pH-sensing properties of poly(aniline) ultrathin films self-assembled on indium-tin oxide

The structural and functional properties of ultrathin (<5 nm) poly(aniline) (PANI) films deposited on indium-tin oxide (ITO) have been investigated using electrochemical and attenuated total reflection (ATR) spectroscopy methods. Layer-by-layer (LbL) self-assembly was used to form films composed of one and two bilayers of PANI and poly(acrylic acid) (PAA), as well as single PANI layers of approximately monolayer thickness. PANI deposited on an ITO electrode is electroactive at neutral pH, both with and without codeposition of an acid dopant such as PAA. In the absence of PAA, it is hypothesized that the acidic surface groups on ITO can function as the counterion. The pH response of PANI single layer, (PANI/PAA)(1), and (PANI/PAA)(2) films was examined using both potentiometry and ATR spectroscopy. Near-Nernstian potentiometric responses over pH 3-9 were observed for all three types of films, consistent with the weak acid-base behavior expected of polymers assembled in a LbL film. The ATR spectral sensitivity to pH increases as the number of layers in the film increases, with the highest sensitivity achieved by monitoring the absorbance at 800 nm (predominately due to the emeraldine salt form) of (PANI/PAA)(2) films. Codeposition of PANI and PAA appears to produce a wide distribution of strengths of acidic and basic sites in the film and thus a large linear dynamic range, up to six pH units. The water contact angle of (PANI/PAA)(2) is approximately 16 degrees, which is considerably more hydrophilic than either the PANI single layer or (PANI/PAA)(1) films ( approximately 40 degrees ). This film is shown to be a suitable substrate for deposition of a planar supported phospholipid bilayer. The supported membrane is highly impermeable to protons, which makes this architecture useful for monitoring transmembrane charge transport.