Synthesis and Multi-Stimuli-Responsive Behavior of Poly(<i>N</i>,<i>N</i>‑dimethylaminoethyl methacrylate) Spherical Brushes under Different Modes of Confinement in Solution

We report the synthesis and solution behavior of photo-, temperature-, pH-, and ion-responsive weak polyelectrolyte spherical brushes under different modes of confinement. The spherical brushes were prepared by copolymerization of <i>N</i>,<i>N</i>-dimethylaminoethyl methacrylate (DMAEMA) and 7-(2-methacryloyloxyethoxy)-4-methylcoumarin anchored to silica nanoparticles via surface-initiated atom transfer radical polymerization. The photo-cross-linking and reversibility of the nanoparticle-attached coumarin entities are detected by UV–visible spectroscopy and dynamic light scattering (DLS). The cross-linking density of poly­(DMAEMA) (i.e., PDMAEMA) brushes could be easily controlled by alternating irradiation at wavelengths of 365 and 254 nm. Moreover, solution behavior under different pH levels and ionic strengths is systematically investigated in the PDMAEMA brush–polyelectrolyte chains confined only by a hard core, the cross-linked PDMAEMA brush–polyelectrolyte chains confined by a hard core and cross-linking points, and the corresponding hollow nanocapsules after removal of silica by etching-polyelectrolyte chains confined only by cross-linking points. These three models represent the different modes of confinement. DLS results indicate that the volume phase transition temperatures of the three models shift to lower temperatures with the increase in pH. The highest temperature is afforded to phase transition for hollow nanocapsules in solution, followed by the cross-linked PDMAEMA brushes. The hydrodynamic radius of the polyelectrolyte brush systems obviously decreases with the increase in ionic strength of the solution when adjusted by NaCl