The association of branched polyethyleneimine (PEI) with a series of octacarboxy-calixresorcinarenes bearing different low-rim substituents leads to the formation of nanosized supramolecular complexes. The PEI–macrocycle complexes have fine-tunable sizes regulated by variations in the self-association capacity of the calixresorcinarenes. In the supramolecular complexes, hydrophobic fragments of the polymer and calixresorcinarenes form cooperative hydrophobic domains which provide synergistic enhancement of guest molecule binding. The formation of the supramolecular complexes was investigated by NMR FT-PGSE, NMR 2D NOESY, DLS and TEM methods. In addition, fluorimetry and UV-vis methods were used with the help of optical probes, namely water-soluble Crystal Violet and water-insoluble Orange OT. The investigation demonstrates the first example of the formation of cooperative hydrophobic domains in supramolecular polyelectrolyte–macrocycle complexes which enhance the binding of both water-soluble and water-insoluble organic compounds. The presented supramolecular systems have potential as sensory and drug delivery systems.

中文翻译：

---

超分子聚合物与带相反电荷的杯芳烃类芳烃形成复合物：疏水结构域的形成和协同结合模式†

支链聚乙烯亚胺（PEI）与一系列带有不同低边缘取代基的八羧基-杯形间苯二酚芳烃的缔合导致纳米级超分子复合物的形成。PEI-大环复合物的大小可根据杯形间苯二酚芳烃的自缔合能力的变化进行调节。在超分子复合物中，聚合物和杯形间苯二酚芳烃的疏水片段形成协同的疏水域，该协同的疏水域提供客体分子结合的协同增强。通过NMR FT-PGSE，NMR 2D NOESY，DLS和TEM方法研究了超分子复合物的形成。另外，在光学探针的帮助下，使用了荧光法和紫外可见法，即水溶性的结晶紫和不溶于水的Orange OT。研究表明，在超分子聚电解质-大环复合物中形成协同疏水结构域的第一个例子可以增强水溶性和水不溶性有机化合物的结合。提出的超分子系统具有作为感觉和药物递送系统的潜力。