Quantitative analysis of extremely strong contiguous hydrogen bond arrays

我们提出了一个程序，定量研究热力学和动力学最强的氢键小分子复合物已知。AAA-DDD三氢键阵列的强度可达核酸碱基对之间形成的三氢键的一亿倍。我们希望测量一系列的AA-DD， AAA-DDD， AAAA-DDDD和AAAAA-DDDDD系统，以建立这种连续氢键阵列的结构-性能曲线。我们将通过Ka测量来测量结合的热力学（根据结合机制，使用核磁共振、紫外、荧光滴定、竞争实验和微量热法，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核磁共振技术测量非常强的配合物的结合动力学。我们还打算开发刺激响应复合物，该复合物可根据外部信号（化学或光子）组装或分解，并可用于组装超分子聚合物。结果将是对这种连续氢键阵列的化学结构和氢键强度之间关系的基本机制理解。

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.