Extending the Scope of “Living” Crystallization-Driven Self Assembly: Well-Defined 1D Micelles and Block Comicelles from Crystallizable Polycarbonate Block Copolymers

John Finnegan, Xiaoming He, Steve Street, Diego Garcia Hernandez, Dominic Hayward, Robert Harniman, Robert Richardson, George Whittell, Ian Manners

Research output: Contribution to journalArticle (Academic Journal)peer-review

35 Citations (Scopus)
208 Downloads (Pure)

Abstract

Fiber-like block copolymer (BCP) micelles offer considerable potential for a variety of applications, however, uniform sam-ples of controlled length and with spatially tailored chemistry have not been accessible. Recently, a seeded growth method, termed ‘living’ crystallization-driven self-assembly (CDSA), has been developed to allow the formation of 1D micelles and block comicelles of precisely controlled dimensions from BCPs with a crystallizable segment. An expansion of the range of core forming blocks that participate in living CDSA is necessary for this technique to be compatible with a broad range of applications. Few examples currently exist of well-defined, water-dispersible BCP micelles prepared using this approach, especially from biocompatible and biodegradable polymers. Herein, we demonstrate that BCPs containing a crystallizable polycarbonate, poly(spiro[fluorene-9,5’-[1,3]dioxin]-2’-one) (PFTMC), can readily undergo living CDSA processes. PFTMC b poly(ethylene glycol) (PEG) BCPs with PFTMC:PEG block ratios of 1:11 and 1:25 were shown to undergo liv-ing CDSA to form near monodisperse fiber like micelles of precisely controlled lengths of up to ~1.6 m. Detailed structur-al characterization of these micelles by TEM, AFM, SAXS and WAXS, revealed that they comprise a crystalline, chain folded PFTMC core with a rectangular cross-section that is surrounded by a solvent swollen PEG corona. PFTMC b PEG fiber-like micelles were shown to be dispersible in water to give colloidally stable solutions. This allowed an assessment of the toxicity of these structures towards WI-38 and HeLa cells. From these experiments, we observed no discernable cytotoxi-city from a sample of 119 nm fiber-like micelles to either the healthy (WI-38) or cancerous (HeLa) cell types. The living CDSA process was extended to PFTMC-b-poly(2-vinylpyridine) (P2VP), and addition of this BCP to PFTMC-b-PEG seed micelles led to the formation of well-defined segmented fibers with spatially localized coronal chemistries.
Original languageEnglish
JournalJournal of the American Chemical Society
Early online date4 Nov 2018
DOIs
Publication statusE-pub ahead of print - 4 Nov 2018

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