Light-, temperature-, and pH-responsive micellar assemblies of spiropyran-initiated amphiphilic block copolymers: Kinetics of photochromism, responsiveness, and smart drug delivery.

Multi-responsive polymer assemblies are a significant class of smart polymers with potential applications in drug-delivery and gen-delivery systems. Poly(dimethylaminoethyl methacrylate) (PDMAEMA) is among the most applicable multi-responsive polymers that changes its physical and chemical properties in response to temperature, pH, and CO2. Herein, different types of light-, temperature-, pH-, and CO2-responsive polymer assemblies were developed based on multi-responsive PDMAEMA and hydrophobic poly(methyl methacrylate) blocks. In addition, spiropyran was incorporated at the chain ends by using spiropyran-initiated atom transfer radical polymerization method. Novel smart drug-delivery systems were developed by self-assembly of these amphiphilic block copolymers to micellar morphologies in aqueous media. Dynamic light scattering results showed that size of the polymer assemblies changed in response to pH variations (from 5 to 9), temperature changes (above the lower critical solution temperature (LCST) of PDMAEMA), and also UV light irradiation (wavelength of 365 nm). The LCST of PPDMAEMA showed a shift from 53 to 60 °C after isomerization of the SP to MC form, as a result of increase of polarity and water-solubility. The PDMAEMA block results in responsivity of the prepared copolymer assemblies to CO2, which display pH variation from 8-8.6 to 5-6 after 2 min of CO2 gas bubbling. All the multi-responsive micellar polymer assemblies showed various loading capacities and release profiles, and the DOX release can be controlled by pH, temperature, and light. The release efficiency is reached to 60-85% at pH 5.3, 80-90% at temperatures higher than the LCST of PDMAEMA (60 °C), and also 90-100% under UV light irradiation after 48 h. In summary, the multi-responsive polymer assemblies based on amphiphilic block copolymers containing spiropyran chain end groups in the current study have potential applications in smart drug-delivery systems, and offer controlling over the drug-release by different triggers, such as light irradiation, pH variation, and temperature change. A very low concentration of spiropyran molecules (one per polymer chain) showed light-controlling of drug-release from the assemblies with high efficiencies.