title: Hierarchical Assembly of Cylindrical Block Comicelles Mediated by Spatially Confined Hydrogen-Bonding Interactions.
abstract: Hydrogen bonds are among the most common interactions used by nature for the creation of hierarchical structures from smaller building blocks. Herein, we describe an in-depth study of the hierarchical assembly of cylindrical block comicelles with a crystallizable poly(ferrocenyldimethylsilane) (PFS) core via H-bonding interactions to form complex supermicellar structures. Well-defined block comicelles bearing H-bond donor (HD) segments (M(PFS-b-PMVSOH)), or H-bond acceptor (HA) segments (M(PFS-b-P2VP)), and non-interacting (N) segments (M(PFS-b-PtBA)) were created by the living crystallization-driven self-assembly (CDSA) method [PMVSOH = hydroxyl-functionalized poly(methylvinylsiloxane), P2VP = poly(2-vinylpyridine), PtBA = poly(tert-butyl acrylate), M = micelle segment]. Due to the control provided by the living CDSA approach, both the block comicelles and the individual segments were virtually monodisperse in length, which facilitated their predictable hierarchical assembly into higher-level structures. Two cases were investigated in detail: first, the interaction of N-HA-N triblock comicelles with the HDhomopolymer PMVSOH, and second, the interaction of N-HD-N triblock comicelles with very short HAcylinders (seeds). By manipulation of several factors, namely coronal steric effects (via the PtBA corona chain) and attractive interaction strength (via the H-bonding interaction between P2VP and PMVSOH), the aggregation of the triblock comicelles could be controlled, and well-defined multi-micrometer-size structures such as "shish-kebab"-shaped supermicelles were prepared. The ability of the seeds adsorbed on the block comicelles to function as initiators for living CDSA to generate fence-like "shish-kebab" superstructures was also explored.
authors.affiliation: School of Chemistry, University of Bristol , Bristol BS8 1TS, United Kingdom.
authors.forename: Xiaoyu
authors.initials: X
authors.lastname: Li
authors.affiliation: School of Chemistry, University of Bristol , Bristol BS8 1TS, United Kingdom.
authors.forename: Yang
authors.initials: Y
authors.lastname: Gao
authors.affiliation: School of Chemistry, University of Bristol , Bristol BS8 1TS, United Kingdom.
authors.forename: Robert
authors.initials: R
authors.lastname: Harniman
authors.affiliation: Department of Chemistry, University of Toronto , Toronto, Ontario M5S 3H6, Canada.
authors.forename: Mitchell
authors.initials: M
authors.lastname: Winnik
authors.affiliation: School of Chemistry, University of Bristol , Bristol BS8 1TS, United Kingdom.
authors.forename: Ian
authors.initials: I
authors.lastname: Manners