The Physical Chemistry-Structures, Energetics, and Reactions-of Self Assembled Metal Cationized Complexes in the Gas Phase

Fridgen小组在研究质子或金属阳离子结合的自组装复合物的物理化学方面享有国际声誉。他们将新型的俘获离子质谱分析方法与基于计算机的工具相结合，以预测其复合物的物理性质，并与实验观察结果进行比较。Fridgen小组使用的实验方法包括振动光谱学、由环境黑体红外辐射激活的解离动力学、碰撞诱导解离和捕获离子的离子-分子反应。所研究的复合物通常由核酸碱基、蛋白质生成和非蛋白质生成的氨基酸以及多肽组成。他们研究了由多个核酸碱甚至多个金属阳离子组成的大型离子配合物的结构和能量学。这些复合物的研究对于我们理解自组装生物材料的物理化学具有重要意义。分子间和分子内的相互作用，通常比普通的化学键弱，负责这些复合物的结构以及它们的组装动力学。研究的复合体也具有生物学意义，例如在针对端粒的癌症和衰老研究中。提出的目的之一是研究核酸碱基通过金属阳离子与氨基酸和肽络合的内在结构、能量学和光谱，这些被认为与诱导基因的遗传毒性和抑制有关。目的二涉及通过振动光谱或通过监测配合物的物理或化学活化产物来研究包封离子配合物。这些研究将为分子开关技术和宿主跨膜传递物质（如药物）的发展提供重要的基础知识。第三个目标是研究质子化的新烟碱及其与金属阳离子的配合物。新烟碱类杀虫剂不仅因其化学成分而令人感兴趣，而且由于对蜜蜂种群的有害影响，许多新烟碱类杀虫剂已被禁止使用。我们对新烟碱-金属阳离子配合物的结构和反应性研究将对杀虫剂化合物的分析产生影响，并很可能为修复受其影响的环境或其分解副产物提供可能的途径。本提案中所述的研究计划将培养出具有广泛技能和对分子水平化学有深刻理解的高素质人才。他们的教育将为他们未来的职业生涯做好准备，成为基础和应用研究领域的科学家，为物理和生物科学、医学等领域做出贡献，并为质谱等分析技术的进步做出贡献。

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.