一类新的氨基酸基配合物的合成、结构和电化学性质。

J. M. Rey, Federico Movilla, S. Suárez, Florencia Di Salvo
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引用次数: 0

摘要

金属蛋白参与新陈代谢的氧化还原过程,是每个生物体健康的基础。利用氨基酸基化合物作为配体来构建仿生配位体系是开发新型催化剂的一个很有前途的选择。本文提出了一个新的铜、锌和镍配位化合物家族,它们具有四、五和六配位的几何形状,是由l -丙氨酸和l -苯丙氨酸得到的席夫碱配体合成的。利用单晶x射线衍射数据、光谱和电化学实验以及DFT计算进行了结构分析和性能研究。分子和超分子结构分析表明,体系中发生的非共价相互作用,以及金属和氨基酸主链的身份,是配合物形成和合成几何结构稳定的决定因素。对CuII配合物作为亚硝酸盐电化学转化还原为NO的候选物进行了测试,发现五配位l -苯丙氨酸配合物是最合适的。最后,对构建仿生配合物配体的合理设计提出了一些见解。
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Synthesis, structural and electrochemical properties of a new family of amino-acid-based coordination complexes.
Metalloproteins involved in oxidation-reduction processes in metabolism are fundamental for the wellbeing of every organism. The use of amino-acid-based compounds as ligands for the construction of biomimetic coordination systems represents a promising alternative for the development of new catalysts. Herein is presented a new family of copper, zinc and nickel coordination compounds, which show four-, five- and six- coordination geometries, synthesized using Schiff base ligands obtained from the amino acids L-alanine and L-phenylalanine. Structural analysis and property studies were performed using single-crystal X-ray diffraction data, spectroscopic and electrochemical experiments and DFT calculations. The analysis of the molecular and supramolecular architectures showed that the non-covalent interactions developed in the systems, together with the identity of the metal and the amino acid backbone, are determinants for the formation of the complexes and the stabilization of the resultant geometries. The CuII complexes were tested as candidates for the electrochemical conversion reduction of nitrite to NO, finding that the five-coordinate L-phenylalanine complex is the most suitable. Finally, some insights into the rational design of ligands for the construction of biomimetic complexes are suggested.
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