l -半胱氨酸和n -乙酰半胱氨酸与顺式[Pt(en)(H2O)2](ClO4)2相互作用的动力学和机理研究

D. K. Baral, A. Dash, A. Pattanaik, P. Mohanty, M. Nanda
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引用次数: 2

摘要

用分光光度法研究了l -半胱氨酸和n -乙酰半胱氨酸与cs [Pt(en)(OH2)2]2+的反应动力学,作为[Pt(en)(OH2)2]2+ T、[l -半胱氨酸]T/[n -乙酰半胱氨酸]T和pH(4.0)温度的函数,其中Pt(II)络合物主要以双水系存在,l -半胱氨酸和n -乙酰半胱氨酸为两性离子。取代反应呈现两个连续的过程;第一步是配体辅助阳离子化,第二步是螯合。n -乙酰半胱氨酸的氨化速率常数大于l -半胱氨酸。l -半胱氨酸的H1(61.6±1.8 kJ mol−1)、H2(47.5±2.0 kJ mol−1)、S1(- 54.4±5.3 kJ mol−1)和S2(- 164.8±6.5 jk−1 mol−1)和n -乙酰半胱氨酸的H1(23.2±0.8 kJ mol−1)、H2(61.5±0.6 kJ mol−1)和S1(- 178.6±2.6 jk−1 mol−1)、S2(- 115.6±2.0 jk−1 mol−1)表明,在连续的两个步骤中,配体取代过程具有联合激活模式。
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Kinetic and Mechanistic Study of the Interaction of L-cysteine and N-acetylcysteine with cis-[Pt(en)(H2O)2](ClO4)2 in Aqueous Medium
The kinetics of the reactions of L-cysteine and N-acetylcysteine with c s[Pt(en)(OH2)2]2+ have been studied spectrophotometrically as a function of [Pt(en) (OH2)2] 2+ T , [L-cysteine]T/[N-acetylcysteine] T and temperature at pH (4.0) where the Pt(II) complex exists predominantly as a diaqua species and L-cysteine and N-acetylcysteine as zwitterions. The substitution reaction shows two consecutive processes; the first step is the ligand assisted anation and the second one is the chelation step. The anation rate constants for N-acetylcysteine were found to be greater than that for L-cysteine. H1 (61.6 ± 1.8 kJ mol −1) H2 (47.5 ± 2.0 kJ mol −1), S1 (−54.4 ± 5.3 J.K−1 mol−1) and S2 (−164.8 ± 6.5 J.K−1 mol−1) for L-cysteine and H1 (23.2 ± 0.8 kJ mol −1), H2 (61.5 ± 0.6 kJ mol −1) and S1 (−178.6±2.6 J.K−1 mol−1), S2 (−115.6±2.0 J.K−1 mol−1) for N-acetylcysteine indicate an associative mode of activation for both the ligand substitution processes in the two consecutive steps.
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