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Third-Order Kinetics for Interaction of Glutathione with a Dinuclear Pd(II) Complex and Their Mechanism, DNA Binding and DFT Study

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Abstract

A kinetics and mechanistic study of the interaction between the bridged dimer \( [{\text{Pd}}({\text{pic}})({\text{OH}})]_{2}^{2 + } \) (where pic = 2-aminomethylpyridine) and glutathione (GSH) has been performed under pseudo-first order conditions using a stopped-flow spectrophotometer. The reaction follows a distinctive third-order kinetics via two consecutive steps. The first step follows the rate law kobs = k1[GSH]2, whereas step two is independent of the GSH concentration. The activation parameters, ΔH‡ and ΔS‡ for both steps, were determined and an associative mode of activation is suggested for the substitution process. Geometry optimizations and HOMO–LUMO energy calculations were done by DFT. The UV spectra of the complexes were compared with theoretically obtained TD-DFT spectra. Complex 2 and 3 interact non-covalently with calf-thymus DNA with binding constants (Kb and KSV) of the order of 104 L·mol−1.

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Acknowledgements

The authors are thankful to National Institute of Technology, Durgapur-713209, and to DST, Government of India for providing financial assistance (Project No. EEQ/2017/000077), and Vienna University of Technology, Vienna, Austria for providing the necessary laboratory assistance, particularly their stopped-flow spectrophotometer facility to follow the fast kinetics of the Pd(II) complex in this work. The authors I. Mitra and S. Mukherjee are thankful to DST-INSPIRE, Government of India for their research fellowship. Also, thanks are due to the reviewers for their valuable suggestions to improve the manuscript.

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  1. Department of Chemistry, National Institute of Technology Durgapur, Durgapur, 713209, W.B., India

    Avradeep Samanta, Ishani Mitra, Subhajit Mukherjee, B. Venkata P. Reddy, Sujay Mahata, Goutam Kr. Ghosh, Sankar Ch. Moi & Abhisake Karmakar

  2. Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt, 9/163 AC, 1060, Vienna, Austria

    Bashkim Misini & Wolfgang Linert

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  1. Avradeep Samanta
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Correspondence to Sankar Ch. Moi.

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Samanta, A., Mitra, I., Mukherjee, S. et al. Third-Order Kinetics for Interaction of Glutathione with a Dinuclear Pd(II) Complex and Their Mechanism, DNA Binding and DFT Study. J Solution Chem 47, 1139–1156 (2018). https://doi.org/10.1007/s10953-018-0783-3

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