Transient Intermediates of Electron and Proton Transfer

电子和质子转移的瞬态中间体

基本信息

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

项目摘要

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.

在这个由化学部化学结构、动力学和机理 B 项目资助的项目中，西雅图华盛顿大学化学系的 Frantisek Turecek 教授正在开发新方法来研究涉及生物相关化合物的化学反应的瞬时中间体，例如如蛋白质和DNA。当蛋白质和 DNA 受损时，会产生离子或化学自由基等瞬态中间体。了解化学过程、其机制以及与蛋白质和 DNA 的电离和化学自由基损伤相关的反应中间体的性质，有助于开发改进的 DNA 和蛋白质保护和修复方法。该项目位于有机化学、物理化学和生物分析化学的交叉领域，并在为各级科学家提供全面教育方面拥有良好的记录。该研究小组欢迎目前或历史上在科学领域代表性不足的学生，并有能力提供最高水平的教育和培训。此外，该小组在全国和国际范围内积极促进与其他研究小组和机构的合作。该研究包括三个主要目标。在目标1中，该小组结合了气相电子转移和紫外光解作用光谱两种技术，以深入了解蛋白质和核酸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，使它们能够进行计算分析。目标 2 涉及非共价生物分子复合物的结构和动力学。该方法将实验质谱研究与玻恩-奥本海默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的特征和大小的有价值的信息。 Aim 3利用新的合成偶联反应进行固相肽衍生化，并改进质谱分析，旨在实现未知肽的从头测序。

项目成果

期刊论文数量（23）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

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
通讯作者：
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。