FRAGMENTATION OF SMALL GAS PHASE IONS: THEORY & EXPERIMENT

小气相离子的碎裂：理论

• 批准号: 7721417
• 负责人: MICHAEL L GROSS
• 金额: $ 0.23万
• 依托单位: WASHINGTON UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-02-01 至 2009-01-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7721417
• 关键词: Area; Biological; Cations; Computer Retrieval of Information on Scientific Projects Database; Computers; Cyclization; Electrospray Ionization; Funding; Furans; Gases; Goals; Grant; Institution; Ions; Isotope Labeling; Kinetics; Mass Spectrum Analysis; Methods; Modeling; Motivation; Pattern; Pharmaceutical Preparations; Phase; Process; Pyrroles; Reaction; Reagent; Research; Research Personnel; Resources; Solutions; Source; Structure; Thiophene; Thiophenes; United States National Institutes of Health; Work; chemical synthesis; cycloaddition; density; furan; interest; research study; small molecule; theories; tool

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. The mechanisms for fragmentation of small ions that have biological significance are being explored by ab initio and density functional methods. The calculations are executed to obtain thermochemical information, structures, and transition states for fragmentation processes, along with ion-molecule reactions of various small molecule ions and their subsequent patterns of fragmentation. To carry out this work, we have set up a small cluster of Dell computers, which we have expanded in this cycle, that are devoted to these calculations. When needed, we couple the theoretical work with experiments using MS/MS (ion trap, three sector, four sector), kinetic-energy release, isotope labeling, reactivity correlation, and other tools that are important in mechanism studies. This is a unique area of research for Research Resources in the mass spectrometry area, and our goal is to provide a resource for solving interesting mass spectral fragmentation problems that apply to biological molecules. Currently, we are finishing work on interesting cyclization reactions that take place in solution and can be modeled in the gas phase by using ESI, MS/MS, and density functional theory. We are applying a similar approach to possible cycloaddition reactions involving five-membered ring heterocycles (furan, thiophene, pyrrole). The motivation is to explore whether these reactions, which occur very slowly for neutral molecules, can be accelerated by making one of the reagents a radical cation, thus offering opportunities in the chemical synthesis of drugs and related materials.

该子项目是利用该技术的众多研究子项目之一 资源由 NIH/NCRR 资助的中心拨款提供。子项目和 研究者 (PI) 可能已从 NIH 的另一个来源获得主要资金， 因此可以在其他 CRISP 条目中表示。列出的机构是 对于中心来说，它不一定是研究者的机构。 具有生物学意义的小离子的碎裂机制正在通过从头算和密度泛函方法来探索。 执行计算以获得裂解过程的热化学信息、结构和过渡态，以及各种小分子离子的离子-分子反应及其随后的裂解模式。为了开展这项工作，我们建立了一个由戴尔计算机组成的小型集群，并在本周期中对其进行了扩展，专门用于这些计算。 需要时，我们将理论工作与使用 MS/MS（离子阱、三扇区、四扇区）、动能释放、同位素标记、反应性相关性和其他机制研究中重要工具的实验结合起来。 这是质谱领域研究资源的一个独特的研究领域，我们的目标是提供资源来解决适用于生物分子的有趣的质谱碎片问题。 目前，我们正在完成有关在溶液中发生的有趣环化反应的工作，这些反应可以使用 ESI、MS/MS 和密度泛函理论在气相中进行建模。 我们正在将类似的方法应用于涉及五元环杂环（呋喃、噻吩、吡咯）的可能的环加成反应。 其动机是探索是否可以通过将其中一种试剂制成自由基阳离子来加速这些对于中性分子发生非常缓慢的反应，从而为药物和相关材料的化学合成提供机会。