Responsive vesicles from the self-assembly of crystalline-coil polyferrocenylsilane-block-poly(ethylene oxide) star-block copolymers

Felix H. Schacher, Johannes Elbert, Sanjib K. Patra, Siti Fairus Mohd Yusoff, Mitchell A. Winnik, Ian Manners

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

We demonstrate the synthesis and characterization of star-shaped crystalline-coil block copolymers with four arms consisting of an inner block of poly(ethylene oxide) and an outer semicrystalline compartment of poly(ferrocenyldimethylsilane), [PEO 50-b-PFDMS 35] 4. The materials were synthesized by transition-metal-catalyzed ring-opening polymerization of dimethylsila[1]ferrocenophane in the presence of silane-functionalized four-arm PEO stars as macroinitiators and they exhibited a moderate polydispersity (PDI≃1.4). Self-assembly in mixtures of THF and different alcohols as selective solvents for the PEO block resulted in the formation of semicrystalline vesicles (ethanol, 1-butanol) or large, rather ill-defined, spherical structures (methanol). Further, both the rate of addition of the selective co-solvent and the overall solvent/non-solvent ratio drastically affected the size and stability of the self-assembled particles. We could also show that a photoacid generator, as a model for an active substance, can be encapsulated and the UV-induced generation of HCl resulted in a straightforward degradation of the organometallic vesicles. Four arms to the wall: The synthesis, characterization and self-assembly of star-shaped crystalline-coil block copolymers with four arms (see figure), consisting of an inner block of poly(ethylene oxide) and an outer semicrystalline compartment of poly(ferrocenyldimethylsilane) [PEO 50-b-PFDMS 35] 4 is reported. Depending on the conditions, responsive organometallic vesicles with a crystalline wall or large compound micelles are formed.

Original languageEnglish
Pages (from-to)517-525
Number of pages9
JournalChemistry - A European Journal
Volume18
Issue number2
DOIs
Publication statusPublished - 9 Jan 2012

Fingerprint

Polyethylene oxides
Self assembly
Block copolymers
Stars
Crystalline materials
Organometallics
Silanes
1-Butanol
Ring opening polymerization
Polydispersity
Micelles
Butenes
Transition metals
Methanol
Alcohols
Ethanol
Degradation

Keywords

  • block copolymers
  • nanostructures
  • self-assembly
  • solvent effects

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Responsive vesicles from the self-assembly of crystalline-coil polyferrocenylsilane-block-poly(ethylene oxide) star-block copolymers. / Schacher, Felix H.; Elbert, Johannes; Patra, Sanjib K.; Mohd Yusoff, Siti Fairus; Winnik, Mitchell A.; Manners, Ian.

In: Chemistry - A European Journal, Vol. 18, No. 2, 09.01.2012, p. 517-525.

Research output: Contribution to journalArticle

Schacher, Felix H. ; Elbert, Johannes ; Patra, Sanjib K. ; Mohd Yusoff, Siti Fairus ; Winnik, Mitchell A. ; Manners, Ian. / Responsive vesicles from the self-assembly of crystalline-coil polyferrocenylsilane-block-poly(ethylene oxide) star-block copolymers. In: Chemistry - A European Journal. 2012 ; Vol. 18, No. 2. pp. 517-525.
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