Artificial self-assembly systems typically exhibit limited capability in creating nature-inspired complex materials with advanced functionalities. Here, an effective coassembly strategy is demonstrated for the facile creation of complex photonic structures with intriguing light reflections. Two different lipophilic and amphiphilic bottlebrush block copolymers (BCPs) are placed within shrinking droplets to enable a cooperative working mechanism of microphase segregation and organized spontaneous emulsification, respectively. Layer assemblies of the lipophilic BCP and uniform water nanodroplets stabilized by the bottlebrush surfactant are both generated, and co-assembled into a bridged lamellar structure with the alternating arrangement of layers and closely packed nanodroplet arrays. Janus microspheres with diverse dual optical characteristics are successfully fabricated, and reflected wavelengths of light are highly tunable simply by changing the formulation or molecular weight of BCP.

Microspheres bearing large pores are useful in the capture and separation of biomolecules. However, pore size is typically poorly controlled, leading to disordered porous structures with limited performances. Herein, ordered porous spheres with a layer of cations on the internal surface of the nanopores are facilely fabricated in a single step for effective loading of DNA bearing negative charges. Triblock bottlebrush copolymers (BBCPs), (polynorbornene‐g‐polystyrene)‐b‐(polynorbornene‐g‐polyethylene oxide)‐b‐(polynorbornene‐g‐bromoethane) (PNPS‐b‐PNPEO‐b‐PNBr), are designed and synthesized for fabrication of the positively charged porous spheres through self‐assembly and in situ quaternization during an organized spontaneous emulsification (OSE) process. Pore diameter as well as charge density increase with the increase of PNBr content, resulting in a significant increase of loading density from 4.79 to 22.5 ng µg−1 within the spheres. This work provides a general strategy for efficient loading and encapsulation of DNA, which may be extended to a variety of different areas for different real applications.

Artificial self-assembly systems typically exhibit limited capability in creating nature-inspired complex materials with advanced functionalities. Here, an effective coassembly strategy is demonstrated for the facile creation of complex photonic structures with intriguing light reflections. Two different lipophilic and amphiphilic bottlebrush block copolymers (BCPs) are placed within shrinking droplets to enable a cooperative working mechanism of microphase segregation and organized spontaneous emulsification, respectively. Layer assemblies of the lipophilic BCP and uniform water nanodroplets stabilized by the bottlebrush surfactant are both generated, and co-assembled into a bridged lamellar structure with the alternating arrangement of layers and closely packed nanodroplet arrays. Janus microspheres with diverse dual optical characteristics are successfully fabricated, and reflected wavelengths of light are highly tunable simply by changing the formulation or molecular weight of BCP.