Thermochemistry of Noncovalent Interactions and Metal-Ligand Bonds of Biological Relevance

韦恩州立大学的Mary T. Rodgers教授在化学测量和成像（CMI）项目的支持下，利用基于质谱的方法对金属离子或质子化有机碱与配体之间的非共价结合物进行基础研究。这项工作将侧重于获得在生物系统中发挥重要作用的复合物的结构和热化学数据，并在其结合相互作用中显示不同的强度和选择性。关于非共价相互作用的可靠热化学数据的可用性将允许对周期性特性和趋势进行评估，以便对数据进行合理解释，从而更好地了解它们所涉及的生化过程。在此背景下，该项目将为重要的生化过程提供新的基础信息，从而促进我们对生命过程的理解。该项目还将促进基于非共价相互作用的实际应用的发展，并提高该技术的灵敏度，从而扩大其对更复杂系统的适用性。在这项工作中，实验测量将与理论计算相结合，以获得定量的热化学数据以及关于非共价相互作用和生物相关金属配体键的动力学和结构信息。利用引导离子束串联质谱（GIBMS）实验来探测目标物质的能量分辨碰撞诱导解离（CID）行为。将进行电子结构计算，以表征感兴趣的物种的结构和能量学及其CID途径。对实验数据进行热化学分析，以提取在CID上裂解的非共价相互作用或金属配体键的能量和结构信息，以及观察到的激活解离途径的机制和能量屏障。此外，研究小组将继续发展GIBMS仪器和相关的数据分析程序，以便研究更复杂的系统。在进行这项研究的过程中，研究生和本科生将在包括化学、生物化学、化学物理和质谱的多学科研究环境中获得宝贵的经验。由此产生的热化学数据将被汇编成一个基于网络的热化学数据库，并将提供给NIST网络手册和CRC化学和物理手册。

Professor Mary T. Rodgers of Wayne State University is supported by the Chemical Measurement and Imaging (CMI) Program in the Division of Chemistry to use mass spectrometry-based methodologies to conduct fundamental studies on noncovalently bound complexes between metal ions, or protonated organic bases, and ligands. The work will focus on acquiring structural and thermochemical data on complexes that play important roles in biological systems and display different strengths and selectivities in their binding interactions. The availability of reliable thermochemical data on noncovalent interactions will allow periodic properties and trends to be assessed such that rational interpretation of the data will provide an improved understanding of the biochemical processes in which they are involved. In this context, the project will provide new fundamental information on important biochemical processes and hence advance our understanding of life processes. The project will also facilitate the development of practical applications based upon noncovalent interactions and improve the sensitivity of the technique and hence broaden its applicability to more complex systems.In this work, experimental measurements will be combined with theoretical calculations to arrive at quantitative thermochemical data and dynamical and structural information regarding noncovalent interactions and metal-ligand bonds of biological relevance. Guided ion beam tandem mass spectrometry (GIBMS) experiments will be conducted to probe the energy-resolved collision-induced dissociation (CID) behavior of the species of interest. Electronic structure calculations will be undertaken to characterize the structures and energetics of the species of interest and their CID pathways. Thermochemical analysis of the experimental data is performed to extract energetic and structural information on the noncovalent interactions or metal-ligand bonds that are cleaved upon CID and on the mechanisms and energetic barrier(s) for the activated dissociation pathways observed. Furthermore the research team will continue to develop the GIBMS instrument and associated data analysis procedures to enable the study of more complex systems. During the course of conducting this research, graduate and undergraduate students will gain valuable experience in a multidisciplinary research environment encompassing chemistry, biochemistry, chemical physics and mass spectrometry. The resulting thermochemical data will be compiled into a web-based thermochemical database and will be made available to NIST Webbook and the CRC Handbook of Chemistry and Physics.