Macrocyclic amphiphiles as an emerging family of artificial amphiphiles have gained considerable attention in recent years on account of their fascinating recognition and assembly properties. Benefiting from a preorganized framework, facile modification and host–guest recognition ability, calixarenes have been widely used to fabricate self-assemblies of both amphiphiles and supra-amphiphiles. In this review, we organized hundreds of reported amphiphilic calixarenes based on their structures and systematically summarized assembling features of calixarene-based amphiphiles and supra-amphiphiles. For amphiphilic calixarenes, the size and conformation of skeletons significantly affect their assembly behaviors, such as lower critical aggregation concentration (CAC) and more diverse morphology than conventional amphiphiles. Besides, we also focus on emerging topics like uniformity, compactness, and kinetic properties of calixarene aggregation. For supra-amphiphiles, the binding affinities of calixarenes endow them with the ability to induce guest assembly. In addition, complexation of guests also improves amphiphilic calixarene aggregation. The obtained assemblies not only possess the advantages of low CAC and compact packing, but also respond to various stimuli. Finally, we pointed out several research topics of calixarene-based amphiphiles and supra-amphiphiles to be further developed in the future, such as the relationship between molecular structures and assembly properties, crosslinking, co-assembly, and utilization of cavities. We hope this review could be a guidance for studying amphiphilic assemblies based on calixarenes and other macrocyclic compounds.

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基于杯芳烃的两亲物和超两亲物的组装特征

大环两亲物作为人工两亲物的新兴家族，由于其引人入胜的识别和装配特性，近年来受到了相当大的关注。得益于预先组织的框架，便捷的修饰和宾客识别能力，杯芳烃已被广泛用于制造两亲和超两亲的自组装体。在这篇综述中，我们根据其结构组织了数百种已报道的两亲杯芳烃，并系统总结了基于杯芳烃的两亲物和超两亲物的组装特征。对于两亲杯芳烃，骨架的大小和构象会显着影响其组装行为，例如比常规两亲物低的临界聚集浓度（CAC）和更多样化的形态。除了，我们还关注新兴主题，例如杯芳烃聚合的均匀性，致密性和动力学性质。对于超两亲来说，杯芳烃的结合亲和力使它们具有诱导客体装配的能力。另外，客体的络合还改善了两亲杯芳烃的聚集。所获得的组件不仅具有低CAC和紧凑包装的优点，而且还响应各种刺激。最后，我们指出了杯芳烃基两亲物和超两亲物在未来将要发展的几个研究主题，例如分子结构与组装性能，交联，共组装和利用腔之间的关系。我们希望这篇综述对研究基于杯芳烃和其他大环化合物的两亲性组装体具有指导意义。