TRIPOD LIGANDS FOR ENZYME MODELS AND ANION COMPLEXATION

配位化学在生物系统中的作用，从 传统的阳离子配位化学，对主客体 阴离子和中性分子的化学，不能被低估。 配位化学和主客体化学在生物中的重要例子 体系的催化性能可以观察到与金属有关 金属酶中的离子，核酸的碱基配对，以及 酶与底物的相互作用。鉴于……的复杂性 生物系统，对较小的合成模型系统的研究可能是 用于提供关键信息，以阐明许多基本信息 生物过程。这项提议的主旨是开发一些新的 模型系统，它将生成有关 阳离子和阴离子物种在生物系统中的作用。 具体目标包括：(1)引入一种用于 建立明确的碳氢化合物的结构和化学模型 脱水酶，一种重要的酶，在呼吸和 细胞内CO2/HCO3平衡，以及(Ii)合成和 新型低配位三脚架受体系统系列的应用 它们被设计成强烈结合，但只与阴离子的一个面结合 底物。这项研究的目的将通过结合 溶液和固态研究。单晶X射线衍射仪 将用于确定金属酶的配位环境 模型，以及中主客交互的详细性质 固态硬盘。~1H、~(13)C和~(17)O核磁共振波谱将进一步提供 金属酶模型的表征以及一种方法 测量动力学和热力学参数。各种各样的 光谱技术(如~(35)C-核磁共振波谱)将被用于 确定关联常数和主客体的强度 互动。将利用标准的化学技术来 研究这些受体系统在以下领域的应用 手性拆分和相转移催化。

The role of coordination chemistry in biological systems, ranging from the traditional coordination chemistry of cations, to the host-guest chemistry of anions and neutral molecules, can not be understated. Important examples of coordination and host-guest chemistry in biological systems can be observed in the catalytic properties associated with metal ions in metalloenzymes, the base-pairing of nucleic acids, and the interaction of enzymes with substrates. In view of the complexity of biological systems, studies on smaller synthetic model systems may be used to provide key information in order to elucidate many fundamental biological processes. The thrust of this proposal is to develop some new model systems that will generate important information regarding the roles of both cationic and anionic species in biological systems. Specific goals include (i) introduction of a modified ligand systems for establishing well-defined structural and chemical models for carbonic anhydrase, an important enzyme with respect to aspects of respiration and intracellular CO2/HCO3- equilibration, and (ii) the synthesis and applications of series of new low-coordinate tripodal receptor systems that are designed to bind strongly, but to only one face of an anionic substrate. The aims of this research will be achieved by a combination of solution and solid-state studies. Single crystal X-ray diffraction will be used to determine coordination environments of the metalloenzyme models and also the detailed nature of the host-guest interaction in the solid state. 1H, 13C and 17O NMR spectroscopy will provide further characterization of the metalloenzyme models and also a means for measuring kinetic and thermodynamic parameters. A variety of spectroscopic techniques (e.g. 35C1 NMR spectroscopy) will be used to determine association constants and the strength of the host-guest interaction. Standard chemical techniques will be utilized to investigate applications of these receptor systems in areas such as chiral resolution and phase transfer catalysis.