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

在这项由实验物理化学计划支持的项目中，韦恩州立大学的玛丽·T·罗杰斯教授和她的团队将进行研究，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。选择用于研究的体系要么具有生物相关性，要么具有分析用途，包括：模型芳香族配体、冠醚、核酸碱基、模型磷酸酯以及与碱、碱土和过渡金属离子相互作用的单核苷酸和二核苷酸。实验技术将包括引导离子束串联质谱(GIBMS)和阈值碰撞诱导解离(TCID)。实验旨在直接测量金属-配体相互作用的绝对强度，或金属-配体络合物激活解离过程的激活能。这些研究还提供了有关这种键活化过程的结构和机理信息，这些信息是通过伴随的理论工作和通过分析分解途径获得的。预计结果将提供关于各种金属-配体络合物的准确热力学信息；这些信息正在汇编到热化学数据库中，从而能够表征和了解周期性质和趋势。生物质谱学是一项快速发展的技术，已经引起了广大研究人员的兴趣。这项研究的结果将有助于该方法的基础，并有助于其持续发展。

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.