Responsive photonic crystals (PCs) have attracted much attention due to their broad applications in the field of chemical and physical sensing through varying optical properties when exposed to external stimuli. In particular, assembly of block copolymers (BCPs) has proven to be a robust platform for constructing PCs in the form of films or bulk. Here, the generation of BCPs photonic microspheres is presented with 3D periodical concentric lamellar structures through confined self-assembly. The structural color of the spherical PCs can be tuned by selective swelling of one block, yielding large change of optical property through varying both layer thickness and refraction index of the domains. The as-formed spherical PCs demonstrate large reflection wavelength shift (≈400-700 nm) under organic solvent permeation and pH adjustment. Spherical shape and structural symmetry endow the formed spherical PCs with rotation independence and monochrome, which is potentially useful in the fields of displays, sensing, and diagnostics.

Due to the near-field coupling effect, non-close-packed nanoparticle (NP) assemblies with tunable interparticle distance (d) attract great attention and show huge potential applications in various functional devices, e.g., organic nano-floating-gate memory (NFGM) devices. Unfortunately, the fabrication of device-scale non-close-packed 2D NPs material still remains a challenge, limiting its practical applications. Here, a facile yet robust "rapid liquid-liquid interface assembly" strategy is reported to generate a non-close-packed AuNP superlattice monolayer (SM) on a centimeter scale for high-performance pentacene-based NFGM. The d and hence the surface plasmon resonance spectra of SM can be tailored by adjusting the molecular weight of tethered polymers. Precise control over the d value allows the successful fabrication of photosensitive NFGM devices with highly tunable performances from short-term memory to nonvolatile data storage. The best performing nonvolatile memory device shows remarkable 8-level (3-bit) storage and a memory ratio over 10 even after 10 years compared with traditional devices with a AuNP amorphous monolayer. This work provides a new opportunity to obtain large area 2D NPs materials with non-close-packed structure, which is significantly meaningful to microelectronic, photovoltaics devices, and biochemical sensors.

Self-assembly of block copolymers (BCPs) has been developed as a promising approach for constructing photonic crystal (PC) microspheres for dynamic optical modulation. However, high curvature in the center of microspheres usually distorts the periodic core structure, leading to an inconsistency of photonic bandgap and poor monochromaticity of structural color. Herein, we report a simple yet robust strategy for fabricating responsive PC microcapsules of polystyrene-b-poly(2-vinylpyridine) through self-emulsification strategy. Interestingly, the microcapsules exhibit bright structural color with significantly enhanced monochromaticity, compared to their solid counterpart, since the microcapsules have no irregular cores. The structural colors of the PC microcapsules not only exhibit a variability through binary mixing of BCPs but also show a responsiveness to pH value. As a colored microcarrier, the PC microcapsules show a potential for visualizing the pH-dependent release behavior of encapsulated hydrophilic cargos on account of pH-responsive structural color.

Although high-boiling non-solvent induced macrophase separation in emulsion droplets has been widely applied for the fabrication of polymeric capsules, precise control of their structures remains a great challenge. Herein, block copolymer capsules with tunable shell structures were fabricated by employing a non-solvent as a liquid template in emulsion droplets. The properties of the non-solvents dictate the phase separation sequence in the droplets and the capsule formation mechanism. Two different pathways for capsule formation were observed, and could be applied to predict the shell structure. The structured capsules could be transformed into mesoporous capsules, which demonstrated an intriguing structure-dependent release behavior. Capsules with spherical shell structures displayed the best permeability, while those with lamellar shell structures showed the slowest release, but with a stepwise profile. After loading with an anticancer drug, different capsules induced different apoptosis ratios in cancer cell studies.

Here we report the structural control of polystyrene-b-polyisoprene-b-poly(2-vinylpyridine) (PS-b-PI-b-P2VP) asymmetric ABC triblock copolymer particles under 3D confinement by tuning the interactions among blocks. The additives, including 3-n-pentadecylphenol, homopolystyrene, and solvents, which can modulate the interactions among polymer blocks, play significant roles in the particle morphology. Moreover, the structured particles can be disassembled into isolated micellar aggregates with novel morphologies or mesoporous particles with tunable pore shape. Interestingly, the formed pupa-like PS-b-PI-b-P2VP particles display interesting dynamic stretch-retraction behavior when the solvent property is changed after partial cross-linking of the P2VP block. We further prove that such dynamic behavior is closely related to the density of cross-linking. The strategies presented here are believed to be promising routes to rationally design and fabricate block copolymer particles with desirable shape and internal structure.