Grant: Discovery Grants Program - Individual

The Fridgen group has an international reputation for their work studying the physical chemistry of self-assembled complexes bound by protons or metal cations. They use a combination of novel trapped-ion mass spectrometry methods coupled with computer-based tools to predict the physical properties of their complexes and compare with their experimental observations. The experimental methods that the Fridgen group uses includes vibrational spectroscopy, dissociation kinetics activated by ambient blackbody infrared radiation, collision-induced dissociation, and ion-molecule reactions of trapped ions. The complexes of study are typically composed of nucleic acid bases, proteinogenic and non-proteinogenic amino acids, and peptides. They have studied the structures and energetics of large ionic complexes composed of many nucleic acid bases and even multiple metal cations. The study of these complexes is important for our understanding of the physical chemistry of self-assembled biomaterials. Inter and intramolecular interactions, typically weaker than normal chemical bonds, are responsible for the structure of these complexes as well as the dynamics of their assembly. The complexes of study also have biological relevance, for example in cancer and aging research aimed at telomeres. Objective one of the proposed is the study of the intrinsic structures, energetics, and spectroscopy of nucleic acid bases complexing with amino acids and peptides through metal cations, and which are believed to be involved in genotoxicity and repression of inducible genes. Objective two involves the study of encapsulated ionic complexes by vibrational spectroscopy or by monitoring the products of physical or chemical activation of the complexes. These studies will provide fundamental knowledge important in molecular switch technology and the development of hosts to deliver substances, such as drugs, across membranes. A third objective is the study of protonated neonicotinoids and complexes with metal cations. Besides being fundamentally interesting because of their chemical make up, neonicotinoids are pesticides, many of which have been banned due to their harmful effects on bee populations in the world. Our structural and reactivity studies on neonicotinoid-metal cation complexes will have an impact on the analysis of insecticide compounds and could very well lead to possible routes for remediation of environments impacted by them or their decomposition byproducts. The research plan described in this proposal will produce highly qualified personnel with broad skills and a deep understanding of chemistry at the molecular level. Their education will prepare them for future careers as scientists in fundamental and applied research, contributing to fields such as the physical and biological sciences, medicine, and contributing to the advancement of analytical technologies such as mass spectrometry.