Polyelectrolyte brush pH-response at the silica-aqueous solution interface: a kinetic and equilibrium investigation.

Autor: Cheesman BT; Priority Research Centre for Advanced Particle Processing and Transport, University of Newcastle, Callaghan, NSW 2308, Australia., Smith EG, Murdoch TJ, Guibert C, Webber GB, Edmondson S, Wanless EJ
Jazyk: angličtina
Zdroj: Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2013 Sep 14; Vol. 15 (34), pp. 14502-10. Date of Electronic Publication: 2013 Jul 29.
DOI: 10.1039/c3cp52281d
Abstrakt: Polymer brushes are commonly used to modify the properties of solid surfaces. Here a family of polybasic poly(2-(diethylamino)ethyl methacrylate) brushes have been grown using ARGET ATRP from a cationic macroinitiator adsorbed on two types of silica surfaces: QCM crystals and oxidised silicon wafers. The pH-response of these brushes is investigated as a function of brush thickness in a constant flow environment in order to focus on the intrinsic dynamics of the polymer brushes. Independent QCM-D and in situ ellipsometry kinetic studies demonstrate the swelling process of protonation and solvent uptake is typically eight times faster than the corresponding neutralisation and solvent expulsion from the collapsing brush. However, the maximum rate of these processes is independent of brush thickness. The initial pH response of the brushes is hysteretic due to brush entanglement, which once overcome allows highly reversible pH-induced conformational changes. Multiple pH cycles demonstrate that the viscoelastic nature of the swollen state relative to the collapsed brush is independent of brush thickness.
Databáze: MEDLINE