Temperature-Sensitive Phase Transition of Dendritic Polyethylene Amphiphiles with Core−Shell Architecture Revealed by a Rayleigh Scattering Technique

Abstract

The phase-transition behavior of unimolecular dendritic polyethylene amphiphiles with core-shell architecture aqueous solutions was investigated by a Rayleigh scattering (RS) technique. Dendritic polyethylene (DPE)-poly(oligo(ethylenegylcol) methacrylate) (POEGMA) with a DPE hydrophobic core and a POEGMA hydrophilic shell was synthesized by the atom-transfer radical polymerization (ATRP) of OEGMA using DPE terminated by the bromine group as a macroinitiator. The fluorescence measurements implied that DPE-POEGMA molecules in aqueous solutions existed as the unimolecular micelles. To understand the phase-transition behavior of dendritic polyethylene amphiphilic unimolecular micelles in aqueous solutions, the temperature dependence of the RS spectra of DPE-POEGMA aqueous solutions under the heating-and-cooling cycle indicated that the heating and cooling processes were reversible but hysteresis existed. The phase transition of DPE-POEGMA aqueous solutions decelerated with increasing levels of PEGylation. DPE-POEGMA exhibited a lower phase-transition temperature in D(2)O than in water.