ИСТИНА

Rational design of well-defined polymeric nanostructures is one of the most important challenges of the modern polymer science as they can be used as nanocontaines/nanoreactors for various needs of medicine, biotechnology, catalysis, diagnostics, etc. To construct such polymeric nanostructures, one can exploit electrostatically driven co-assembly, which takes place in aqueous solutions of the oppositely charged polymeric components and results in the formation of interpolyelectrolyte complexes (IPECs). In this contribution, we highlight a new approach to preparation of such macromolecular co-assemblies with tunable morphologies (spherical, worm-like, and vesicular), taking advantage of a star-shaped architecture of one of the polymeric components, bis-hydrophilic ionic/non-ionic heteroarm star-shaped block copolymer PEO-(qPDMAEMA)N composed of a few ionic arms of quaternized poly(2-(dimethylamino)ethyl methacrylate) (qPDMAEMA) and one non-ionic but hydrophilic arm of poly(ethylene oxide) (PEO). The qPDMAEMA arms of the PEO-(qPDMAEMA)N can electrostatically interact with the oppositely charged linear polyions such as poly(sodium styrenesulfonate) (PSSNa) or poly(sodium acrylate) (PANa), generating water-insoluble part of IPECs, while the PEO arms imparts colloidal stability to the formed macromolecular co-assemblies. As evidenced by scattering techniques, analytical ultracentrifugation, and transmission electron microscopy, the average number of ionic arms per non-ionic hydrophilic arm, NqPDMAEMA/PEO, in the system under investigation is a decisive parameter, which controls morphology of the macromolecular co-assemblies formed at the equimolar (1 : 1) charge-to-charge ratio between the oppositely charged polymeric components. Apart from a rather demanding synthetic route, this parameter could also be easily adjusted by simple blending the PEO-(qPDMAEMA)N with the corresponding linear diblock copolymer, PEO-b-PDMAEMA, at different ratios. When the blended polymeric component, PEO-(qPDMAEMA)N + PEO-b-PDMAEMA, electrostatically interacts with PSSNa (or PANa), morphology of the resultant IPECs changes with the increasing NqPDMAEMA/PEO from spherical star-like micelles to worm-like micelles and further to vesicular structures (polymersomes). The described macromolecular co-assemblies with tunable morphology can hold promise for targeted delivery and triggered/controlled release of various (bio)payloads. (2.10, p. 45)