Free radical chemistry in green solvents and development of novel spectroscopic techniques to study transient intermediates

绿色溶剂中的自由基化学和研究瞬态中间体的新型光谱技术的开发

• 批准号: 326989-2009
• 负责人: Ghandi, Khashayar
• 金额: $ 2.91万
• 依托单位: Mount Allison University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2010
• 资助国家: 加拿大
• 起止时间: 2010-01-01 至 2011-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=457717
• 关键词: Free; radical; chemistry; green; solvents

We would like to conduct studies of chemical dynamics in room temperature ionic liquids and in sub- and supercritical fluids. Ionic liquids are almost completely made of ions, while a supercritical fluid is any fluid above its critical temperature and pressure where there is no distinct gas and liquid phase. Our studies, in the long term, will give us information that will be useful to design novel industrial processes that are both economical and environmentally-friendly. In particular, we will be able to contribute in finding the optimum thermodynamic conditions for supercritical fluid based processes or types of ionic liquids in ionic liquid based processes. For many of our studies we use muons which from a chemical point of view can be considered as light protons. We would also like to expand a new technique, laser-pump muon probe technique, that we have recently developed to study the Kinetic Isotope Effects of atomic hydrogen reactions in the exited states, to probe transients in ionizing radiation processes, as well as free radical intermediates in excited states. We would also like to develop other novel spectroscopic methods. One such method would be the development of electrochemical-muon spectroscopy techniques in order to produce novel reactive intermediates electrochemically, or using a combination of electrochemical methods followed by muon irradiation. We will then investigate the electronic structure of these reactive intermediates through the coupling of nuclei to unpaired electrons (hyperfine interactions) by muon methods. I will continue to use the interdisciplinary setting and state-of-the-art experimental tools at the two major facilities that we use, TRIUMF national laboratory in Vancouver, Canada, and Rutherford Appleton laboratory in the UK, combined with the computational chemistry methods and conventional lab methods to provide a unique training environment for undergraduate and Master students involved in this research program. For our research on supercritical fluids and ionic liquids, we will focus on providing mechanistic and dynamics information related to free radical chemistry and intermolecular interactions that are relevant to potential chemical and manufacturing industries.

我们想在室温离子液体以及亚临界液中进行化学动力学研究。离子液体几乎完全由离子制成，而超临界流体在没有明显的气相和液相的临界温度和压力之上均高于其临界温度和压力。从长远来看，我们的研究将为我们提供有关设计既经济且环保友好型的新型工业过程非常有用的信息。特别是，我们将能够为基于离子液体的过程中的超临界流体过程或离子液体类型的最佳热力学条件做出贡献。对于我们的许多研究，我们使用的插座可以将其视为光质子。我们还想扩展一种新技术，即激光泵拟探针技术，该技术最近开发了用于研究原子氢反应在退出状态中的动力学同位素效应，以探测电离辐射过程中的瞬变，以及激发态中的自由基中间体。我们还想开发其他新型的光谱法。一种这样的方法是开发电化学膜光谱技术，以便以电化学生产新颖的反应性中间体，或者使用电化学方法的组合，然后是muon辐照。然后，我们将通过MUON方法通过核与未配对电子（超精细相互作用）的偶联来研究这些反应性中间体的电子结构。我将继续使用我们使用的两个主要设施的跨学科环境和最先进的实验工具，即加拿大温哥华的TriumF国家实验室和英国的Rutherford Appleton实验室，并结合计算化学方法和常规实验室方法，可为涉及该研究计划的学生提供独特的培训环境。对于我们对超临界液和离子液体的研究，我们将专注于提供与自由基化学和分子间相互作用有关的机械和动态信息，这些信息与潜在的化学和制造业相关。