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

在实验物理化学计划资助的这个项目中，玛丽T.韦恩州立大学的罗杰斯和她的小组将进行研究，旨在获得关于金属离子和配体之间非共价相互作用的绝对定量热化学，动力学和结构信息。 选择用于研究的系统具有生物相关性或分析实用性，并且包括：模型芳香配体、冠醚、核酸碱基、模型磷酸酯以及与碱金属、碱土金属和过渡金属离子相互作用的单核苷酸和二核苷酸。 实验技术包括引导离子束串联质谱（GIBMS）和阈值碰撞诱导解离（TCID），直接测量金属-配体相互作用的绝对强度或金属-配体络合物活化解离过程的活化能。 这些研究还提供了结构和机制的信息，这些键的活化过程中获得的形式伴随的理论工作，并通过分解途径的分析。 结果预计将提供准确的热力学信息的各种各样的金属配位体络合物，这些信息正在被编译成热化学数据库，这将使周期性的特性和趋势的表征和理解。生物质谱是一种快速发展和不断发展的技术，已经引起了广泛的研究人员的兴趣。这项研究的结果将有助于该方法的基础，并增加其持续发展。

In this project supported by the Experimental Physical Chemistry Program, Professor Mary T. Rodgers of Wayne State University and her group will carry out research designed to obtain absolute quantitative thermochemical, dynamical, and structural information regarding noncovalent interactions between metal ions and ligands. The systems chosen for study are of either biological relevance or analytical utility and include: model aromatic ligands, crown ethers, nucleic acid bases, model phosphate esters, and mono- and dinucleotides interacting with alkali, alkaline-earth, and transition metal ions. Experimental techniques will include guided ion-beam tandem mass spectrometry (GIBMS)and threshold collision-induced dissociation (TCID).The experiments are designed to measure directly either the absolute strength of the metal-ligand interaction, or the activation energy for activated dissociation processes of the metal-ligand complexes. These studies also provide structural and mechanistic information regarding such bond activation processes obtained in the form of concomitant theoretical work and through the analysis of decomposition pathways. Outcomes are expected to provide accurate thermodynamic information on a wide variety of metal-ligand complexes; this information is being compiled into thermochemical databases that will enable the characterization and understanding of periodic properties and trends. Biological mass spectrometry is a rapidly growing and evolving technology that has captured the interest of a broad community of researchers. Outcomes from this research will contribute to the underpinnings of the methodology, and add to its continuing development.