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

基本信息

批准号：
1954142
负责人：
Peter Armentrout
金额：
$ 65万
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：
2020
资助国家：
美国
起止时间：
2020-09-01 至 2023-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954142&HistoricalAwards=false
关键词：
Thermochemistry Metal Ligand Bonds Singly

项目摘要

In this project funded by the Chemical Structure, Dynamics, and Mechanisms A (CSDM-A) program of the Chemistry Division, Professor Peter B. Armentrout and his students at the University of Utah are exploring the structure and reactivity of various molecules in the gas-phase, including metal cations (“cation” means positively charged) and complexes composed of metal cations and other molecules such as water (H2O), carbon monoxide (CO) and biologically relevant amino acids and peptides. These studies are being conducted in the gas phase because it is important to understand the inherent structure and properties of these molecular systems, in other words in the absence of the countless water molecules they would encounter in an aqueous solution. The Armentrout research group is actually developing new techniques to deliver charged molecules and complexes into the gas phase, either free of water or with a selected number of water molecules or other organic solvent molecules. The research includes four main thrusts: how strongly bound are solvent molecules to doubly charged metals? How does the reactivity of a molecular ion change when its electrons are excited by laser light or collisions? How do ionized peptides decompose, and what are the molecular structures of decomposition products? Such information is valuable in developing new catalytic systems, in understanding biological function (including effects on health), and in environmental remediation efforts. In all cases, these experimental studies are complemented by theoretical examinations of the same phenomena. Students engaged in this research project are gaining valuable experience in state-of-the-art physical and analytical methods, including a technique called guided ion beam mass spectrometry (GIBMS), and quantum mechanical calculations.The research is conducted using two types of instrumentation. Thermodynamic experiments are enabled by using a guided ion beam tandem mass spectrometer that permits measurement of absolute reaction cross sections as a function of kinetic energy. This enables the direct measurement of the energies required for cationized peptides to decompose or for desolvation of metal dications or metal hydroxide cations. This apparatus is also being fitted with an ion mobility source that allows separation of metal cations in different electronic states or of different conformers of cationized peptides. This instrumental combination enables quantitative studies of spin-orbit coupling effects and direct measurements of the energetic differences between different conformers, both of which are potentially transformative studies. Structural studies involve the use of infrared multiple photon dissociation spectroscopy conducted at the FELIX facility in the Netherlands, which include experiments concerning cationized peptides and alkane activation by metal cations. Broader impacts of these studies include a better understanding of how to elicit sequence information in proteins, providing thermodynamic benchmarks for theory, and elucidating mechanistic information regarding transition metal catalysis, in addition to the educational aspects of involving both undergraduate and graduate students in a full range of experimental and theoretical work. A software package (CRUNCH) developed to obtain thermochemical information from the experiments is undergoing continuous updates and refinement and continues to be made available to other groups interested in mass spectrometry based thermodynamic measurements.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.

在该项目中，化学部门的化学结构，动力学和机制A（CSDM-A）计划（CSDM-A）计划，彼得·B·ArmentRout教授及其犹他大学的学生正在探索气相中各种分子的结构和反应性，包括金属阳离子（包括阳离子阳离子）（阳离子式载体）和其他分子材料（如金属杂种）（赫2型，赫2）。（CO）和与生物学相关的氨基酸和肽。这些研究是在气相进行的，因为重要的是要了解这些分子系统的内部结构和特性，换句话说，在没有无数的水分子中，它们在水溶液中会遇到。实际上，ArmentRout研究小组正在开发新技术，以将带电的分子和复合物传递到无水或选定数量的水分子或其他有机溶解性分子的气相中。这项研究包括四个主要推力：溶剂分子与双电荷金属有多大约束？当分子离子电子被激光或碰撞激发时，分子离子的反应性如何变化？离子辣椒如何分解，分解产物的分子结构是什么？此类信息对于开发新的催化系统，了解生物学功能（包括对健康的影响）以及环境补救工作很有价值。在所有情况下，这些实验研究都是通过对同一现象的理论检查完成的。从事该研究项目的学生正在获得最先进的物理和分析方法的价值经验，包括一种称为引导离子束质谱法（GIBM）和量子机械计算的技术。该研究是使用两种仪器进行的。通过使用引导的离子束串联质谱仪来启用热力学实验，该量子质谱仪允许测量绝对反应横截面随动能的函数。这可以直接测量阳离子肽分解或脱脱脱脱裂所需的能量。该设备还配备了一个离子迁移率来源，该离子迁移率允许在不同电子状态或阳离子肽的不同构象中分离金属阳离子。这种仪器组合可以对自旋轨道耦合效应和对不同构象异构体之间能量差的直接测量进行定量研究，这两者都是潜在的转化性研究。结构研究涉及在荷兰Felix设施进行的红外多个光子解离光谱，其中包括有关金属阳离子的阳离子辣椒和烷烃激活的实验。这些研究的更广泛影响包括更好地了解如何在蛋白质中引起蛋白质中的序列信息，为理论提供热力学基准，并阐明有关过渡金属催化的机械信息，此外，还包括涉及本科和研究生的教育方面。开发的软件包（CRUNCH）是为了从实验中获取热化学信息而开发的，正在进行不断的更新和完善，并继续向对基于质谱的热力学测量感兴趣的其他群体提供，该奖项反映了NSF的法定任务，并通过基金会的知识优点和广泛的影响来通过评估来诚实地通过评估来诚实地进行评估。

