Versatile Method to Expand the Morphology Library of Block Copolymer Solution Self-Assemblies with Tubular Structures

Abstract

Self-assembly of block copolymers (BCPs) in solution is a powerful technology to achieve a broad range of structures, such as spheres, cylinders, vesicles, and other hierarchical structures. However, the BCP self-assembly library is limited, especially with respect to tubular structures. Here we show a versatile strategy to expand the morphology library of block copolymer solution self-assemblies with tubular structures (including tubular dumbbells and tubules) via self-assembly of the most common diblock copolymers P4VP-b-PS BCPs in methanol. No special chemistry is needed in this strategy, which proves the universality of this method. The novelty of the strategy is to keep the BCPs both highly asymmetric and with very high molecular weight. The underlying formation mechanism and kinetics of these tubular structures were elucidated. The prepared tubular structures expand the structure library of BCP solution self-assemblies and open up a new avenue for the further applications of a variety of tubular materials.

Interplay of Solvation and Size Effects Induced by the Counterions in Ionic Block Copolymers on the Basis of Hofmeister Series

“…The self‐assembly of amphiphilic block copolymers (BCPs) in selective solvents is increasingly attracting the attention of researchers in the past decades due to their potential applications in biological drug delivery, microreactor chemistry, and in novel nanostructural templating . In selective solvents, neutral BCPs can form various morphologies such as spheres, cylinders, vesicles, and lamellae, which can be regulated by many factors, such as block length, solvent composition, pH, and inorganic salt . Self‐assembly behaviors of these BCPs are well documented …”

Synthesis of Low‐Dimensional Polyion Complex Nanomaterials via Polymerization‐Induced Electrostatic Self‐Assembly

“…Figure 2s hows ap ure phase of vesicle at 12 %w/w solids.S urprisingly,v esicles were compartmentalized into two chambers at 16 %w/w solids.T he compartmentalization into 3-4 discrete vesicular chambers was fulfilled at 20 %w/w solids.A nalysis of 400 particles per sample indicated ar oughly constant thickness of membrane and septum over 63-67 nm. [24] Polymerization at 25-50 %w/w solids always resulted in large-area flexible film (Figure 2). Minor dumbbell-shape vesicles coexist at 15 %w/w solids ( Figure S7), which infers that the vesicular compartmentalization proceeds via the inelastic collisionfusion mechanism.…”

“…Minor dumbbell-shape vesicles coexist at 15 %w/w solids ( Figure S7), which infers that the vesicular compartmentalization proceeds via the inelastic collisionfusion mechanism. [24] Polymerization at 25-50 %w/w solids always resulted in large-area flexible film (Figure 2). Basically,i ntra-complex reformation led to al adder-like ordered structure in PIC-driven self-assembly.…”

CO2‐Breathing Polymer Assemblies via One‐Pot Sequential RAFT Dispersion Polymerization

“…For a typical PISA process, a solvophilic homopolymer is chain extended with a second monomer to form an amphiphilic block copolymer that undergoes in situ self‐assembly to produce nanoparticles in one pot . Therefore, PISA represents an extremely versatile, efficient, and cost‐effective approach toward fabrication of block copolymer nanoparticles . Introducing stimuli‐responsive functional groups to PISA system provides a convenient route to stimuli‐responsive polymer nanoparticles.…”