Abstract
Crystallization-driven self-assembly of diblock copolymers into cylindrical micelles of controlled length has emerged as a promising approach to the fabrication of functional nanoscale objects with high shape anisotropy. Here we show the preparation of a series of crystallizable diblock copolymers with appropriate wettability and chemical reactivity, and demonstrate their self-assembly into size-specific cylindrical micelle building blocks for the hierarchical construction of mechanically robust colloidosomes with a range of membrane textures, surface chemistries and optical properties. The colloidosomes can be structurally elaborated post assembly by in situ epitaxial elongation of the membrane building blocks to produce microcapsules covered in a chemically distinct, dense network of hair-like outgrowths. Our approach provides a route to hierarchically ordered colloidosomes that retain the intrinsic growth activity of their constituent building blocks to permit biofunctionalization, and have potential applications in areas such as biomimetic encapsulation, drug delivery, catalysis and biosensing.
Highlights
Crystallization-driven self-assembly of diblock copolymers into cylindrical micelles of controlled length has emerged as a promising approach to the fabrication of functional nanoscale objects with high shape anisotropy
Cylindrical micelles with appropriate levels of wettability were prepared by chemical modification of the diblock copolymer PFS25-b-PMVS245 (Mn = 27,250 g mol−1, polydispersity index (PDI) = 1.18; Supplementary Fig. 1)[38, 39]
Thiol-ene photoirradiation of PFS25-b-PMVS245 in the presence of 3-mercaptopropionic acid and 2,2-dimethoxy-2-phenylacetophenone (DMPA, photoinitiator) was used to produce PFS25-b-PMVSCOOH245 (BCP1; Fig. 1b, Supplementary Fig. 2 and Methods), which consisted of a hydrophobic and crystallizable short PFS core-forming block along with a longer PMVS corona-forming domain comprising hydrophilic carboxylic acid groups
Summary
Crystallization-driven self-assembly of diblock copolymers into cylindrical micelles of controlled length has emerged as a promising approach to the fabrication of functional nanoscale objects with high shape anisotropy. We develop a complementary approach using chemically transformed poly(ferrocenyldimethylsilane) (PFS)–poly (methylvinylsiloxane) (PMVS) diblock copolymers to prepare size-specific cylindrical micelles comprising a crystalline PFS core and disordered carboxylated PMVS corona by a seeded growth process known as living crystallization-driven self-assembly (CDSA)[37,38,39,40,41] We exploit these specialized BCP building blocks for the hierarchical construction of mechanically robust polymer colloidosomes with a range of membrane textures, surface chemistries and optical properties. Our results provide a step towards the interfacial assembly of colloidosomes that retain the intrinsic growth activity of their constituent building blocks This approach could open up new routes to bespoke hierarchical structures for use in biomimetic encapsulation, drug delivery, catalysis and biosensing
Sign-in/Register to view highlights & summary 
Published Version (
Free)
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call