典型电极微环境中儿茶酚胺类神经递质氧化机理的理论研究

Catecholamine is an important neurotransmitter in human body, including adrenaline, noradrenaline, and dopamine. The active groups of catecholamine neurotransmitters, such as catechol groups, are sensitive to the microenvironment around electrode surface. By studying the microenvironmental effects, experimental workers have gained much significant phenomenological knowledge in the field of catecholamine. However, as the theoretical study is few, the microscopic nature and law for the function of catecholamine controlled by electrode microenvironment have not been revealed yet. By performing quantum chemistry methods, molecular dynamics, and ONIOM, in this project, we will construct some typical electrode surface microenvironmenal models to study the impact of them on the oxidation ability of catecholamine, clarify the essence of the weak interaction between catecholamine and the common biomolecules in physiological medium, and study the oxidation mechanisms of catecholamine in different electrodes modified with nanometer materials at atomic and molecular level. The research results of the project will deepen the knowledge and understanding to the mechanisms of catecholamine electro-oxidation in different microenvironment, and supply the valuable information and theoretical guidance for the microenvironmental control on the function of catecholamine, the selection of modified electrodes, and the design and development of high-activity catecholamine receptors, respectively.

儿茶酚胺包括肾上腺素、去甲肾上腺素和多巴胺，是人体内一类重要的神经递质。因为含有邻苯二酚等多种活性基团，儿茶酚胺对电极表面附近环境的变化有着高度的敏感性。实验工作者通过对儿茶酚胺微环境效应的研究已经取得了大量有意义的现象学知识。但由于理论研究工作较少，人们尚未揭示出儿茶酚胺功能受电极微环境调控的微观本质和规律。本项目拟以量子化学计算为主要研究方法，结合分子动力学和ONIOM等手段，通过构建各种典型电极表面微环境模型来研究它们对儿茶酚胺氧化能力的影响，弄清儿茶酚胺与生理介质中常见生物分子之间弱相互作用本质，并从原子分子水平上探讨儿茶酚胺在不同纳米材料修饰电极上的氧化机理。项目的研究成果将加深人们对不同电极微环境中儿茶酚胺氧化机理的认识和理解，为儿茶酚胺功能的微环境调控、修饰电极的选择以及高活性儿茶酚胺受体的设计与开发提供有价值的信息和理论参考。

应用量子化学方法，从理论上构建了适合研究儿茶酚胺氧化反应的金电极模型，研究了金电极对儿茶酚胺氧化反应的催化性能，揭示了金电极促进儿茶酚胺氧化的机理，模拟生物体内的生理环境，深入研究了氨基酸、冠醚等生物模型化合物与儿茶酚胺形成的超分子结构及弱相互作用，通过改变儿茶酚胺受体取代基团的方式调节其与儿茶酚胺的弱相互作用，计算了相应的弱相互作用能、吉布斯自由能以及氧化还原电位等数据，定量地分析了生理介质这一微环境因素对儿茶酚胺电化学氧化能力和分子识别作用的影响，完成了项目计划中规划的主要工作。但是对于纳米材料修饰电极促进儿茶酚胺氧化的机理尚需进一步研究。另外，我们研究了一些重要的有机催化反应，如：1）NHC催化反应中的选择性和活性问题；2）不同催化剂对有机环化反应的影响以及催化环化异构化选择性问题；3）C-H 键的催化活化问题；4）添加物和溶剂等对反应选择性影响的问题，等等。

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