Elucidating the Organic-OMS Interface and Its Implications for Solid Enantioselective Catalysts

阐明有机-OMS 界面及其对固体对映选择性催化剂的影响

• 批准号: 0624813
• 负责人: Daniel Shantz
• 金额: $ 19.1万
• 依托单位: Texas A&M Engineering Experiment Station
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-09-15 至 2010-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0624813&HistoricalAwards=false
• 关键词: Elucidating; Organic; OMS; Interface; Its

AbstractProposal Title: Elucidating the Organic-OMS Interface and Its Implications for Solid Enantioselective Catalysts Proposal Number: CTS-0624813Principal Investigator: Daniel ShantzInstitution: Texas Engineering Experiment StationAnalysis (rationale for decision):Ordered Mesoporous Silica (OMS) organic hybrids have attracted great interest as potential heterogeneous analogues of homogeneous catalysts. This project will lead to a rigorous description of the inorganic-organic interface by using solid-state nuclear magnetic resonance (NMR) spectroscopy to determine: (1) the rotational mobility of groups attached to OMS surfaces, and (2) the local structure and conformation of the organic group with respect to the OMS surface. When coupled with catalytic testing, this work will show how structure and dynamics at the nanometer length scale influence reactivity, leading to new design paradigms for hybrid materials and their use in catalysis. This work will investigate chemically simple functional groups such as alkylamine groups attached to surfaces, surface tethered homogeneous catalysts such as Schiff bases (e.g. Al-salen), and short peptides which are of interest for enantioselective organocatalysis. The intellectual merit of this work is fourfold. A molecular description of the local structure (first) and dynamics (second) of organic groups covalently attached to ordered mesoporous silica surfaces and how they are affected by surface hydrophobicity, loading, and solvation is lacking. This type of information is essential to designing organic-inorganic interfaces in materials that are catalytically relevant. Third, how reactivity is modified by these local structural phenomena is not understood. Fourth, this knowledge will provide new paradigms for rationally designing organic-inorganic interfaces in general, and organic layers on ordered mesoporous silica for catalysis in particular.The broader impact of this work is also fourfold. First, the ability to relate local structure and dynamics to function will lead to more efficient design of organic-inorganic hybrids. The work proposed here relates specifically to organocatalysis and enantioselective reactions but will also be generally relevant to researchers in catalysis as well as impact fields including molecular recognition and separations. Second, the ability to design enantioselective solid catalysts, particularly those without a metal center, will have implications for both the fine chemicals and pharmaceutical industries. Third, the curriculum development will introduce Chemical Engineers to solid-state NMR methods. Fourth, this research will involve undergraduate students through existing programs on the Texas A&M campus and the results of this work will also be disseminated through a K-12 program.

摘要提案标题：阐明有机-OMS 界面及其对固体对映选择性催化剂的影响提案编号：CTS-0624813 首席研究员：Daniel Shantz 机构：德克萨斯工程实验站分析（决定理由）：有序介孔二氧化硅 (OMS) 有机杂化物引起了人们的极大兴趣均相催化剂的潜在多相类似物。 该项目将通过使用固态核磁共振 (NMR) 光谱来对无机-有机界面进行严格的描述，以确定：(1) 附着在 OMS 表面的基团的旋转迁移率，以及 (2) 局部结构和有机基团相对于 OMS 表面的构象。 与催化测试相结合，这项工作将展示纳米长度尺度的结构和动力学如何影响反应性，从而为混合材料及其在催化中的应用带来新的设计范例。 这项工作将研究化学上简单的官能团，例如附着在表面的烷基胺基团、表面束缚的均相催化剂，例如希夫碱（例如 Al-salen），以及对映选择性有机催化感兴趣的短肽。 这项工作的智力价值有四个方面。 缺乏对共价连接到有序介孔二氧化硅表面的有机基团的局部结构（第一）和动力学（第二）以及它们如何受到表面疏水性、负载和溶剂化的影响的分子描述。 此类信息对于设计催化相关材料中的有机-无机界面至关重要。 第三，这些局部结构现象如何改变反应性尚不清楚。 第四，这些知识将为合理设计有机-无机界面，特别是用于催化的有序介孔二氧化硅上的有机层提供新的范例。这项工作的更广泛的影响也是四重的。 首先，将局部结构和动力学与功能联系起来的能力将有助于更有效地设计有机-无机杂化物。 这里提出的工作具体涉及有机催化和对映选择性反应，但通常也与催化以及分子识别和分离等影响领域的研究人员相关。 其次，设计对映选择性固体催化剂的能力，特别是那些没有金属中心的催化剂，将对精细化学品和制药行业产生影响。 第三，课程开发将向化学工程师介绍固态核磁共振方法。 第四，这项研究将通过德克萨斯农工大学校园现有的项目让本科生参与，这项工作的结果也将通过 K-12 项目进行传播。