A Redox-Active Heterocyclic Capsule: Radical Generation, Oxygenation, and Guest Uptake/Release
A Redox-Active Heterocyclic Capsule: Radical Generation, Oxygenation, and Guest Uptake/Release
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氧化还原活性杂环胶囊：自由基生成、氧化和客体吸收/释放
DOI：
10.1021/jacs.9b03419
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发表时间：
2019
影响因子：
15
通讯作者：
Yoshizawa Michito
中科院分区：
文献类型：
--
作者：
Satoh Yoshiyuki;Catti Lorenzo;Akita Munetaka;Yoshizawa Michito
为了开发具有主体功能的氧化还原活性超分子胶囊，我们使用能够采用三种不同状态的吩噻嗪面板合成了弯曲的杂环两亲物，即，中性、自由基和含氧状态。在水中，两亲分子通过疏水作用和π-堆积作用自发地定量组装成平均直径约为1.2 nm的杂环结构.产物结构通过NMR、UV-可见光、DLS、AFM和分子模拟研究的组合来确认。胶囊的电化学和化学氧化在室温下以可逆的方式产生相对稳定的自由基阳离子胶囊。中性胶囊有效地吸收大的疏水性化合物（例如，颜料蓝15和富勒烯C60）通过研磨方案进入杂环空腔，随后产物的化学氧化产生自由基主体-客体复合物。此外，主-客体复合物的化学氧化显示出通过吩噻嗪面板的二氧化分解胶囊结构来诱导客体在水中的释放。
For the development of a redox-active supramolecular capsule with host function, we synthesized a bent heterocyclic amphiphile using phenothiazine panels capable of adopting three different states, i.e., neutral, radical, and oxygenated states. In water, the new amphiphiles spontaneously and quantitatively assemble into a heterocycle-based capsule with an average diameter of ∼2 nm, through the hydrophobic effect and π-stacking interactions. The product structure was confirmed by the combination of NMR, UV–visible, DLS, AFM, and molecular modeling studies. Electrochemical and chemical oxidation of the capsule generates relatively stable radical cation capsules at room temperature in a reversible fashion. The neutral capsule efficiently takes up large hydrophobic compounds (e.g., pigment blue 15 and fullerene C60) into the heterocyclic cavity through a grinding protocol and subsequent chemical oxidation of the products generates radical host–guest complexes. Moreover, chemical oxygenation of the host–guest complexes was shown to induce guest release in water via disassembly of the capsular structure through dioxygenation of the phenothiazine panels.