Multi-Stimuli Responsive Sequence Defined Multi-Arm Star Diblock Copolymers for Controlled Drug Release.

Star-shaped polymeric materials provide very high efficiency toward various engineering and biomedical applications. Due to the absence of straightforward and versatile synthetic protocols, the synthesis of sequence-defined star-shaped (co)polymers has remained a major challenge. Here, a facile approach is developed that allows synthesis of a series of unprecedented discrete, multifunctional four-, six-, and eight-arm star-shaped complex macromolecular architectures based on a well-defined triple (thermo/pH/light)-stimuli-responsive poly(N-isopropylacrylamide)-block-poly(methacrylic acid)-umbelliferone (PNIPAM-b-PMAA)n-UMB diblock copolymer, based on temperature responsive PNIPAM segment, pH-responsive PMAA segment, and photoresponsive UMB end groups. Thus, developed star-shaped copolymers self-assemble in water to form spherical nanoaggregates of diameter 90 ± 20 nm, as measured by FESEM. The star-shaped copolymer's response to external stimuli has been assessed against changes in temperature, pH, and light irradiation. The star-shaped copolymer was employed as a nanocarrier for pH responsive release of an anticancer drug, doxorubicin. This study opens up new avenues for efficient star-shaped macromolecular architecture construction for engineering and biomedical applications.