Synthesis of poly[N-isopropylacrylamide-g-poly(ethylene glycol)] with a reactive group at the poly(ethylene glycol) end and its thermosensitive self-assembling character

Poly[N-isopropylacrylamide-g-poly(ethylene glycol)]s with a reactive group at the poly(ethylene glycol) (PEG) end were synthesized by the radical copolymerization of N-isopropylacrylamide with a PEG macromonomer having an acetal group at one end and a methacryloyl group at the other chain end. The temperature dependence of the aqueous solutions of the obtained graft copolymers was estimated by light scattering measurements. The intensity of the light scattering from aqueous polymer solutions increased with increasing temperature. In particular, at temperatures above 40 degrees C, the intensity abruptly increased, indicating a phase separation of the graft copolymer due to the lower critical solution temperature (LCST) of the poly(N-isopropylacrylamide) segment. No turbidity was observed even above the LCST, and this suggested a nanoscale self-assembling structure of the graft copolymer. The dynamic light scattering measurements confirmed that the size of the aggregate was in the range of several tens of nanometers. The acetal group at the end of the PEG graft chain was easily converted to the aldehyde group by an acid treatment, which was analyzed by H-1 NMR. Such a temperature-induced nanosphere possessing reactive PEG tethered chains on the surface is promising for new nanobased biomedical materials. (c) 2006 Wiley Periodicals, Inc.