Synthetic model study of reactive species involved in biological reactions for chemical elucidation of redox regulatory mechanism

位于蛋白质内部裂隙中的半胱氨酸残基受到空间上的限制，不能形成分子间或分子内的桥键。它们与活性氧和氮物种反应产生的活性中间体在氧化还原调节中起着至关重要的作用。然而，其中许多中间体在人工系统中是出了名的不稳定，由于它们的不稳定，对这些物种的模型研究一直很困难。在这项研究中，开发了一种新型的具有碗状骨架的纳米分子腔来模拟这种空间隔离环境，并应用于氧化还原调节中涉及的高活性化学物种的稳定。利用这些模型系统对提出的一些生物转化机制进行了实验验证。

Cysteine residues located in clefts within the proteins are sterically restrained from forming inter- or intramolecular bridging bonds. The reactive intermediates generated by their reactions with reactive oxygen and nitrogen species play a crucial role in redox regulation. However, many of these intermediates are notoriously unstable in artificial systems, and model studies on these species have been difficult due to their instability. In this study, novel nano-sized molecular cavities with bowl-shaped frameworks were developed for modeling such sterically isolated environment and applied for the stabilization of highly reactive chemical species involved in redox regulations. Some of the mechanisms proposed for biological transformations were demonstrated experimentally by utilizing these model systems.