Prolate and temperature-responsive self-assemblies of amphiphilic random copolymers with perfluoroalkyl and polyoxyethylene side chains in solution

Two amphiphilic random copolymers, PEGMAx-co-FAy (x = 90 and 70 mol%), were synthesized by ATRP and their solutions were investigated as a function of solvent, concentration and temperature by DLS and SANS analyses. Both copolymers self-assembled in nanostructures by single-chain folding in water solutions over a wide range of temperatures. The values of the DLS hydrodynamic radius and the SANS radius of gyration were found to be ~4 nm and ~3.4–3.7 nm, respectively. Moreover, SANS showed the self-folded nanoassemblies to be prolated spheroids with ratio of polar/equatorial axes ~5:1 for PEGMA90-co-FA10 and ~2:1 for PEGMA70-co-FA30. On heating above a critical temperature Tc, multi-chain microassemblies were formed that reverted back to nanoassemblies on cooling below Tc. This temperature-responsive transition was fully and sharply reversible.