Multilayer Polymeric Nanoparticles Based on Specific Interactions in Solution: Polystyrene-block-poly(methacrylic acid) Micelles with Linear Poly(2-vinylpyridine) in Aqueous Buffers

Abstract

Polymeric micelles of polystyrene-block-poly(methacrylic acid) with the shell containing various amounts of poly(2-vinylpyridine) chains were prepared by dialysis from 1,4-dioxane-rich mixtures into alkaline aqueous solutions. The structure of the polymeric nanoparticles was studied by light scattering, atomic force microscopy, fluorometry, and capillary zone electrophoresis. The presence of both weak polyacid and weak polybase in the corona allows the micelles to form fairly stable solutions in a broad pH range. Poly(methacrylic acid) blocks are dissociated in basic buffers, while poly(2-vinylpyridine) chains stabilize the micelles in acidic solutions. Besides the water-swollen shell, the inner parts of the micelles consist of the kinetically frozen polystyrene core and relatively rigid layer of poly(methacrylic acid) and poly(2-vinylpyridine) segments. An insufficient number of stabilizing polymer chain segments results in the aggregation of the micelles into clusters.

Grand-Reaction Method for Simulations of Ionization Equilibria and Ion Partitioning in a Broad Range of pH and Ionic Strength

“…Similar effect on the swelling of weak polyelectrolyte micelles was observed experimentally by Matějíček et al 82 . Later, they confirmed it in simulations, combining explicit-particle representation of the polymers with mean-field treatment of small ions on the Poisson-Boltzmann level 83 . The molecular theory of Longo et al 56 also combined molecular representation of polyelectrolytes with mean-field treatment of small ions to observe a similar effect on the swelling of polyelectrolyte gels grafted to a surface.…”