Transient Intermediates of Electron and Proton Transfer

电子和质子转移的瞬态中间体

• 批准号: 1661815
• 负责人: Frantisek Turecek
• 金额: $ 50.4万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-09-01 至 2021-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1661815&HistoricalAwards=false
• 关键词: Transient; Intermediates; Electron; Proton; Transfer

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Frantisek Turecek of the Department of Chemistry at University of Washington, Seattle, is developing new methods of investigating transient intermediates of chemical reactions involving biologically relevant compounds such as proteins and DNA. Transient intermediates such as ions or chemical radicals occur when proteins and DNA are damaged. Understanding of the chemical processes, their mechanisms, and nature of reactive intermediates associated with ionization and chemical radical damage to proteins and DNA helps to develop improved means for DNA and protein protection and repair. The project lies at the interface of organic, physical, and bioanalytical chemistry, and has a proven record of providing all-round education to scientists at all levels. This research group welcomes students currently or historically underrepresented in science and is well-positioned to provide the highest level of education and training. In addition, the group is active both nation-wide and internationally in fostering collaborations with other research groups and institutes. The research consists of three main aims. In Aim 1, the group combines two techniques, gas-phase electron transfer and UV photodissociation action spectroscopy, to achieve insight into the electronic structure of transient radical intermediates of biological reactions of proteins and nucleic acids. Studying these biomolecules with model systems of limited size, such as peptides and DNA fragments, makes them amenable to computational analysis. Aim 2 concerns the structure and dynamics of non-covalent biomolecular complexes. The approach, which combines experimental mass spectrometry studies with Born-Oppenheimer molecular dynamics calculations, is likely to produce valuable information on the character and magnitude of non-covalent bonding in biomolecular complexes. Aim 3 utilizes a new synthetic coupling reaction for solid-phase peptide derivatization and improves mass-spectrometric analysis with the aim of achieving de novo sequencing of unknown peptides.

在化学结构，动态和机制B计划资助的该项目中，西雅图华盛顿大学化学系的Frantisek Turecek教授正在开发研究的新方法，以研究涉及涉及生物学相关化合物（例如蛋白质和DNA）的化学反应的瞬时中间体。 当蛋白质和DNA受损时，会发生瞬态中间体，例如离子或化学自由基。 了解化学过程，它们的机制以及与电离和化学上对蛋白质和DNA化学自由基损害相关的反应性中间体的性质有助于开发改善的DNA和蛋白质保护和修复的方法。 该项目位于有机，物理和生物分析化学的界面，并在为各个层面的科学家提供全方位教育方面有了可靠的记录。该研究小组欢迎目前或历史上的科学人数不足的学生，并具有良好的位置，以提供最高水平的教育和培训。 此外，该小组在全国和国际上都活跃于与其他研究小组和机构的合作。该研究由三个主要目标组成。在AIM 1中，该组结合了两种技术，即气相电子转移和紫外光解离动作光谱，以深入了解蛋白质和核酸的生物反应的瞬时自由基中间体的电子结构。使用有限尺寸的模型系统（例如肽和DNA片段）研究这些生物分子，使它们可以接受计算分析。 AIM 2涉及非共价生物分子复合物的结构和动力学。该方法将实验性质谱研究与出生的分子动力学计算相结合，可能会产生有关生物分子复合物中非共价键合的特征和幅度的有价值的信息。 AIM 3利用新的合成耦合反应进行固相肽衍生化并改善质谱分析，以实现未知肽的从头测序。

项目成果

Cytosine Radical Cations: A Gas-Phase Study Combining IRMPD Spectroscopy, UVPD Spectroscopy, Ion-Molecule Reactions, and Theoretical Calculations

• DOI: 10.1002/cphc.201700281
• 发表时间: 2017-05-19
• 期刊: CHEMPHYSCHEM
• 影响因子: 2.9
• 作者: Lesslie, Michael;Lawler, John T.;Ryzhov, Victor
• 通讯作者: Ryzhov, Victor

Non-Covalent Interactions of a Neuroprotective Peptide Revealed by Photodissociative Cross-Linking in the Gas Phase

• DOI: 10.1002/chem.201802174
• 发表时间: 2018-07-02
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Liu, Yang;Ramey, Zachary;Turecek, Frantisek
• 通讯作者: Turecek, Frantisek

Near-UV Photodissociation of Tryptic Peptide Cation Radicals. Scope and Effects of Amino Acid Residues and Radical Sites

• DOI: 10.1007/s13361-016-1586-7
• 发表时间: 2017-02
• 期刊: Journal of The American Society for Mass Spectrometry
• 影响因子: 3.2
• 作者: H. T. Nguyen;F. Tureček

Cerium(IV) based oxidative free radical cyclization of active methylene compounds with some cyclic alkenes: A useful annulation method for terpene functionalization

活性亚甲基化合物与某些环状烯烃的基于铈（IV）的氧化自由基环化：一种有用的萜烯官能化环化方法

• DOI: 10.1016/j.tet.2019.03.039
• 发表时间: 2019
• 期刊: Tetrahedron
• 影响因子: 2.1
• 作者: Světlík, Jan;Tureček, František;Hartwich, Katarzyna;Kozieł, Krzysztof;Pakulski, Paweł;Pałasz, Aleksandra;Kalinowska-Tłuścik, Justyna;Cież, Dariusz
• 通讯作者: Cież, Dariusz

Non-covalent complexes of the peptide fragment Gly-Asn-Asn-Gln-Gln-Asn-Tyr in the gas-phase. Photodissociative cross-linking, Born–Oppenheimer molecular dynamics, and ab initio computational binding study

气相中肽片段 Gly-Asn-Asn-Gln-Gln-Asn-Tyr 的非共价复合物。

• DOI: 10.1039/c8cp06893c
• 发表时间: 2019
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Huang, Shu R.;Liu, Yang;Tureček, František
• 通讯作者: Tureček, František