Monitoring Collapse of Uniform Cylindrical Brushes with a Thermoresponsive Corona in Water

Density effects on collapse, compression, and adhesion of thermoresponsive polymer brushes.

We probe, using the surface forces apparatus, the thermal response of poly(N-isopropylacrylamide) (PNIPAM) brushes of various grafting densities, grown from plasma-activated mica by means of surface-initiated polymerization. We thus show that dense thermoresponsive brushes collapse gradually as temperature is increased and that grafting density greatly affects their ability to swell: the swelli...

Ionic effects in collapse of polyelectrolyte brushes.

We investigated the effect of counterion valence on the structure and swelling behavior of polyelectrolyte brushes using a nonlocal density functional theory that accounts for the excluded-volume effects of all ionic species and intrachain and electrostatic correlations. It was shown that charge correlation in the presence of multivalent counterions results in collapse of a polyelectrolyte brus...

Two-stage collapse of unimolecular micelles with double thermoresponsive coronas.

Phase transition behavior of unimolecular dendritic three-layer nanostructures with dual thermoresponsive coronas is studied. Successive reversible addition-fragmentation transfer (RAFT) polymerizations of N-isopropylacrylamide (NIPAM) and 2-(dimethylamino)ethyl methacrylate (DMA) were conducted using fractionated fourth-generation hyperbranched polyester (Bolton H40) based macroRAFT agent. At ...

The Conformation of Thermoresponsive Polymer Brushes Probed by Optical Reflectivity.

We describe a microscope-based optical setup that allows us to perform space- and time-resolved measurements of the spectral reflectance of transparent substrates coated with ultrathin films. This technique is applied to investigate the behavior in water of thermosensitive polymer brushes made of poly(N-isopropylacrylamide) grafted on glass. We show that spectral reflectance measurements yield ...

New perspectives for the design of molecular actuators: thermally induced collapse of single macromolecules from cylindrical brushes to spheres.