Bioinspired selective heterogeneous organic photoredox catalysis
仿生选择性多相有机光氧化还原催化
基本信息
- 批准号:10580485
- 负责人:
- 金额:$ 41.86万
- 依托单位:
- 依托单位国家:美国
- 项目类别:
- 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:
- 关键词:AddressAutomobile DrivingBinding SitesBiochemicalBiologicalBiomedical ResearchCatalysisChemicalsComplexDescriptorDevelopmentDiffusionEconomicsEnergy TransferEngineeringEnvironmentEnzymesExcitonGeometryHalogensHarvestHydrogen BondingIridiumKnowledgeLeadLifeLightMathematicsMetalsMethodologyMethodsMolecularMolecular StructureOxidation-ReductionPathway interactionsPharmaceutical PreparationsPhotosensitizing AgentsPorosityProcessPropertyReactionRecyclingResearchRouteRutheniumSavingsScienceSeriesSiteSolidStructurebasebiomedical scientistcatalystchemical propertychromophorecrystallinitydesigndrug discoveryinterestmetallicitymigrationmolecular assembly/self assemblymolecular recognitionmolecular scalenanonovelnovel therapeuticsquantumscience educationstereochemistrytool
项目摘要
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
项目总结PI:Deria,Pravas
光氧化还原反应为开发新药合成路线提供了独特的机会
通过sp3 C-H和C-X(X)形成C-C键,
=卤素)活化。然而,采用金属(例如钌)的当前方法学并不适用。
和铱)络合物或显式有机光敏剂(PS)需要两个关键挑战
与实现原子经济立体选择性有关(对生物医学活动至关重要)
和易于分离和再循环(大规模合成所需)。异构
需要具有酶样选择性的光催化剂,但仍然难以捉摸-主要是由于
与扩散相关的挑战,与热活化转化不同,反应物,
衬底和手性诱导基团需要在短(通常是纳米到纳米)内接近。
微秒)时标。我们建议用多孔晶体来解决现有的挑战
分子框架作为光敏剂,以在其明确定义的范围内驱动选择性催化
孔隙
讨论了与扩散有关的挑战和相关的生物物理要求
在某些晶体金属有机框架(MOFs)中,
充当捕光天线。光激发能量转移(也被视为分子
激子迁移),沿着分子扩散的优选方向,可以被调节并
准备好了有效的优先激子迁移率可以利用PS扩散的需要,
激发基质。因此,该区域提案将开创新的MOF组合物,该组合物:
(i)控制光电性能作为关键所需的框架结构的函数,
非均相光氧化还原催化,(ii)阐明MOF光催化的一般性
反应和产品的可及性,以及(iii)揭示关键微环境所需的
立体选择性转化。MOFs具有分子尺度的多孔性和可调谐性,
提供可扩展的、定义明确的、模块化的异构平台,
发展理念该方法,结合分子组件来收获光驱动,
在其有限的,但选择性的多孔腔中的光化学转化,将提供
可转让和潜在的变革性基础知识,用于开发可回收和
选择性多相光催化剂用于发现拯救生命的药物。
项目总结/摘要
项目成果
期刊论文数量(0)
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Pravas Deria的其他文献
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