Multi-Stimuli-Responsive Janus Hollow Polydopamine Nanotubes.

A tubular-shaped Janus nanoparticle based on polydopamine that responds to near-infrared, magnetic, and pH stimuli is reported. The robust tubular polydopamine structure was obtained by optimizing the halloysite template-to-dopamine ratio during synthesis. The inner and outer surfaces of the tube were exposed at different steps of the template-sonication--etching process, enabling the differential surface modification of these surfaces. Poly(ethylene glycol) (PEG) and poly(-isopropylacrylamide) (PNIPAM) were grafted to the outer and inner surface of the nanotube, respectively. The PEG-coated surface limited aggregation of the nanoparticles at elevated temperatures. The PNIPAM-coated interior enhanced doxorubicin loading and endowed the nanoparticle with temperature-responsive behavior. The deposition of precipitated FeO nanoparticles further modified the nanoparticles. The resulting magnetic Janus nanoparticles responded to pH, temperature, and magnetic fields. Temperature changes could be induced by near-infrared laser, and all three stimuli were found to influence release rates of adsorbed doxorubicin from the nanoparticles. The interaction of the stimuli on release kinetics was elucidated using a linear mixed model; reduced pH and NIR irradiation enhanced release while applying a static magnetic field retarded release. Furthermore, the mechanism was shifted toward Fickian behavior by applying a static magnetic field and low pH conditions. However, NIR irradiation only shifted the behavior toward Fickian behavior at low pH.