Thermochemistry of Metal-Ligand Bonds and Protonated Peptides

金属-配体键和质子化肽的热化学

• 批准号: 2313553
• 负责人: Peter Armentrout
• 金额: $ 55万
• 依托单位: University of Utah
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-15 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2313553&HistoricalAwards=false
• 关键词: Thermochemistry; Metal; Ligand; Bonds; Protonated

With support from the Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) program in the Division of Chemistry, Professor Peter B. Armentrout and his group at the University of Utah will use a guided ion beam tandem mass spectrometer coupled with electrospray, flow tube, and ion mobility sources to study gas-phase organometallic and biological ion chemistry. These studies will seek to examine the complex challenges associated with quantifying the chemistry of excited electronic states of transition metal cations and determining absolute energies differences between specific conformations of biomolecular ions. Professor Armentrout and his students will investigate angular momentum effects in collision-induced dissociation experiments, state-specific chemistry of transition metal (TM) ions, energetics for decomposition of protonated peptides along with their structures, as well as species formed by transition metal activation of C-H bonds involving methane and larger hydrocarbons. Their studies could lead to better understandings of spin-orbit coupling effects in reactions of transition metal ions, peptide degradation processes especially for conformation-specific energetics, and industrially important C-H bond activation and C-C coupling processes. In addition to these broader impacts in science, the work performed will also further the education of an informed science, technology, engineering, and mathematics (STEM) workforce, including both graduate and undergraduate students. Under this award, the Armentrout group at the University of Utah will examine several interrelated areas; a recently developed IM source will be enhanced by the addition of novel ion sources and a compact SLIM (structures for lossless ion manipulation) device for enhanced resolution. The IM source will be used to study state-specific chemistry of TM ions and the energetics for decomposition of conformer-specific protonated peptides. The latter processes are important in understanding analytical applications for protein sequence identification and will experimentally establish the true ground conformer for the first time. Systems of focus will include those containing asparagine, where deamidation is believed to be a major molecular process contributing to aging and the onset of neurodegenerative diseases. Infrared action spectroscopy will be used to determine structures of biological systems as well as to probe structures of species formed by CH bond activation and CC coupling reactions of TM cations with hydrocarbons. All areas of study will be complemented by theoretical calculations. Potentially transformative studies include quantitative characterization of spin-orbit coupling effects, absolute measurements of energy differences between conformations, and methane activation processes. In all these endeavors, the studies will provide thermodynamic data and educate future scientists.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学结构，动力学和机制-A（CSDM-A）计划中的支持下，彼得·B·AarmentRout教授及其在犹他大学的小组将使用带导的离子光束串联质谱仪与电腐蚀，流管和流动管迁移率一起研究气体实体和生物学有机化化学的化学方法。这些研究将试图检查与量化过渡金属阳离子激发电子状态的化学关系相关的复杂挑战，并确定生物分子离子特定构象之间的绝对能量差异。 ArmentRout教授及其学生将研究碰撞引起的解离实验，过渡金属的州特异性化学（TM）离​​子，质子化肽及其结构的分解的能量，以及由涉及甲烷和较大氢键的C-H键形成的物种。他们的研究可能导致对过渡金属离子反应，肽降解过程的自旋轨道耦合效应的更好理解，尤其是对于构象特异性能量学以及工业上重要的C-H键激活和C-C耦合过程。除了在科学方面产生更广泛的影响外，所做的工作还将进一步教育知情的科学，技术，工程和数学（STEM）劳动力，包括研究生和本科生。根据该奖项，犹他大学的ArmentRout小组将研究几个相互关联的领域。 通过添加新型离子源和一种紧凑的纤薄（无损离子操纵结构）设备以增强分辨率，将增强最近开发的IM源。 IM来源将用于研究TM离子的特异性化学和用于构象异构特异性质子化肽的分解的能量。后一个过程对于理解蛋白质序列识别的分析应用很重要，并将首次实验建立真实的地面构象体。重点系统将包括含有天冬酰胺的系统，其中脱氨化被认为是导致衰老和神经退行性疾病发作的主要分子过程。红外作用光谱将用于确定生物系统的结构以及由CH键激活形成的物种的探测结构和TM阳离子与碳氢化合物的CC偶联反应。所有研究领域将由理论计算补充。潜在的变革性研究包括自旋轨道耦合效应的定量表征，构象之间能量差异的绝对测量以及甲烷激活过程。在所有这些努力中，这些研究将提供热力学数据并教育未来的科学家。该奖项反映了NSF的法定任务，并使用基金会的知识分子优点和更广泛的影响审查标准，被认为值得通过评估来提供支持。

项目成果

IR spectroscopic characterization of products of methane and cyclopropane activation by Ru cations

Ru 阳离子活化甲烷和环丙烷产物的红外光谱表征

• DOI: 10.1016/j.ijms.2023.117165
• 发表时间: 2024
• 期刊: International Journal of Mass Spectrometry
• 影响因子: 1.8
• 作者: Wensink, Frank J.;Pradeep, Deepak;Armentrout, P.B.;Bakker, Joost M.
• 通讯作者: Bakker, Joost M.

Quantitative Aspects of Gas-Phase Metal Ion Chemistry: Conservation of Spin, Participation of f Orbitals, and C–H Activation and C–C Coupling

气相金属离子化学的定量方面：自旋守恒、f 轨道参与、C–H 激活和 C–C 偶联

• DOI: 10.1021/acs.jpca.3c06023
• 发表时间: 2023
• 期刊: The Journal of Physical Chemistry A
• 作者: Armentrout, P. B.

Infrared multiple photon dissociation spectra of cesiated complexes of the aliphatic amino acids: Challenges for conformational-space calculations by density functional theory

脂肪族氨基酸铯配合物的红外多光子解离光谱：密度泛函理论构象空间计算的挑战

• DOI: 10.1016/j.ijms.2024.117201
• 发表时间: 2024
• 期刊: International Journal of Mass Spectrometry
• 影响因子: 1.8
• 作者: Armentrout, P.B.;Steele, Ryan P.;Stevenson, Brandon C.;Jones, Roland M.;Martens, Jonathan;Berden, Giel;Oomens, Jos
• 通讯作者: Oomens, Jos

Determining gas-phase chelation of zinc, cadmium, and copper cations with HisHis dipeptide using action spectroscopy and theoretical calculations

使用作用光谱和理论计算测定锌、镉和铜阳离子与组氨酸二肽的气相螯合

• DOI: 10.1016/j.ijms.2023.117154
• 发表时间: 2024
• 期刊: International Journal of Mass Spectrometry
• 影响因子: 1.8
• 作者: Stevenson, Brandon C.;Berden, Giel;Martens, Jonathan;Oomens, Jos;Armentrout, P.B.
• 通讯作者: Armentrout, P.B.