Self-Assembly of Rod-Coil Block Copolymers on Carbon Nanotubes: A Route toward Diverse Surface Nanostructures.

In this work, it is reported that poly(γ-benzyl-l-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) rod-coil block copolymers (BCPs) can disperse carbon nanotubes (CNTs) in solution and form various surface nanostructures on the CNTs via solution self-assembly. In an organic solvent that dissolves the BCPs, the PBLG rod blocks adsorb on CNT surfaces, and the BCPs form conformal coatings. Then, by the introduction of water, a selective solvent for PEG blocks, the BCPs in the coatings further self-assemble into diverse surface nanostructures, such as helices (left-handed or right-handed), gyros, spheres, and rings. The morphology of the surface nanostructure can be tailored by initial organic solvent composition, preparation temperature, feeding ratio of BCPs to CNTs, degree of polymerization of PBLG blocks, and diameter of the CNTs.

Spiral- and meridian-patterned spheres self-assembled from block copolymer/homopolymer binary systems.

Spiral nanostructures, mainly in the 2D form, have been observed in polymer self-assembly, while well-defined 3D spirals are rarely reported. Here we report that a binary system containing polypeptide-based block copolymers and homopolymers can self-assemble into well-defined spiral spheres (3D spirals), in which the homopolymers form the core and the copolymers form the spirals. Upon increasing the preparation temperature, meridian spheres were obtained. Mixing polypeptide block copolymers with opposite backbone chirality also leads to the formation of meridian spheres. In the meridian patterns, a tighter packing manner of the phenyl groups appended to the polypeptide blocks was observed, which is responsible for the spiral-to-meridian transitions. This work enriches the research of spiral assemblies and provides a facile route to switch chiral/achiral nanostructures by regulating the packing manner of the pendant groups.

Assembly of silica rods into tunable branched living nanostructures mediated by coalescence of catalyst droplets.

Branched nanostructures with tunable arm numbers were prepared through the assembly of silica rods mediated by coalescence of catalyst droplets on the end of the rods. The formed primary branched colloids retain living characteristics similar to the original ones, that is, they can further assemble into multilevel and hierarchical branched structures.

Ordered Surface Nanostructures Self-Assembled from Rod-Coil Block Copolymers on Microspheres.

An ordered surface nanostructure endows materials advanced functions. However, fabricating ordered surface-patterned particles via the polymer self-assembly approach is a challenge. Here we report that poly(γ-benzyl-l-glutamate)-block-poly(ethylene glycol) rod-coil block copolymers are able to form uniform-surface micelles on polystyrene microspheres through a solution self-assembly approach. The size of the surface micelles can be varied by the molecular weight of the block copolymers. These surface micelles are arranged in a manner consistent with the Euler theorem. Most of the micelles are six-fold coordinated, and the number difference between the five-fold and the seven-fold coordination is 12. Simulations on model systems qualitatively reproduced the experimental findings and provided direct observations for the surface-patterned particles, including the polymer chain packing manner in surface micelles at the molecular level and the array feature of the surface micelles through 2D projections of the surface patterns.