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

金属-配体键（单电荷和多电荷）和质子化肽的热化学

• 批准号: 0748790
• 负责人: Peter Armentrout
• 金额: $ 66.3万
• 依托单位: University of Utah
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-03-01 至 2011-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0748790&HistoricalAwards=false
• 关键词: Thermochemistry; Metal; Ligand; Bonds; Singly

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.

该奖项由化学系实验物理化学项目资助，将支持犹他大学Peter B. Armentrout教授及其博士后、研究生和本科生研究气相有机金属和生物离子化学和化学动力学。该工作利用引导离子束串联质谱（GIBMS）。通过精确测量热能和超热能下的绝对反应概率，然后对所获得的动能相关横截面进行详细分析，获得详细的动力学和热力学数据。 正在研究化学相互作用的四个相关领域。首先，将研究旨在测量各种氢、氧和碳配体的键解离能（BDE）的第三行过渡金属离子的化学性质。将研究第二行和第三行TM离子的特定状态化学，重点是自旋轨道耦合（SOC）效应的定量评估。其次，将定量评估多电荷金属离子的溶剂化能，并开发明确量化此类系统中电荷分离通道的势能表面的方法。第三，金属离子和生物相关分子之间的 BDE 将被探索并扩展到质子化肽分解的能量学。第四，将继续开发涉及多个竞争性和顺序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，一个特别令人感兴趣的系统是阐明天冬酰胺脱酰胺的能量学，天冬酰胺被认为是导致衰老的主要分子过程。 该研究项目的一个关键组成部分是其教育目标，其中涉及大量学生（本科生、研究生和博士后），他们充分参与研究项目的各个方面。用于分析数据的方法是免费提供的，目前已被全球数十个实验室使用。