We report on the evaporation-induced confinement assembly (EICA) of polystyrene-b-polybutadiene-b-poly­(methyl methacrylate) (PS-b-PB-b-PMMA, SBM) triblock terpolymers into multicompartment microparticles and follow their morphological evolution during solvent-adsorption annealing. We initially obtain elliptic microparticles with axially stacked PS/PB/PMMA morphology using cetyltrimethylammonium bromide (CTAB) as surfactant. Exchanging the surfactant to poly­(vinyl alcohol) (PVA) during solvent vapor annealing with chloroform (CHCl3), PMMA preferentially interacts with the interface, and microparticles change their shape into spheres with concentric morphology. Surprisingly, this transformation initiates at both poles of the microparticles simultaneously and then proceeds toward the equator, resulting in particles with inner morphology and patchy topography. We observed this evolution for different PB fractions, suggesting the mechanism to be more general and the EICA process to be a suitable method to generate patchy particle surfaces.

A straightforward method is presented for the preparation of nano‐ to micrometer‐sized Janus discs with controlled shape, size, and aspect ratio. The method relies on cross‐linkable ABC triblock terpolymers and involves first the preparation of prolate ellipsoidal microparticles by combining Shirasu porous glass (SPG) membrane emulsification with evaporation‐induced confinement assembly (EICA). By varying the pore diameter of the SPG membrane, we produce Janus discs with controlled size distributions centered around hundreds of nanometers to several microns. We further transferred the discs to water by mild sulfonation of PS to polystyrene sulfonic acid (PSS) and verified the Janus character by subsequent labelling with cationic nanoparticles. Finally, we show that the sulfonated Janus discs are amphiphilic and can be used as efficient colloidal stabilizers for oil‐in‐water (O/W) emulsions.

Self-assembly of block copolymers (BCPs) in three-dimensional (3D) confinement of emulsion droplets has emerged as a versatile route for the formation of functional micro- and nanoparticles. While the self-assembly of amorphous coil–coil BCPs is fairly well documented, less is known about the behavior of crystalline–coil BCPs. Here, we demonstrate that confining a linear ABC triblock terpolymer with a crystallizable middle block in oil-in-water (O/W) emulsions results in a range of microparticles with frustrated inner structure originating from the conflict between crystallization and curved interfaces. Polystyrene-block-polyethylene-block-poly­(methyl methacrylate) (PS-b-PE-b-PMMA, S32E36M32 93) in toluene droplets was subjected to different preparation protocols. If evaporation was performed well above the bulk crystallization temperature of the PE block (T evap > T c), S32E36M32 93 first microphase-separated into microparticles with lamella morphology followed by crystallization into a variety of frustrated morphologies (e.g., bud-like, double staircase, spherocone). By evaporating at significantly lower temperatures that allow the PE block to crystallize from solution (T evap < T c), S32E36M32 93 underwent crystallization-driven self-assembly into patchy crystalline-core micelles, followed by confinement assembly into lenticular microparticles with compartmentalized hexagonal cylinder lattices. The frequency of these frustrated morphologies depends on polymer concentration and the evaporation protocol. These results provide a preliminary understanding of the morphological behavior of semicrystalline block copolymers in 3D soft confinement and may provide alternative routes to structure multicompartment microparticles from a broader range of polymer properties.

Self-assembly of block copolymers in three-dimensional (3D) soft confinement has become a versatile method for the preparation of functional microparticles. While the morphological behavior of AB diblock copolymers in confinement is fairly well understood, only sporadic examples exist for ABC triblock terpolymers. Considering the more complex morphological space of terpolymers, a better understanding of their behavior in confinement would be desirable to gain access to a large variety of multicompartment microparticles (MMs). Here, we report on the 3D confinement self-assembly of MMs from a library of polystyrene-blockpolybutadiene-block-poly(tert-butyl methacrylate) (PS-b-PB-b-PT or SBT) triblock terpolymers with widely different block volume fractions (ϕ), which can be mapped into a ternary microphase diagram. Equal-sized end blocks (ϕ S ≈ ϕ T ) result in MMs with lamella−lamella (LL) morphology and a tulip-bulb or pinecone shape, irrespective of ϕ B . For asymmetric end blocks (ϕ S > ϕ T ) at low ϕ B , prolate ellipsoids develop a hexagonally packed core−shell ring (HCR) morphology, which changes with increasing ϕ B to a transition structure between HCR and a concentric sphere-in-lamella (CSL) morphology. Further increasing ϕ B to ϕ S ≈ ϕ B at low ϕ T , the structure transforms entirely to CSL in an onion-like shape. Selective cross-linking of the PB middle block and disassembly of the MMs give access to a variety of nanostructures such as core−shell rings, Janus nanobowls, and nanocups.

A series of novel guanidinium-based magnetic ionic liquids were synthesized. Among them, [TMG]­Cl/1.5FeCl3 exhibited a very strong paramagnetic strength with the value of magnetic susceptibility as great as 59.1 × 10–6 emu/g, which exceeded any other reported magnetic IL so far. By virtue of good physical and chemical properties, it was representatively selected to extract dibenzothiophene (DBT) and thiophene (T) from model oils with sulfur content of 900–1000 μg/g, which was compared with commonly reported imidazolium magnetic ionic liquid [BMIM]­Br/1.5FeCl3. The results revealed that [TMG]­Cl/1.5FeCl3 had perfect desulfurization efficiency (nearly 100%) with mass ratio of oil to MIL (g/g) of 1–4 within only 5 min at room temperature, and the method could easily meet the latest European sulfur emission standard (Euro 5). It showed significant selectivity for sulfur over toluene, as well as little pollution of the model oils, which were both better than [BMIM] Br/1.5FeCl3. Satisfactory desulfurization performance for 93 gasoline was further achieved by [TMG]­Cl/1.5FeCl3. Furthermore, it could be recycled at least 7 times without any noticeable decrease in desulfurization efficiency. The novel MIL demonstrates promise in practical application in the future.