MEDIUM EFFECTS ON CONFORMATIONAL ISOMERISM

对构象异构的中等影响

• 批准号: 3277618
• 负责人: NANCY S TRUE
• 金额: $ 7.9万
• 依托单位: UNIVERSITY OF CALIFORNIA AT DAVIS
• 依托单位国家: 美国
• 财政年份: 1982
• 资助国家: 美国
• 起止时间: 1982-02-01 至 1988-01-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3277618
• 关键词: amides; chemical group; conformation; cyclic amine; diazo compound; ketones; microwave spectrometry; nuclear magnetic resonance spectroscopy; phase change; thermodynamics

We propose complementary gas and liquid phase NMR studies of conformational equilibria and conformational dynamics in both polar and nonpolar cyclic and acyclic molecules which model biologically important functional groups. This research is aimed at elucidating the direction and extent of solvent perturbations on torsional potential functions and conformational processes. Below we will demonstrate that for many model compounds such as amides, cyclic amines, and diazoketones it is possible with techniques we have recently developed to measure the temperature dependence of conformer populations and interconversion rates in the gas phase with NMR spectroscopy to yield a complete set of thermodynamic and kinetic parameters characterizing each conformational process. Comparison with corresponding liquid phase results will allow elucidation of the magnitude of intrinsic and environmental contributions to each internal rotation potential function. For each class of compounds, a series of molecules with systematic variations in substituent size and polarity will be investigated. Intramolecular effects on torsional potentials and conformational dynamics will be probed by comparison of gas phase thermo-dynamic and kinetic data within each series. Intermolecular effects will be probed by comparison of gas and solution data for each molecule within a series. Complementary microwave spectral data will provide additional structural and dynamic information. These studies will yield widely applicable parameters for solvent contribution to torsional potentials of biologically important functional groups and their associated conformational equilibria and dynamics. This information is essential for progress in elucidating molecular potentials, dynamics and mechanisms of conformational processes in biomolecules.

我们提出了构象的气相和液态核磁共振互补研究。 极性和非极性环中的平衡和构象动力学 以及模拟具有重要生物学意义的官能团的非环分子 组。这项研究的目的是阐明人类社会发展的方向和程度 扭势函数和构象上的溶剂微扰 流程。下面我们将演示许多模型化合物，例如 酰胺、环胺和重氮酮通过我们的技术 最近开发了测量构象的温度依赖性的方法 用核磁共振研究气相中的布居数和相互转化率 光谱学产生一套完整的热力学和动力学 表征每个构象过程的参数。与 相应的液相结果将有助于阐明其大小 对每一次内部旋转的内在和环境贡献 势函数。 对于每一类化合物，一系列具有系统性的分子 将研究取代基大小和极性的变化。 扭势和构象动力学的分子内效应 将通过气相热力学和动力学数据的比较来探讨 在每个系列中。将通过比较分子间效应来探讨分子间效应 一系列中每个分子的气体和溶液数据。互补性 微波光谱数据将提供额外的结构和动态 信息。这些研究将产生广泛适用的参数 溶剂对生物重要分子扭转势的贡献 官能团及其相关的构象平衡和 动力学。这一信息对于阐明 构象过程的分子势能、动力学和机理 在生物分子中。