Construction of polyelectrolyte-responsive microgels, and polyelectrolyte concentration and chain length-dependent adsorption kinetics.

Abstract

We report on the construction of a polyelectrolyte-responsive system evolved from sterically stabilized protonated poly(2-vinylpyridine) (P2VPH(+)) microgels. Negatively charged sodium dodecylbenzenesulfonate (SDBS) surfactants could be readily internalized into the cationic microgels by means of electrostatic interactions, resulting in microgel collapse and concomitant formation of surfactant micellar domains (P2VPH(+)/SDBS)-contained electrostatic complexes. These internal hydrophobic domains conferred the opportunity of fluorescent dyes to be loaded. The obtained fluorescent microgel complexes could be further disintegrated in the presence of anionic polyelectrolyte, poly(sodium 4-styrenesulfonate) (PNaStS). The stronger electrostatic attraction between multivalent P2VPH(+) microgels and PNaStS polyelectrolyte than single-charged surfactant led to triggered release of the encapsulated pyrene dyes from the hydrophobic interiors into microgel dispersion. The process was confirmed by laser light scattering (LLS) and fluorescence measurements. Furthermore, the entire dynamic process of PNaStS adsorption into P2VPH(+) microgel interior was further studied by stopped-flow equipment as a function of polyelectrolyte concentration and degree of polymerization. The whole adsorption process could be well fitted with a double-exponential function, suggesting a fast (τ1) and a slow (τ2) relaxation time, respectively. The fast process (τ1) was correlated well with the approaching of PNaStS with P2VPH(+) microgel to form a nonequilibrium complex within the microgel shell, while the slow process (τ2) was consistent with the formation of equilibrium complexes in the microgel deeper inside. This simple yet feasible design augurs well for the promising applications in controlled release fields.