Thermochemistry of Metal-Ligand Bonds (Singly and Multiply Charged) and Protonated Peptides

在这个奖项，由化学系的实验物理化学计划，教授彼得B资助。犹他州大学的Armentrout教授、他的博士后研究员、研究生和本科生将获得资助，研究气相有机金属和生物离子化学以及化学动力学。这项工作利用引导离子束串联质谱（GIBMS）。详细的动力学和热力学数据是通过精确测量绝对反应概率在热和超热能量，然后通过详细的分析所获得的动能依赖的横截面。 正在研究四个相关的化学相互作用领域。首先，第三行过渡金属离子的化学设计测量键离解能（BDE）与各种氢，氧，碳配体将被追求。第二和第三行TM离子的状态特定的化学将被研究，重点是自旋轨道耦合（SOC）效应的定量评价。第二，溶剂化能的多电荷金属离子将进行定量评估和明确的量化的势能面在这样的系统中的电荷分离通道的方法将被开发。第三，将探索金属离子和生物相关分子之间的溴化二苯醚，并将其扩展到质子化肽分解的能量学。第四，将继续开展涉及多个竞争性和顺序性途径的日益庞大和复杂的系统的阈值碰撞诱导解离（TCID）分析，这些研究中获得的热力学信息与表面科学、有机金属化学、催化、可持续能源、环境和生物系统以及健康相关。例如，一个特别感兴趣的系统是阐明天冬酰胺脱酰胺的能量学，认为这是导致衰老的主要分子过程。 该研究计划的一个关键组成部分是其教育目标，涉及一些学生（本科生，研究生和博士后），他们完全参与研究计划的各个方面。用于分析数据的手段是免费提供的，目前被世界各地的数十个实验室使用。

In this award, funded by the Experimental Physical Chemistry Program of the Division of Chemistry, Professor Peter B. Armentrout of the University of Utah, his post-doctoral fellows, graduate, and undergraduate students will be supported to study gas-phase organometallic and biological ion chemistry and chemical dynamics. The work utilizes guided ion beam tandem mass spectrometry (GIBMS). Detailed kinetic and thermodynamic data are obtained by accurately measuring absolute reaction probabilities at thermal and hyperthermal energies followed by a detailed analysis of the kinetic energy dependent cross sections obtained. Four related areas of chemical interactions are being studied. First, the chemistry of 3rd row transition metal ions designed to measure bond dissociation energies (BDEs) with various hydrogen, oxygen, and carbon ligands will be pursued. State-specific chemistry of 2nd and 3rd row TM ions will be studied with an emphasis on a quantitative evaluation of spin-orbit coupling (SOC) effects. Second, solvation energies of multiply charged metal ions will be quantitatively assessed and methods for explicit quantification of the potential energy surface for charge separation channels in such systems will be developed. Third, BDEs between metal ions and biologically relevant molecules will be explored and expanded to the energetics for decomposition of protonated peptides. Fourth, analysis of threshold collision-induced dissociation (TCID) of increasingly large and complex systems involving multiple competitive and sequential pathways will continue to be developed.The thermodynamic information acquired in these studies is of relevance to surface science, organometallic chemistry, catalysis, sustainable energy, environmental and biological systems, as well as health. For example, one system of particular interest is elucidation of the energetics for the deamidation of asparagine, believed to be a major molecular process contributing to aging. A key component of this research program is its educational objectives, which involve a number of students (undergraduate, graduate, and postdoctoral) who are fully engaged in all aspects of the research program. The means used to analyze the data are made freely available and are presently used by dozens of laboratories worldwide.