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 lamellae and vesicles by taking advantage of the wavelength orthogonality of UV-induced disulfide exchange and visible light-initiated polymerization-induced electrostatic self-assembly (PIESA). Disulfide-containing PIC vesicles are synthesized at scale using this PIESA, undergoing a small sphere-to-larger sphere-tolamella-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 electrostatic hierarchical self-assembly and disassembly upon adding ethanol into aqueous dispersion and subsequent dialysis.

The noncovalent locking of nanostructured thermoresponsive polyion complexes can be achieved via polymerization-induced electrostatic self-assembly (PIESA) using an arginine-like cationic monomer.

We herein present sequence-controlled polymerizationinduced self-assembly (PISA) via photoswitchable reversible addition−fragmentation chain transfer (RAFT) copolymerization of oppositely-charged monomers using polyethylene glycol chain transfer agent in water at 25 °C. Thorough block copolymerization leads to a polymerization-induced electrostatic self-assembly named ABC-mode polymerization-induced electrostatic self-assembly (PIESA), by which PEGylated (PEG, polyethylene glycol) polyion complex (PIC) spheres, lamellae, and vesicles are achieved. We demonstrate the inherent spontaneous zwitterionic alternating copolymerization nature, which leads to the charge-dictated alternating or gradient zwitterionic sequence. As such, we developed sequencecontrolled synthesis of nanostructured block-gradient zwitterionic terpolymer PICs via complete zwitterionic copolymerization starting from photoswitched incomplete first polymerization, i.e., AB(BC)-mode PIESA. This sequence-controlled PISA method provides the unprecedented control of the low-dimensional polyelectrolyte complex nanostructure involving not only shape but also size and thickness of micrometer-sized ultrathin PIC vesicles and lamellae, without necessarily changing the whole chemical composition and degree of polymerization.

Scalable synthesis of multicompartment polyion complex (PIC) systems has been achieved via visible light-initiated RAFT polymerization of cationic monomer in the presence of anionic diblock copolymer micelles in water at 25 °C. This polymerization-induced hierarchical electrostatic self-assembly (hierarchical PIESA) implements structural hierarchy via programmable self-assembly to form multicompartment PIC micelles and their monolayer colloidal nanosheets and nanocages. The anionic micelles play decisive roles in such a hierarchical PIESA to access biologically relevant yet otherwise inaccessible multicompartment PIC systems.

Polymerization-induced self-assembly (PISA) is a powerful method for the synthesis of polymeric kinetically frozen core nanoparticles. However, the PISA synthesis of biologically important polymeric fluidic materials is unexplored. Herein we present a liquid–liquid phase separation mode PISA. The proof of concept is established by means of complex coacervation in visible light-initiated RAFT dispersion polymerization of anionic monomer in the presence of a protonated polyethylenimine in water at 25 °C. We demonstrate a stage-by-stage nano to micron droplet growth mechanism via an increase in growing chain DP or electrical neutralization. Liquid coacervate droplets and their glassy nanowires or vesicles can be interconverted upon changing the ethanol/water solvent. As such, tunable construction of coacervate droplets and nanowires or vesicles can be achieved using this smart PISA method.

Summary Reinforced concrete (RC) shear walls have been extensively used as lateral load resisting structural members in tall buildings. However, in the past, strong earthquake events RC structural walls in some buildings suffered severe damage, which concentrated at the bottom and was very difficult to be repaired. The installation of the replaceable corner components (RCCs) at the bottom of the structural wall is a new method to form an earthquake resilient structural wall whose function can be quickly restored by replacing the RCCs after the strong earthquake because of the damage concentrating on RCCs. In this study, a new kind of replaceable energy‐dissipation component installed at the bottom corner of RC structural walls was proposed. To study the seismic performance of the new structural wall with RCCs, the cyclic loading tests on three new structural wall specimens and one conventional RC structural wall specimen were conducted. One of the new structural wall specimens experienced replacement and reloading process to verify the feasibility of replacement. The results show that the structural behavior of all specimens was flexure dominating. The damage in the new shear specimens mainly concentrated on RCCs. The replacement of RCCs can be implemented conveniently after the residual deformation occurred in the structure. Compared with the conventional structural wall specimen, the seismic performance of new structural wall specimens was improved significantly. Copyright © 2017 John Wiley & Sons, Ltd.

Electrostatic manipulation of triblock terpolymer nanofilm compartmentalization has been achieved via visible light-initiated reversible addition–fragmentation chain transfer aqueous dispersion polymerization of diacetone acrylamide monomer using cationic–neutral diblock copolymer macro-chain transfer agent (macro-CTA) at 25 °C. This photoinitiated polymerization-induced self-assembly (photo-PISA) evolves into two modes depending on solution pH. At pH 2.5, this macro-CTA dissolves in water with a fully cationic block; electrostatic repulsion leads to conventional aqueous photo-PISA and the formation of monolayer colloidal nanofilms. At pH 7.3, the cationic block transforms to a hydrophobic ionomer block with 10% cationic repeat units, and the copolymer chains self-assemble into weakly cationic micelles, which leads to seeded photo-PISA via self-assembly into discrete nanoclusters within the hydrophobic lamellar framework to form multicompartmentalized monolayer nanofilms. The nanoscale phase-separated 2D-confined nanoclusters and the lamellar structure can be tuned by the ABC/BAC block sequence, the degree of polymerization of the growing block, and the copolymer concentration. This electrostatic manipulation sheds new light on the rational design and preparation of multicompartmentalized block copolymer 2D nanoobjects.

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