Thermochemistry of Noncovalent Interactions and Metal-Ligand Bonds of Biological Relevance

非共价相互作用的热化学和生物相关的金属配体键

• 批准号: 1709789
• 负责人: Mary Rodgers
• 金额: $ 47.5万
• 依托单位: Wayne State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1709789&HistoricalAwards=false
• 关键词: Thermochemistry; Noncovalent; Interactions; Metal; Ligand

In this project funded by the Chemical Structure, Dynamics and Mechanisms-A (CSDM-A) Program in the Division of Chemistry, Professor Mary T. Rodgers of Wayne State University is using mass spectrometry techniques to obtain information about the weak interactions that hold two or more molecules together without the formation of a strong "covalent" bond. Covalent bonds involve the actual sharing of electrons between the two molecules. "Non-covalent" interactions are generally weaker than covalent bonds. They play roles such things as the boiling point of liquids and the ability of insects to stick to walls. Professor Rodgers' research focuses on non-covalent interactions relevant to living systems, for example metal atom binding with nucleic molecules (these are constituents of DNA) and the binding of peptide molecules (constituents of proteins). The results of this research may advance our understanding of the chemical basis for biological processes and aid in the design of new technologies for sensing biologically relevant molecules. Graduate and undergraduate students involved in this project are gaining valuable experience in a multidisciplinary research environment encompassing chemistry, biochemistry, chemical physics and mass spectrometry. The resulting thermochemical data are being compiled and made available to the community via a web-based thermochemical database, the National Institutes of Standards and Technology (NIST) Chemistry Webbook and the CRC Handbook of Chemistry and Physics.In this work, experimental measurements and theoretical calculations are synergistically combined to elucidate quantitative thermochemical data and dynamical and structural information regarding noncovalent interactions and metal-ligand bonds of biological relevance. Guided ion beam tandem mass spectrometry (GIBMS) experiments are employed to probe the energy-resolved collision-induced dissociation (CID) behavior of the species of interest. Electronic structure calculations characterize the structures and energetics of the species of interest and their CID pathways. Thermochemical analysis of the experimental data are yielding energetic and structural information on the noncovalent interactions or metal-ligand bonds that are cleaved upon CID and on the mechanisms and energetic barrier(s) for the observed activated dissociation pathways. Continued development of the custom-built GIBMS instrument and associated data analysis procedures is an expected outcome of this work that may enable future studies on increasingly complex systems.

在化学系化学结构、动力学和机理-A（CSDM-A）项目资助的这个项目中，玛丽T。韦恩州立大学的罗杰斯正在使用质谱技术来获得有关弱相互作用的信息，这种弱相互作用将两个或多个分子结合在一起，而不形成强的“共价”键。 共价键涉及两个分子之间电子的实际共享。 “非共价”相互作用通常比共价键弱。 它们扮演着诸如液体的沸点和昆虫粘在墙上的能力等角色。 罗杰斯教授的研究重点是与生命系统相关的非共价相互作用，例如金属原子与核酸分子（这些是DNA的组成部分）的结合和肽分子（蛋白质的组成部分）的结合。 这项研究的结果可能会促进我们对生物过程的化学基础的理解，并有助于设计用于传感生物相关分子的新技术。参与该项目的研究生和本科生在包括化学，生物化学，化学物理和质谱的多学科研究环境中获得宝贵的经验。由此产生的热化学数据正在汇编，并通过基于网络的热化学数据库、美国国家标准与技术研究院（NIST）化学网络手册和CRC化学和物理手册提供给社区。实验测量和理论计算协同结合，以阐明定量的热化学数据和动力学和结构信息有关的非共价相互作用和金属，与生物相关的配体键。引导离子束串联质谱（GIBMS）实验，探测能量分辨碰撞诱导解离（CID）的行为的物种的兴趣。电子结构计算表征感兴趣的物种的结构和能量及其CID途径。热化学分析的实验数据产生的能量和结构信息的非共价相互作用或金属配体键裂解后CID和机制和能量障碍（S）所观察到的活化解离途径。继续开发定制的GIBMS仪器和相关的数据分析程序是这项工作的预期成果，这可能使今后对日益复杂的系统进行研究成为可能。

项目成果

Impact of the 2′- and 3′-Sugar Hydroxyl Moieties on Gas-Phase Nucleoside Structure

• DOI: 10.1007/s13361-019-02155-0
• 发表时间: 2019-03
• 期刊: Journal of The American Society for Mass Spectrometry
• 影响因子: 3.2
• 作者: L. Hamlow;Zachary J. Devereaux;H. Roy;N. A. Cunningham;G. Berden;J. Oomens;M. Rodgers

Structural and Energetic Effects of O2′-Ribose Methylation of Protonated Pyrimidine Nucleosides

质子化嘧啶核苷 O2α-核糖甲基化的结构和能量效应

• DOI: 10.1007/s13361-019-02300-9
• 发表时间: 2019
• 期刊: Journal of The American Society for Mass Spectrometry
• 影响因子: 3.2
• 作者: He, C. C.;Hamlow, L. A.;Zhu, Y.;Nei, Y.-w.;Fan, L.;McNary, C. P.;Maître, P.;Steinmetz, V.;Schindler, B.;Compagnon, I.
• 通讯作者: Compagnon, I.

Protonated Asparaginyl-Alanine Decomposition: a TCID, SORI-CID, and Computational Analysis

质子化天冬酰胺酰丙氨酸分解：TCID、SORI-CID 和计算分析

• DOI: 10.1007/s13361-018-2052-5
• 发表时间: 2018
• 期刊: Journal of The American Society for Mass Spectrometry
• 影响因子: 3.2
• 作者: Boles, Georgia C.;Wu, R. R.;Rodgers, M. T.;Armentrout, P. B.
• 通讯作者: Armentrout, P. B.

Impact of Sodium Cationization on Gas-Phase Conformations of DNA and RNA Cytidine Mononucleotides

• DOI: 10.1007/s13361-019-02274-8
• 发表时间: 2019-09-01
• 期刊: JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
• 影响因子: 3.2
• 作者: Hamlow, L. A.;Nei, Y. -w.;Rodgers, M. T.
• 通讯作者: Rodgers, M. T.

Modified Quadrupole Ion Trap Mass Spectrometer for Infrared Ion Spectroscopy: Application to Protonated Thiated Uridines

• DOI: 10.1007/s13361-018-2047-2
• 发表时间: 2018-11-01
• 期刊: JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
• 影响因子: 3.2
• 作者: Hamlow, L. A.;Zhu, Y.;Rodgers, M. T.
• 通讯作者: Rodgers, M. T.