence of oxygen, ϵ(RSSR.−) = 9 × 103 dm3 mol−1 cm−1 and the stability constant (K4/5) of 2·3 × 104 dm3 ml−1 was determined. K4/5 is in good agreement with that determined kinetically, k4/k5 = 2·6 × 104 dm3 mol−1. The stability constant K15/16 of the thiylperoxyl radical, RSOO., was determined to be 5·5 × 103 dm3 mol−1." @default.
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• W2052682112 date "1995-01-01" @default.
• W2052682112 modified "2023-09-26" @default.
• W2052682112 title "Generation and Reactions of the Disulphide Radical Anion Derived from Metallothionein: A Pulse Radiolytic Study" @default.
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• W2052682112 doi "https://doi.org/10.1080/09553009514551421" @default.
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