Switchable selectivity for gating ion transport with mixed polyelectrolyte brushes: approaching 'smart' drug delivery systems

A pH-responsive mixed polyelectrolyte brush from tethered polyacrylic acid (PAA) and poly(2-vinylpyridine) (P2VP) (PAA: P2VP = 69: 31 by weight) was prepared and used for selective gating transport of anions and cations across the thin film. An ITO glass electrode was modified with the polymer brush and used to study the switchable permeability of the mixed brush triggered by changes in pH of the aqueous environment in the presence of two soluble redox probes: [Fe(CN)(6)](4-) and [Ru(NH3)(6)](3+). The responsive behavior of the brush was also investigated using the in situ ellipsometric measurements of the brush swelling, examination of the brush morphology with atomic force microscopy (AFM), and contact angle measurements of the brush samples extracted from aqueous solutions at different pH values. The mixed brush demonstrated a bipolar permselective behavior. At pH < 3 the positively charged P2VP chains enabled the electrochemical process for the negatively charged redox probe, [Fe(CN)(6)](4-), while the redox process for the positively charged redox probe was effectively inhibited. On the contrary, at pH > 6 a reversible redox process for the positively charged redox probe, [Ru(NH3)(6)](3+), was observed, while the redox process for the negatively charged redox species, [Fe(CN)(6)](4-), was fully inhibited. Stepwise changing the pH value and recording cyclic voltammograms for the intermediate states of the polymer brush allowed electrochemical observation of the brush transition from the positively charged state, permeable for the negatively charged species, to the negatively charged state, permeable for the positively charged species. The data of ellipsometric, AFM and contact angle measurements are in accord with the electrochemical study. The discovered properties of the brush could be used for the development of 'smart' sensors and drug delivery systems, for example, a smart drug delivery capsule which could release negatively charged molecules of drugs in acidic conditions, while positively charged molecules of drugs will be released in neutral conditions.