Colloidal Stable PIC Vesicles and Lamellae Enabled by Wavelength-Orthogonal Disulfide Exchange and Polymerization-Induced Electrostatic Self-Assembly
Leilei Huang, Yi Ding, Yajie Ma, Lei Wang, Qizhou Liu, Xinhua Lu, and Yuanli Cai*（蔡远利）
State-Local Joint Engineering Laboratory of Novel Functional Polymeric Materials, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Macromolecules2019, 52, 4703--4712
Block copolymer nanoparticles have been widely used for advanced materials. However, the stabilization is challenging. Herein, we present a method for convenient yet reliable synthesis of stabilized polyion complex (PIC) nanometer-sized spheres and micrometer-sized ultrathin lamellaeand vesicles by taking advantage of the wavelength orthogonality of UV-induced disulfideexchangeand visible light-initiated polymerization-inducedelectrostaticself-assembly (PIESA). Disulfide-containing PICvesicles are synthesized at scale using this PIESA, undergoing a small sphere-to-larger sphere-to-lamella-to-vesicle transition. As such, surface-neutralized and surface-charged micrometer-sized vesicles can be achieved. UV irradiation of the vesicles (5.0 mg/mL in water) in ambient air induces very fast exchange reaction of locally confined/enriched disulfide motifs, leading to cross-linking, shape transition, and cystamine salt release in 4 min. As such, cross-linked PIC spheres, lamellae, and vesicles can be achieved, in one pot, from one single vesicle precursor. The wavelength orthogonality is evident from disabled PIESA synthesis under UV light and ineffective postpolymerization functionalization under visible light. The cross-linked PIC spheres and micrometer-sized ultrathin lamellae and vesicles show outstanding shape/size stability and high reversibility in the solution-adaptive electrostatichierarchical self-assembly and disassembly upon adding ethanol into aqueous dispersion and subsequent dialysis.