Bioinspired selective heterogeneous organic photoredox catalysis

仿生选择性多相有机光氧化还原催化

• 批准号: 10580485
• 负责人: Pravas Deria
• 金额: $ 41.86万
• 依托单位: SOUTHERN ILLINOIS UNIVERSITY CARBONDALE
• 依托单位国家: 美国
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-15 至 2025-08-31
• 项目状态: 未结题
• 来源: https://reporter.nih.gov/project-details/10580485
• 关键词: Address; Automobile Driving; Binding Sites; Biochemical; Biological; Biomedical Research; Catalysis; Chemicals; Complex; Descriptor; Development; Diffusion; Economics; Energy Transfer; Engineering; Environment; Enzymes; Exciton; Geometry; Halogens; Harvest; Hydrogen Bonding; Iridium; Knowledge; Lead; Life; Light; Mathematics; Metals; Methodology; Methods; Molecular; Molecular Structure; Oxidation-Reduction; Pathway interactions; Pharmaceutical Preparations; Photosensitizing Agents; Porosity; Process; Property; Reaction; Recycling; Research; Route; Ruthenium; Savings; Science; Series; Site; Solid; Structure; base; biomedical scientist; catalyst; chemical property; chromophore; crystallinity; design; drug discovery; interest; metallicity; migration; molecular assembly/self assembly; molecular recognition; molecular scale; nano; novel; novel therapeutics; quantum; science education; stereochemistry; tool

Project Summary PI: Deria, Pravas Photoredox reactions offer unique opportunities to develop synthetic routes for new drug discoveries that are otherwise unattainable via C-C bond formation through sp3 C-H and C-X (X = halogen) activations. However, current methodologies that employ metallic (such as ruthenium and iridium) complexes or explicit organic photosensitizer (PS) entail two critical challenges relevant to the implementation of atom-economic stereoselectivity (critical for biomedical activity) and easy separability and recyclability (required for large-scale syntheses). Heterogeneous photocatalysts with enzyme-like selectivity are required but remained elusive –mainly due to diffusion-related challenges where, unlike thermally activated transformations, the reactants, substrates, and chirality-inducing groups need to come close within a short (typically nano-to- microsecond) timescale. We propose to address the incumbent challenges with porous crystalline molecular frameworks as a photosensitizer to drive selective catalysis within their well-defined pore cavities. The diffusion-related challenge and relevant photophysical requirements are addressed within certain crystalline metal–organic frameworks (MOFs) where tens of photoactive linkers serve as light-harvesting antennas. The photoexcited energy transfer (also treated as molecular exciton migration), along the preferred direction of the molecular diffusion, can be tuned and primed. Efficient preferential exciton mobility can leverage the need for PS diffusion required to excite the substrates. Therefore, this AREA proposal will pioneer novel MOF compositions that: (i) control optoelectronic properties as a function of framework structure critically required for heterogeneous photoredox catalysis, (ii) elucidate the generality of the MOF photocatalytic reaction and products accessibility, and (iii) unveil the critical microenvironment needed for stereoselective transformations. Endowed with molecular-scale porosity and tunability, MOFs provide scalable, well-defined, modular heterogeneous platforms for fundamental photochemical developments. The methods, combining molecular assemblies to harvest light driving photochemical transformations within its confined, yet selective porous cavity, will provide transferrable and potentially transformative fundamental knowledge for developing recyclable and selective heterogeneous photocatalysts for the discovery of life-saving drugs. Project Summary/Abstract

项目摘要PI：Deria，Pravas Photoredox反应为开发新药的合成路线提供了独特的机会 通过C-C键通过SP3 C-H和C-X形成而无法实现的发现（X =卤素）激活。但是，当前采用金属的方法（例如 和虹膜）复合物或明确的有机光敏剂（PS）需要两个关键挑战 与实施原子经济立体选择性有关（生物医学活动至关重要） 以及易于分离和可回收性（大规模合成所需的）。异源 需要具有类似酶的选择性的光催化剂，但仍然难以捉摸 扩散相关的挑战，与热激活转化不同，反应物， 底物和手性诱导的群体需要在短暂的一小段（通常是纳米到纳米）之内 微秒）时间尺度。我们建议通过多孔晶体解决现有的挑战 分子框架作为光敏剂，以驱动其定义明确的选择性催化 孔咖啡馆。 解决了与扩散有关的挑战和相关的光物理要求 在某些晶体金属有机框架（MOF）中，有数十个光活性接头 用作轻捕获天线。光激发能量传递（也被视为分子 刺激迁移），沿分子扩散的首选方向，可以调节，并且 启动。有效的优先刺激移动性可以利用PS扩散所需的需求 激发底物。因此，该领域的建议将开拓新颖的MOF组成： （i）控制光电属性作为框架结构的函数，至关重要 异质光毒素催化，（ii）阐明了MOF光催化的一般性 反应和产品可及性，（iii）揭示了所需的关键微环境 立体选择性转换。具有分子尺度的孔隙率和可线性，MOF 为基本光化学提供可扩展，定义明确的模块化异构平台 发展。方法结合了分子组件以收获光驱动 其受限但选择性多孔腔内的光化学转换将提供 可转移且潜在的变革性基本知识，用于开发可回收和 选择性的异质光催化剂，用于发现挽救生命的药物。 项目摘要/摘要