pH- and Electro-Responsive Properties of Poly(acrylic acid) and Poly(acrylic acid)-block-poly(acrylic acid-grad-styrene) Brushes Studied by Quartz Crystal Microbalance with Dissipation Monitoring.

We report on the synthesis of novel pH- and electro-responsive polyelectrolyte brushes from a gold substrate by direct one-step nitroxide-mediated polymerization of acrylic acid (AA) or copolymerization of AA and styrene (S). In the latter case, amphiphilic brushes of block-gradient copolymers PAA-b-(PAA-grad-PS) comprising one PAA block and one block with the gradient sequence of AA and S were obtained. The block-gradient copolymers are initiated from the surface by the start of the PAA block. The brushes were characterized by XPS and ellipsometry. (1)H NMR confirmed the gradient sequence of the PAA-grad-PS copolymer block. The pH- and electro-responsive properties of the brushes were studied by quartz crystal microbalance with dissipation monitoring (QCM-D) in combination with electrochemistry. This method provides evidence of swelling of the PAA brushes proportional to the contour length of the chains at elevated pH, whereas the response functions of the block-gradient copolymers are more complex and point to intermolecular aggregation in the brush at low pH. Monitoring of the changes in resonance frequency and dissipation of the QCM-D also demonstrates that application of negative voltage to the substrate leads to swelling of the brush; application of a positive voltage provokes only a transient collapse of the brush in proportion to the applied voltage.