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

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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.