Uniform, High Aspect Ratio Fiber-like Micelles and Block Co-micelles with a Crystalline π-Conjugated Polythiophene Core by Self-Seeding

Abstract

Monodisperse fiber-like micelles with a crystalline π-conjugated polythiophene core with lengths up to ca. 700 nm were successfully prepared from the diblock copolymer poly(3-hexylthiophene)-block-polystyrene using a one-dimensional self-seeding technique. Addition of a polythiophene block copolymer with a different corona-forming block to the resulting nanofibers led to the formation of segmented B-A-B triblock co-micelles by crystallization-driven seeded growth. The key to these advances appears to be the formation of a relatively defect-free crystalline micelle core under the self-seeding conditions.

Two-dimensional assemblies from crystallizable homopolymers with charged termini

“…The seeded growth process is likely to be extendable to a wide range of crystallizable polymers, including -conjugated and biodegradable materials, 19,23 and allows precise control of dimensions and access to hierarchical 2D segmented comicelles and also other complex architectures. The resulting shaped 2D platelets possess a lipophilic charged surface and offer potential applications as carriers for nanoparticles, biomolecules, and therapeutic agents, as liquid crystals and adhesives, and in composite reinforcement.…”

“…Seeded-growth of crystallizable BCPs from 1D cylindrical seeds prepared by sonication of long, polydisperse cylinders with a crystalline core provides a recently established route to low dispersity cylindrical micelles of controlled length [18][19][20] and also complex architectures such as block comicelles, [21][22][23] branched cylindrical micelles, 24 and multi-armed micelles. 25 The key to this approach is that the core termini of the seeds remain active to the addition of further BCP unimer, leading to a process that is analogous to a living covalent polymerization of molecular monomers.…”

A design strategy for the hierarchical fabrication of colloidal hybrid mesostructures

“…Although the specific proof of concept example described here involved PFS 30 -b-P2VP 300 as the micelle forming polymer, the fabrication protocol should in principle apply to any BCP that forms elongated core-crystalline micelles and to any substrate to which the corona chains of the seed crystallites can attach. For example, we have recently shown that CDSA can be extended to BCP micelles with a conjugated crystalline polythiophene core 22,37 Electron microscopy. Bright-field transmission electron microscopy (TEM) images were taken using a Hitachi H-7000 instrument.…”

Controlling supramolecular polymerization through multicomponent self‐assembly

“…381 Next to the single component micelles, B-A-B triblock comicelles were obtained by CDSA using P3HT-b-PS unimers for the A block, and P3HT-b-PDMS for the B block in the multicomponent cylindrical micelles. 382 Hayward and coworkers reported the sonocrystallization of a twocomponent mixture of a perylene diimide (PDI) derivative with P3HT, which acts as a soluble crystal modifier. Nanowires of welldefined dimensions are obtained by tuning the P3HT molecular weight, the ratio of P3HT to PDI, and the sonification temperature.…”