Thermoresponsive Reversible Unimer Micelles of Amphiphilic Fluorinated Copolymers

Elisa Guazzelli, Elena Masotti, Manfred Kriechbaum, Frank Uhlig, Giancarlo Galli, Elisa Martinelli*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Amphiphilic fluorinated copolymers PEGMAx-co-FAy and TEGMAx-co-FAy are prepared by activators regenerated by electron transfer atom transfer radical polymerization (ARGET-ATRP). All polymers present a reversible thermoresponsive lower critical solution temperature-type behavior, and a cloud point temperature (T c) in the range of 30–60 °C strictly dependent on the length of the oxyethylene side chain, the content of the hydrophobic counits, and the concentration of the solution. Combined small angle X-ray scattering (SAXS) and dynamic light scattering measurements are used to study the self-assembly behavior in water, organic solvents (tetrahydrofuran [THF] and dimethylformamide [DMF]), and a fluorinated solvent (hexafluorobenzene [HFB]). SAXS confirms the formation of compact-globular single-chain self-folded unimer micelles in water below T c, which generally presents small hydrodynamic diameters (D h ≤ 8 nm) as a result of the folding of the hydrophobic perfluorohexylethyl acrylate counits. The copolymers are also able to form reverse unimer micelle in HFB. The copolymers are not able to self-assemble in unimer micelles in THF or DMF solutions, in which they adopt conventional random coil conformations.

Original languageEnglish
JournalMacromolecular Chemistry and Physics
Early online date4 Dec 2022
Publication statusE-pub ahead of print - 4 Dec 2022


  • amphiphilic polymers
  • lower critical solution temperature
  • reverse micelles
  • single-chain nanoparticles
  • small angle X-ray scattering
  • thermoresponsive polymers

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Materials Chemistry
  • Polymers and Plastics
  • Physical and Theoretical Chemistry
  • Organic Chemistry


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