Department of Chemical and Biological Engineering, Korea University, 145 Anam-Ro, Seongbuk-Gu, Seoul 02841, Korea.
Org Biomol Chem. 2020 Jan 22;18(3):420-424. doi: 10.1039/c9ob02515d.
The aim of this work is to show that by increasing the number of donor substituents in a donor/acceptor system, the sensitivity of the azobenzene linkage towards a reductive cleavage reaction can be enhanced to unprecedented high levels. For instance, in a triple-donor system, less than a second constitutes the half-life of the azo (N[double bond, length as m-dash]N) bond. Synthetic access to such redox active scaffolds is highly practical and requires only 1-2 synthetic steps. The fundamental molecular design is also adaptable. This is demonstrated through scaffold functionalization by azide, tetraethylene glycol, and biotin groups. The availability of the azide group is shown in a copper-free 'click' reaction suitable in context with protein conjugation and proteomics application. Finally, the clean nature of the scission process is demonstrated with the help of liquid chromatography coupled with mass analysis. This work, therefore, describes development of cleavable azobenzene linkers that can be accessed with synthetic ease, can be multiply functionalized, and show a clean and rapid response to mild reducing conditions.
这项工作的目的是表明，通过增加供体/受体系统中供体的数量，可以将偶氮苯键对还原裂解反应的敏感性提高到前所未有的高水平。例如，在三供体系统中，不到一秒就构成了偶氮（N[双键，长度为破折号]N）键的半衰期。这种氧化还原活性支架的合成方法非常实用，只需要 1-2 步合成步骤。基本的分子设计也具有适应性。这通过通过叠氮化物、四乙二醇和生物素基团对支架进行功能化来证明。叠氮基团的可用性在适合蛋白质缀合和蛋白质组学应用的无铜“点击”反应中得到了展示。最后，借助液相色谱与质谱联用，证明了裂解过程的清洁性质。因此，这项工作描述了可开发的可裂解偶氮苯键，这些键易于合成、可多次官能化，并对温和的还原条件表现出清洁快速的响应。
