RUI: Isotopically Different Tunneling-Ready-State Structures in Hydride Transfer Reactions in Solution

RUI：溶液中氢化物转移反应中同位素不同的隧道就绪态结构

• 批准号: 1800194
• 负责人: Yun Lu
• 金额: $ 32万
• 依托单位: Southern Illinois University at Edwardsville
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800194&HistoricalAwards=false
• 关键词: RUI; Isotopically; Different; Tunneling; Ready

In this project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professors Yun Lu, James E. Eilers, and Kevin R. Tucker of the Department of Chemistry at Southern Illinois University Edwardsville are investigating how reactions in the human body work. Hydrogen transfer reactions are common in chemistry and biology. About 50% of the biological reactions in the body involve hydrogen transfer. This project may help scientists understand these biological processes. The project involves expertise in three different areas of chemistry (organic, analytical and computational). The chemistry department at Southern Illinois University Edwardsville (SIUE) holds workshops that target high school teachers in the St. Louis Metro-East area, which has a large African-American population living below the poverty line. This program provides an opportunity for the research teams to involve the high school teachers and their students in the project, preparing them for college and a STEM career. The project investigates a new concept in the contemporary models for hydrogen (H)-wave transfer, i.e., H-tunneling. The new concept is that H-tunneling and its heavier isotope (deuterium (D) or tritium (T))-tunneling have different donor-acceptor distance (DAD) at the tunneling-ready-state (TRS) structures due to different masses thus different wave properties. Since a heavier isotope possesses shorter wavelength, its transfer requires a shorter donor-acceptor distance (DAD). The confirmation of the concept could change the traditional views about the H-transfer chemistry and the theory of the kinetic isotope effects (KIE). The investigators use physical organic mechanistic analysis methods to distinguish the isotopically different TRS structures for various hydride- vs. deuteride-transfer reactions in solution. They plan to study the primary isotope dependence of the secondary KIEs to distinguish the isotopically different TRS conformations. They also investigate the primary isotope dependence of Hammett correlations to differentiate the isotopically different TRS electronic structures.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.

在这个由化学系化学结构、动力学和机理B计划资助的项目中，南伊利诺伊大学爱德华兹维尔大学化学系的卢云教授、詹姆斯·E·埃尔斯教授和凯文·R·塔克教授正在研究人体内的反应是如何工作的。氢转移反应在化学和生物中都很常见。人体内约50%的生物反应涉及氢转移。这个项目可能会帮助科学家了解这些生物过程。该项目涉及化学的三个不同领域(有机、分析和计算)的专业知识。南伊利诺伊大学爱德华兹维尔(SIUE)化学系举办研讨会，目标是圣路易斯大都会东部地区的高中教师，该地区有大量非裔美国人生活在贫困线以下。该计划为研究团队提供了一个机会，让高中教师和他们的学生参与到这个项目中来，为他们进入大学和STEM职业生涯做好准备。该项目研究了当代氢(H)波传输模型中的一个新概念，即H隧道效应。新的概念是，由于不同的质量和不同的波性质，氢隧穿及其较重的同位素(氚(D)或氚(T))隧穿在隧道就绪(TRS)结构上具有不同的施主-受体距离(DAD)。由于较重的同位素具有较短的波长，其转移所需的施主-受主距离(DAD)较短。这一概念的确立将改变人们对氢转移化学和动力学同位素效应理论的传统看法。研究人员使用物理有机机理分析方法来区分溶液中不同的氢化物与重氢转移反应的同位素不同的TRS结构。他们计划研究次级KIE的初级同位素依赖性，以区分不同同位素构象的TRS。他们还调查了Hammett关联的主要同位素相关性，以区分不同的同位素不同的TRS电子结构。这一裁决反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Direct Correlation between Donor–Acceptor Distance and Temperature Dependence of Kinetic Isotope Effects in Hydride-Tunneling Reactions of NADH/NAD + Analogues

NADH/NAD 类似物氢化物隧道反应中供体-受体距离与动力学同位素效应的温度依赖性之间的直接相关性

• DOI: 10.1021/acs.joc.1c00497
• 发表时间: 2021
• 期刊: The Journal of Organic Chemistry
• 作者: Bai, Mingxuan;Koirala, Shailendra;Lu, Yun
• 通讯作者: Lu, Yun

Substituent Effects on Temperature Dependence of Kinetic Isotope Effects in Hydride-Transfer Reactions of NADH/NAD + Analogues in Solution: Reaction Center Rigidity Is the Key

溶液中 NADH/NAD 类似物氢化物转移反应中取代基对动力学同位素效应温度依赖性的影响：反应中心刚性是关键

• DOI: 10.1021/acs.orglett.0c02049
• 发表时间: 2020
• 期刊: Organic Letters
• 影响因子: 5.2
• 作者: Maness, Peter;Koirala, Shailendra;Adhikari, Pratichhya;Salimraftar, Nasim;Lu, Yun
• 通讯作者: Lu, Yun

Hydride transfer tunneling-ready-state structure as a function of donor-acceptor distance: A full gating coordinate for the vibrational tunneling-ready-state

氢化物传输隧道准备状态结构作为供体-受体距离的函数：振动隧道准备状态的完整门控坐标

• DOI: 10.1016/j.chemphys.2019.03.003
• 发表时间: 2019
• 期刊: Chemical Physics
• 影响因子: 2.3
• 作者: Sakhaee, Nader;Ackad, Edward;Lu, Yun
• 通讯作者: Lu, Yun

Imbalanced Transition States from α-H/D and Remote β-Type N -CH/D Secondary Kinetic Isotope Effects on the NADH/NAD + Analogues in Their Hydride Tunneling Reactions in Solution

α-H/D 和远程 β-型 N -CH/D 二次动力学同位素对 NADH/NAD 类似物在溶液中氢化物隧道反应中的不平衡过渡态影响

• DOI: 10.1021/acs.joc.9b00412
• 发表时间: 2019
• 期刊: The Journal of Organic Chemistry
• 作者: Ma, Li;Sakhaee, Nader;Jafari, Shabnam;Wilhelm, Samantha;Rahmani, Paniz;Lu, Yun
• 通讯作者: Lu, Yun