Self-Assembled Supramolecular Nanocarrier Hosting Two Kinds of Guests in the Site-Isolation State

Hyperbranched polyethylenimine (HPEI) was simply mixed with a solution of amphiphilic calix[4]arene (AC4), which possesses four phenol groups and four aliphatic chains, in chloroform. This resulted in the novel supramolecular complex HPEI-AC4 through the noncovalent interaction of the amino groups of HPEI with the Phenol groups of AC4. The formed HPEI-AC4 supramolecular complexes were characterized by H-1 NMR spectroscopy and dynamic light scattering. The cationic water-soluble dye methyl blue (MB) and the anionic water-soluble dye methyl orange (MO) were used as the model guests to test the performance of HPEI-AC4 as a supramolecular nanocarrier. It was found that HPEI-AC4 could accommodate the anionic water-soluble MO guests into the HPEI core. The MO encapsulation capacity I of HPEI-AC4 was pH sensitive, which reached maximum loading under weakly acidic conditions. The loaded MO molecules could be totally released when the pH value was reduced to be around 4.5 or raised to be around 9.5, and this process was reversible. HPEI-AC4 could not only accommodate the anionic MO with the HPEI core but could also simultaneously load the cationic MB molecules using the formed AC4 shell, thereby realizing the site isolation of the two kinds of functional units. The amount of MO and MB encapsulated by HPEI-AC4 could be controlled by varying the ratio of hydroxyl groups of AC4 to amino groups of HPEI.