RUI: Kinetic and Mechanistic Studies of Reactive Intermediates in Solution and Confined Environments.

在化学系有机动力学项目的支持下，Peter de Lijser教授提出的研究将提供关于氧肟和相关化合物光氧化过程中形成的高能中间体的结构和反应性的动力学和机理信息。这些活性中间体，肟自由基阳离子，以及由它们衍生的其他活性氧或活性氮，如亚胺氧基和亚胺基自由基，将在溶液中以及在密闭环境（沸石）中进行研究，以便为活性中间体提供额外的稳定性。本课题的主要研究目标是：1)研究肟基阳离子的结构-反应性关系。这将需要PI和他的研究小组找到直接观察这些反应性中间体的条件。醛肟和酮肟都将被研究，醛肟形成腈是特别感兴趣的。2)探讨肟醚的结构-反应性关系，特别是这些物种在氮上发生亲核加成或取代的假设。PI的工作将集中在分子内反应上。3)选择性地生成和研究亚胺氧基和亚胺氧基自由基，这两种自由基分别是酮肟和醛肟光氧化的中间体。肟类及相关化合物已被用作杀虫剂和药物。将这些化学物质释放到环境中（包括植物和高等动物的细胞和组织）可能导致光化学（敏化或直接）或酶氧化，从而形成活性中间体，如自由基离子和自由基。这类物质的化学性质和潜在危险实际上是未知的，因此需要精确的动力学和其他反应性数据，以便形成一个一般的结构-反应性模式。从这些基本的机械和动力学研究中获得的知识将为理解实验观察奠定基础。这项研究还将提供急需的工具，以成功地利用自由基离子和其他高能物质进行新的化学合成过程，并可能在材料应用中。建议的研究也将为学生提供一个优秀的教育经验。学生将学习基本的化学实验室原理，如如何合成，纯化，并通过光谱技术表征化合物。此外，他们将在学习机械方法和高级问题技能方面接受扎实的教育。学生还将接受非传统技术和领域的培训，如电化学、计算化学和纳秒瞬态吸收光谱；最后一项将通过新购买的激光闪光光解仪器来实现，该仪器的资金来自该奖项。de Lijser教授继续建立他的记录，增加本科生参与科学活动。加州州立大学富勒顿分校的化学与生物化学系（CSUF）长期以来一直被认为提供严格和现代的课程，以响应未来的发展，反映化学科学的跨学科性质和多样性，使学生成为成功的专业人士、学者和科学素养的公民。由于加州州立大学提供了相当大比例的技术劳动力、教师和研究生申请者，让学生接触现代研究方法和环境将维持地区、州和国家的化学科学本科生和硕士学生的教育和培训能力。

With support of the Organic Dynamics Program in the Chemistry Division, Professor Peter de Lijser's proposed research will provide kinetic and mechanistic information on structure and reactivity of high-energy intermediates formed in the photooxidation of oximes and related compounds. These reactive intermediates, oxime radical cations, and other reactive oxygen or nitrogen species derived from these, such as iminoxyl and iminoyl radicals, will be studied in solution as well as in a confined environment (zeolites) in order to provide extra stabilization for the reactive intermediates. The proposal's primary research goals are: 1)To investigate the structure-reactivity relationships of oxime radical cations. This will require the PI and his research group to find conditions to observe these reactive intermediates directly. Both aldoxime and ketoximes will be studied and the formation of nitriles from aldoximes is of specific interest. 2)To probe the structure-reactivity relationships of oxime ethers, specifically the hypothesis that these species undergo nucleophilic addition or substitution at nitrogen. The PI's efforts will be focused on intramolecular reactions. 3)To selectively generate and study iminoxyl and iminoyl radicals, which are the proposed intermediates in the photooxidation of ketoximes and aldoximes, respectively.Oximes and related compounds have found use as pesticides and drugs. Release of these chemicals into the environment (including cells and tissue of plants and higher animals) may result in photochemical (sensitized or direct) or enzymatic oxidations leading to the formation of reactive intermediates such as radical ions and radicals. The chemistry and potential dangers of these types of species are virtually unknown, and there exists a need for accurate kinetic and other reactivity data so that a general structure-reactivity pattern can be developed. The knowledge gained from these fundamental mechanistic and kinetic studies will establish a foundation for understanding experimental observations. The research will also provide much-needed tools to successfully utilize radical ions and other high-energy species for new chemical processes in synthesis and possibly in materials applications.The proposed research will also provide an outstanding educational experience for students. Students will learn basic chemical laboratory principles such as how to synthesize, purify, and characterize compounds by means of spectroscopic techniques. Additionally, they will receive a solid education in learning mechanistic methodologies and advanced problem skills. Students will also receive training in less traditional techniques and areas such as electrochemistry, computational chemistry and nanosecond transient absorption spectroscopy; the last will be achieved by means of the newly purchased laser flash photolysis instrumentation with funds from this award. Professor de Lijser continues to build on his track record for increasing involvement of undergraduate students in scientific activities. The Department of Chemistry and Biochemistry at California State University, Fullerton (CSUF) has long been recognized as offering a rigorous and contemporary curriculum that is responsive to future developments, reflects the interdisciplinary nature and diversity of the chemical science and enables students to become successful professionals, scholars, and scientifically literate citizens. Because the CSU provides a substantial percentage of the technical workforce, teachers and graduate student applicants in California, exposing students to modern research methods and environments will sustain regional, state-wide and national capabilities for education and training of undergraduates and Masters' students in the chemical sciences.