CAS: Photochemistry of spatially confined organic molecules

CAS：空间受限有机分子的光化学

• 批准号: 2204046
• 负责人: Vaidhyanathan Ramamurthy
• 金额: $ 61万
• 依托单位: University of Miami
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2026-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2204046&HistoricalAwards=false
• 关键词: CAS; Photochemistry; spatially; confined; organic

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Prof. Vaidhyanathan Ramamurthy of University of Miami, taking the cue from nature, aims to find ways to control the behavior of light activated molecules by confining them in cavities that are just slightly larger than them. With the current emphasis on sustainability and safety, his undertaking will use light as the energy source and water as the solvent. The long term goal is to find efficient ways to capture and store the inexhaustible solar energy into chemical energy. This interdisciplinary research project, which involves US and international collaborations, provides a unique platform for training graduate students on different aspects of light activated chemistry. Recognizing the importance of making the young researchers aware of the pathways involved in developing new science, Prof. Ramamurthy will present lectures in an open forum titled ‘Being a Scientist’ that include information on the roles of a discoverer and the time-line of the discoveries along with contextual placement of the concepts. He will continue to organize weekly online informal lecturers by active research scientists that have already proven to be of great value to students and young researchers working at smaller and underprivileged Institutions all over the world.The main goal of this research project is to find ways to perform useful and selective reactions under sustainable conditions without involving toxic reagents and solvents. This study employing light as the energy source and water as the solvent integrates supramolecular principles. Water-soluble synthetic hosts with cavity dimensions of a few angstroms will be utilized as reaction containers for organic molecules that are not water-soluble. The overarching goal of this program is to finding conditions under which light activated reactions that would yield high-value products could be carried out in a selective, sustainable and catalytic fashion. The reactions to be explored would include synthetically useful and mechanistically interesting addition, electron- and proton transfer initiated transformations, fragmentation reactions, oxidations etc. To get an insight into the above processes mechanistic studies that include ultrafast spectroscopic experiments and theoretical calculations will be performed.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.

在化学系大分子、超分子和纳米化学项目的支持下，迈阿密大学的vaidyhyanathan Ramamurthy教授从大自然中获得灵感，旨在找到控制光激活分子行为的方法，方法是将它们限制在比它们稍微大一点的空腔中。由于目前对可持续性和安全性的重视，他的事业将以光为能源，水为溶剂。长期目标是找到有效的方法，将取之不尽、用之不竭的太阳能捕获并储存为化学能。这个涉及美国和国际合作的跨学科研究项目，为培养光活化化学不同方面的研究生提供了一个独特的平台。Ramamurthy教授认识到让年轻研究人员意识到发展新科学的途径的重要性，他将在一个名为“成为一名科学家”的开放论坛上发表讲座，内容包括发现者的角色、发现的时间线以及概念的背景定位。他将继续组织每周由活跃的研究科学家举办的在线非正式讲座，这些讲座已经被证明对在世界各地较小和贫困机构工作的学生和年轻研究人员有很大的价值。本研究项目的主要目标是寻找在可持续条件下进行有用和选择性反应的方法，而不涉及有毒试剂和溶剂。本研究以光为能源，以水为溶剂，结合超分子原理。具有几埃空腔尺寸的水溶性合成载体将被用作非水溶性有机分子的反应容器。该项目的总体目标是寻找条件，在这种条件下，光激活反应可以以选择性、可持续和催化的方式产生高价值的产品。要探索的反应将包括合成上有用的和机械上有趣的加成反应、电子和质子转移引发的转化、裂解反应、氧化反应等。为了深入了解上述过程，将进行包括超快光谱实验和理论计算在内的机理研究。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值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

Role of supramolecular steric compression during photoinduced intramolecular hydrogen abstraction reactions of ketones and thioketones

超分子空间压缩在酮和硫酮光诱导分子内夺氢反应中的作用

• DOI: 10.1016/j.jphotochem.2022.114442
• 发表时间: 2023
• 期刊: Journal of Photochemistry and Photobiology A: Chemistry
• 作者: Khadka, Dipendra;Kulasekharan, Revathy;Ramamurthy, Vaidhyanathan
• 通讯作者: Ramamurthy, Vaidhyanathan