Mechanistic insights into the redox reactions of chromium complexes containing picolinates as ligands, interaction with biomolecules

IF 1.7 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Transition Metal Chemistry Pub Date : 2025-01-31 DOI:10.1007/s11243-025-00635-9

Mildred Rodríguez-Cordero, Vito Lubes, Hector Roman, Joe Berroteran, Fernando Hernández-Medina, William Castro

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Abstract

Proton-coupled electron transfer (PCET) is a common reaction in biological systems, with potential implications for DNA damage and repair. This study showed that tris-(2-pyridine carboxylate) chromium (III) (complex 1) exhibited an increased electrochemical reaction rate in the presence of a strong acid, suggesting that PCET via proton donation promotes the reduction reaction. Conversely, complex 1 with picolinic acid showed a decreased electrochemical exchange constant, suggesting kinetic control by slow electronic exchange, consistent with PCET. Bis(pyridine-2,6-dicarboxylate) chromate (III) of sodium (complex 2), showed potential shifts and broadening of signals in the presence of dipicolinic and ascorbic acids, further supporting the involvement of PCET. Overall, the study highlighted the modulation of the electrochemical behavior of the chromium complexes through proton-coupled shifts in reduction potentials and kinetics, shedding light on their potential interactions with cellular reductant agents and protons. The weaker interactions of complexes 1 and 2 with BSA and DNA, together with their lower bioavailability and solubility compared to CQDP, contribute to our understanding of the potential biological effects of the chromium complexes studied. This abstract provides a comprehensive overview of the results of the study, highlighting the significance of the PCET reactions and their potential implications for biological processes and health effects.

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以吡啶甲酸酯为配体的铬配合物氧化还原反应的机理及与生物分子的相互作用

质子耦合电子转移（PCET）是生物系统中常见的反应，对DNA损伤和修复具有潜在的意义。本研究表明，三-（2-吡啶羧酸盐）铬（III）（配合物1）在强酸存在下的电化学反应速率增加，表明PCET通过质子捐赠促进了还原反应。相反，配合物1与吡啶酸的电化学交换常数降低，表明通过缓慢的电子交换进行动力学控制，与PCET一致。钠的二（吡啶-2,6-二羧酸盐）铬酸盐（III）（配合物2）在二吡啶酸和抗坏血酸存在时显示出电位变化和信号拓宽，进一步支持PCET的参与。总的来说，该研究强调了通过还原电位和动力学的质子耦合位移对铬配合物的电化学行为的调节，揭示了它们与细胞还原剂和质子的潜在相互作用。与CQDP相比，配合物1和2与BSA和DNA的相互作用较弱，生物利用度和溶解度也较低，这有助于我们了解所研究的铬配合物的潜在生物学效应。该摘要提供了研究结果的全面概述，强调了PCET反应的重要性及其对生物过程和健康影响的潜在影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Transition Metal Chemistry 化学-无机化学与核化学

CiteScore

3.60

自引率

0.00%

发文量

审稿时长

1.3 months

期刊介绍： Transition Metal Chemistry is an international journal designed to deal with all aspects of the subject embodied in the title: the preparation of transition metal-based molecular compounds of all kinds (including complexes of the Group 12 elements), their structural, physical, kinetic, catalytic and biological properties, their use in chemical synthesis as well as their application in the widest context, their role in naturally occurring systems etc. Manuscripts submitted to the journal should be of broad appeal to the readership and for this reason, papers which are confined to more specialised studies such as the measurement of solution phase equilibria or thermal decomposition studies, or papers which include extensive material on f-block elements, or papers dealing with non-molecular materials, will not normally be considered for publication. Work describing new ligands or coordination geometries must provide sufficient evidence for the confident assignment of structural formulae; this will usually take the form of one or more X-ray crystal structures.