The self-assembly inducing the formation of different supramolecular assemblies has been widely explored as a kind of facilitated nanocontainers. The success of this application requires the development of a versatile mechanism of a self-aggregation for producing the nanocontainers with controlled functions and structures. There are several strategies for their creation, and alternatively, a nanocontainer structure can be achieved through the self-assembly of macrocyclic platforms. Within the latter methodology, the calix[4]arene platform has demonstrated its potential for building up these systems.
We report the novel classes of self-assembling nanoparticles formed with two types of calix[4]arene compounds, namely resorcin[4]arene cavitands and calix[4]resorcinarenes. Cavitand assemblies are designed via “click” chemistry to form self-assembled noncovalently connected aggregates through counter-ion displacement. Another type of assembly are created from calix[4]resorcinarenes and surfactants with the formation of super-amphiphiles, which further self-assemble into ordered aggregates. The way of controlling the super-amphiphile formation depends on the ionic nature of surfactant. A supramolecular system based on the calix[4]resorcinarene sulfonatoalkylated at lower rim and amine-methylated at upper rim and the cationic surfactant can be derived spontaneously by electrostatic attraction. However, this is not so in the case of anionic surfactant since pH-induced signal generation is required for the super-amphiphile formation. Importantly, in all cases the supramolecular amphiphilic systems with controlled structure and binding behavior could be fabricated. These self-assembling particles can be used as nanocontainers with controllable binding capacity toward hydrophobic compounds and find their applications in delivery system.
The work was supported by Russian Foundation for Basic Research (projects 12-03-00379, 14-03-31141) and Russian Presidential Fellowship (SP-6310.2013.4).
kashapov@iopc.ru
