Hu Dengwen, Chang Xiaohua, Xu Youquan, Yu Qunli, Zhu Yutian
College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, No. 2318 Yuhangtang Rd., Cangqian, Yuhang District, Hangzhou 311121, China.
ACS Macro Lett. 2021 Jul 20;10(7):914-920. doi: 10.1021/acsmacrolett.1c00356. Epub 2021 Jul 2.
Confined self-assembly of block copolymers (BCPs) is effective to manipulate various shapes of particles. In emulsion confined self-assembly, reversibly light-trigged switchable BCP particles are extremely expected, yet rarely reported. Herein, a novel strategy is developed to realize reversibly light-responsive shape-transformation of BCP particles by constructing functional surfactants with light-active azobenzene (azo) groups in the confined self-assembly of BCPs within emulsion droplet. Ultraviolet and visible lights can reversibly modulate the amphiphilicity and interfacial affinity of the surfactants to different blocks, triggering the reversible microphase structure transformation of BCP particles with high temporal-spatial resolution. We can realize shape and morphological transitions of BCP particles from onion-shaped spherical particles to striped ellipsoids and, ultimately, to inverse onion-like particles by ultraviolet irradiation. More importantly, this shape transformation is reversible by the irradiation of visible light, attributed to the reversible - isomerization of azo groups. We also demonstrate that the light-triggered shape transformation of BCP particles can be employed in a controllable drug release through a noncontacted and programmed manner, showing promising potential in clinic and biomedicine.
嵌段共聚物(BCPs)的受限自组装对于操控各种形状的颗粒是有效的。在乳液受限自组装中,人们极其期待具有可逆光触发特性的可切换BCP颗粒,但相关报道却很少。在此,我们开发了一种新策略,通过在乳液滴内BCPs的受限自组装中构建带有光活性偶氮(azo)基团的功能性表面活性剂,来实现BCP颗粒的可逆光响应形状转变。紫外光和可见光可以可逆地调节表面活性剂对不同嵌段的亲水性和界面亲和力,以高时空分辨率触发BCP颗粒的可逆微相结构转变。通过紫外光照射,我们可以实现BCP颗粒从洋葱状球形颗粒到条纹状椭球体,最终到反洋葱状颗粒的形状和形态转变。更重要的是,由于偶氮基团的可逆异构化,这种形状转变在可见光照射下是可逆的。我们还证明,BCP颗粒的光触发形状转变可通过非接触和程序化方式用于可控药物释放,在临床和生物医学领域显示出广阔的应用前景。