Quantitative analysis of extremely strong contiguous hydrogen bond arrays

极强连续氢键阵列的定量分析

• 批准号: EP/G013519/1
• 负责人: David Leigh
• 金额: $ 47.21万
• 依托单位: University of Edinburgh
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2009
• 资助国家: 英国
• 起止时间: 2009 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FG013519%2F1
• 关键词: Quantitative; analysis; extremely; strong; contiguous

We propose a programme to quantitatively investigate the thermodynamics and kinetics of the strongest hydrogen bonded small molecule complexes known. AAA-DDD triple hydrogen bond arrays can be up to a hundred million times stronger than the triple hydrogen bonds formed between nucleic acid base pairs. We wish to measure a series of AA-DD, AAA-DDD, AAAA-DDDD and AAAAA-DDDDD systems to build up a structure-property profile of such contiguous hydrogen bonding arrays. We will measure the thermodynamics of binding through Ka measurements (using NMR, UV, fluorescence tritrations, competition experiments and microcalorimetry, depending on the binding regime, and use evolutionary algorithms to improve on the values currently obtained using titration methods). We will measure the kinetics of binding in very strong complexes using EXSY NMR techniques. We also intend to develop stimuli-responsive complexes which assemble or fall apart in response to an external signal (chemical or photonic) and can be used to assemble supramolecular polymers. The result will be a fundamental mechanistic understanding of the relationship between chemical structure and hydrogen bonding strength for such contiguous hydrogen bonding arrays.

我们提出了一个方案，以定量研究已知的最强的氢键小分子复合物的热力学和动力学。AAA-DDD三氢键阵列可以比核酸碱基对之间形成的三氢键强高达一亿倍。我们希望测量一系列AA-DD，AAA-DDD，AAAA-DDDD和AAAAA-DDDDD体系，以建立这种连续氢键阵列的结构-性质曲线。我们将通过Ka测量来测量结合的热力学（使用NMR、UV、荧光研磨、竞争实验和微量热法，取决于结合状态，并使用进化算法来改进目前使用滴定方法获得的值）。我们将使用EXSY NMR技术测量非常强的复合物中结合的动力学。我们还打算开发刺激响应复合物，其响应于外部信号（化学或光子）而组装或分解，并可用于组装超分子聚合物。其结果将是一个基本的机械理解的化学结构和氢键强度之间的关系，这种连续的氢键阵列。