项目成果

期刊论文数量（28）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Cis-trans isomerization is not rate determining for b2 ion structures: A guided ion beam and computational study of the decomposition of H+(GlyProAla)

顺反异构化不是 b2 离子结构的速率决定：A 引导离子束和 H (GlyProAla) 分解的计算研究

DOI：
10.1016/j.ijms.2020.116434
发表时间：
2020
期刊：
International Journal of Mass Spectrometry
影响因子：
1.8
作者：
Jones, Roland M.;Boles, Georgia C.;Armentrout, P.B.
通讯作者：
Armentrout, P.B.

Comment on “Gas-phase ion-molecule interactions in a collision reaction cell with triple quadrupole-inductively coupled plasma mass spectrometry: Investigations with N2O as the reaction gas” by Khadouja Harouaka, Caleb Allen, Eric Bylaska, Richard M Cox,

Khadouja Harouaka、Caleb Allen、Eric Bylaska、Richard M Cox 评论“采用三重四极杆电感耦合等离子体质谱的碰撞反应池中的气相离子-分子相互作用：以 N2O 作为反应气体的研究”，

DOI：
10.1016/j.sab.2021.106345
发表时间：
2021
期刊：
Spectrochimica Acta Part B: Atomic Spectroscopy
影响因子：
0
作者：
Armentrout, P.B.
通讯作者：
Armentrout, P.B.

Influence of a Hydroxyl Group on the Deamidation and Dehydration Reactions of Protonated Asparagine-Serine Investigated by Combined Spectroscopic, Guided Ion Beam, and Theoretical Approaches

通过结合光谱、引导离子束和理论方法研究羟基对质子化天冬酰胺-丝氨酸脱酰胺和脱水反应的影响

DOI：
10.1021/jasms.0c00468
发表时间：
2021
期刊：
Journal of the American Society for Mass Spectrometry
影响因子：
3.2
作者：
Boles, Georgia C.;Kempkes, Lisanne J.;Martens, Jonathan;Berden, Giel;Oomens, Jos;Armentrout, P. B.
通讯作者：
Armentrout, P. B.

Infrared multiple photon dissociation action spectroscopy of protonated unsymmetrical dimethylhydrazine and proton-bound dimers of hydrazine and unsymmetrical dimethylhydrazine

质子化不对称二甲肼以及肼和不对称二甲肼质子结合二聚体的红外多光子解离作用光谱

DOI：
10.1039/d1cp03781a
发表时间：
2021
期刊：
Physical Chemistry Chemical Physics
影响因子：
3.3
作者：
McNary, Christopher P.;Demireva, Maria;Martens, Jonathan;Berden, Giel;Oomens, Jos;Hamlow, L. A.;Rodgers, M. T.;Armentrout, P. B.
通讯作者：
Armentrout, P. B.

Periodic trends in gas‐phase oxidation and hydrogenation reactions of lanthanides and 5d transition metal cations

镧系元素和 5d 过渡金属阳离子气相氧化和氢化反应的周期性趋势