Preparation and Characterization of a pH-Responsive Nanogel Based on a Photo-Cross-Linked Micelle Formed From Block Copolymers with Controlled Structure

Poly(ethylene glycol)-<i>b</i>-poly(2-(diethylamino)ethyl methacrylate-<i>co</i>-2-cinnamoyloxyethyl acrylate) (PEG-<i>b</i>-P(DEAEMA/CEA)) was prepared by reversible addition−fragmentation chain transfer (RAFT)-controlled radical polymerization. As solution pH is increased from an acidic pH, the hydrodynamic radius (<i>R</i><sub>h</sub>) increases abruptly near pH 7, indicative of the micelle formation at pH > 7. The micelle formation at pH > 7 was supported by <sup>1</sup>H NMR and light scattering data. Upon irradiation of light, polymer chains in the core of the polymer micelle are cross-linked as a result of the photodimerization of the cinnamoyl groups, yielding a nanogel. The nanogel was characterized by gel-permeation chromatography (GPC), light scattering, small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and fluorescence techniques. The nanogel displayed an ability to solubilize <i>N</i>-phenyl-1-naphthylamine (PNA) and 1-pyrenemethanol (hydrophobic guest molecules) into the hydrophobic core at pH > 7. It was confirmed with PNA that the solubilization of a guest molecule occurred at polymer concentrations (<i>C</i><sub>p</sub>) lower than the critical micelle concentration (cmc) for PEG-<i>b</i>-P(DEAEMA/CEA) because the nanogel retains its micellar structure at <i>C</i><sub>p</sub> < cmc. 1-Pyrenemethanol is strongly captured by the nanogel at pH 10, whereas it is easily released from the nanogel when pH is reduced to 3. This indicates that the hydrophobicity of the core of the nanogel can be modulated by a change in the degree of protonation of the DEAEMA units in the core, and thus the capture of a guest molecule and its release can be controlled by a change in solution pH.