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.

该奖项由化学学部实验物理化学项目资助，资助犹他大学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以及化学动力学。这项工作利用了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热和超热能下的绝对反应概率，然后对所得到的与动能相关的截面进行详细分析而得到的。目前正在研究化学相互作用的四个相关领域。首先，第三行过渡金属离子被设计用来测量与各种氢、氧和碳配体的键解离能（BDEs）的化学性质。将研究第二和第三行TM离子的状态特异性化学，重点是自旋轨道耦合（SOC）效应的定量评估。其次，定量评估多重带电金属离子的溶剂化能，并开发出明确量化此类体系中电荷分离通道势能面的方法。第三，探索金属离子与生物相关分子之间的BDEs，并将其扩展到质子化肽分解的能量学。第四，阈值碰撞诱导解离（TCID）的分析日益庞大和复杂的系统涉及多个竞争和顺序路径将继续发展。在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有关。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，这被认为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，这涉及到一些学生（本科生，研究生和博士后），他们充分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，目前全世界有几十个实验室在使用这些手段。