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

位于蛋白质内裂缝中的半胱氨酸残基在空间上受到限制，不能形成分子间或分子内桥键。它们与活性氧和氮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，这些中间体中的许多在人工系统中是出了名的不稳定，并且由于它们的不稳定性，对这些物种的模型研究一直很困难。在这项研究中，新型的纳米尺寸的分子空腔与碗状框架的开发建模这种空间隔离的环境和应用的稳定性高活性的化学物种参与氧化还原调节。利用这些模型系统，实验证明了一些生物转化的机制。

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.