An effective and universal method for delivering structurally diverse biomolecules in vivo would greatly benefit modern drug therapy, but has yet to be discovered. Self‐assembled supramolecular complexes containing vesicles of amphiphilic cyclodextrin and linker molecules with an azobenzene guest unit and a charged functionality have been established as nanoscale carriers for proteins and DNA, making use of multivalent electrostatic attraction. However, light‐induced cargo release is only feasible up to a maximum net charge of the biomacromolecules. Herein, it is shown that it is possible to fine‐tune macromolecular complex stability and size by addition of a competitive guest molecule that acts as a stopper, partly blocking the vesicle surface. The superior performance of arylazopyrazoles in photoisomerization compared to azobenzenes, which enables a lower surface charge density of the vesicles in the photostationary state, is also demonstrated. Both strategies allow reversible supramolecular aggregation of high molecular weight DNA (2 and 4.8 kbp).

中文翻译：

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控制光响应性高分子宿主-客体系统中的复杂稳定性：通过环糊精囊泡实现DNA的可逆捕获

在体内递送结构多样的生物分子的有效且通用的方法将大大有益于现代药物治疗，但尚未发现。利用多价静电吸引作用，已建立了包含两亲环糊精和带有偶氮苯客体单元的连接分子的囊泡和带电官能团的自组装超分子复合物，作为蛋白质和DNA的纳米级载体。但是，光诱导的货物释放只有在达到生物大分子的最大净电荷的情况下才可行。本文显示，通过加入竞争性客体分子作为塞子，部分阻断囊泡表面，可以微调大分子复合物的稳定性和大小。与偶氮苯相比，芳基偶氮吡唑在光致异构化方面具有优异的性能，还证明了其在光平稳状态下能够降低囊泡的表面电荷密度。两种策略均允许高分子量DNA（2和4.8 kbp）的可逆超分子聚集。