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Fluorescent block copolymer micelles that can self-report on their assembly and small molecule encapsulation
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Robin, Mathew P., Osborne, Shani A. M., Pikramenou, Zoe, Raymond, Jeffery E. and O’Reilly, Rachel K. (2016) Fluorescent block copolymer micelles that can self-report on their assembly and small molecule encapsulation. Macromolecules, 49 (2). pp. 653-662. 5b02152. doi:10.1021/acs.macromol.5b02152 ISSN 0024-9297 .
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Official URL: http://dx.doi.org/10.1021/acs.macromol.5b02152
Abstract
Block copolymer micelles have been prepared with a dithiomaleimide (DTM) fluorophore located in either the core or shell. Poly(triethylene glycol acrylate)-b-poly(tert-butyl acrylate) (P(TEGA)-b-P(tBA)) was synthesized by RAFT polymerization, with a DTM-functional acrylate monomer copolymerized into either the core forming P(tBA) block or the shell forming P(TEGA) block. Self-assembly by direct dissolution afforded spherical micelles with Rh of ca. 35 nm. Core-labeled micelles (CLMs) displayed bright emission (Φf = 17%) due to good protection of the fluorophore, whereas shell-labeled micelles (SLMs) had lower efficiency emission due to collisional quenching in the solvated corona. The transition from micelles to polymer unimers upon dilution could be detected by measuring the emission intensity of the solutions. For the core-labeled micelles, the fluorescence lifetime was also responsive to the supramolecular state, the lifetime being significantly longer for the micelles (τAv,I = 19 ns) than for the polymer unimers (τAv,I = 9 ns). The core-labeled micelles could also self-report on the presence of a fluorescent hydrophobic guest molecule (Nile Red) as a result of Förster resonance energy transfer (FRET) between the DTM fluorophore and the guest. The sensitivity of the DTM fluorophore to its environment therefore provides a simple handle to obtain detailed structural information for the labeled polymer micelles. A case will also be made for the application superiority of core-labeled micelles over shell-labeled micelles for the DTM fluorophore.
Item Type: | Journal Article | ||||||
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Subjects: | Q Science > QD Chemistry | ||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||
Library of Congress Subject Headings (LCSH): | Micelles, Fluorescence spectroscopy | ||||||
Journal or Publication Title: | Macromolecules | ||||||
Publisher: | American Chemical Society | ||||||
ISSN: | 0024-9297 | ||||||
Official Date: | 26 January 2016 | ||||||
Dates: |
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Volume: | 49 | ||||||
Number: | 2 | ||||||
Number of Pages: | 10 | ||||||
Page Range: | pp. 653-662 | ||||||
Article Number: | 5b02152 | ||||||
DOI: | 10.1021/acs.macromol.5b02152 | ||||||
Status: | Peer Reviewed | ||||||
Publication Status: | Published | ||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||
Funder: | University of Warwick. Institute of Advanced Study (IAS), European Research Council (ERC), Engineering and Physical Sciences Research Council (EPSRC), Leverhulme Trust (LT), University of Birmingham, Birmingham Science City, Advantage West Midlands (AWM), European Regional Development Fund (ERDF) | ||||||
Grant number: | 615142 (ERC) |
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