Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device. 17. Improvement in detection limits using ultrathin perfluorosulfonated ionomer films in conjunction with continuous sample flow

We report herein an attenuated total reflectance (ATR) absorbance-based spectroelectrochemical sensor for tris(2,2'-bipyridyl)ruthenium(II) ion [Ru(bpy)(3)(2+)] that employs ultrathin (24-50 nm) Nation films as the charge-selective layer. This film serves to sequester and preconcentrate the analyte at the optically transparent electrode surface such that it can be efficiently detected optically via electrochemical modulation. Our studies indicate that use of ultrathin films in tandem with continuous flow of sample solution through the cell compartment leads to a 100-500-fold enhancement in detection limit (10 nM) compared to earlier absorbance-based spectroelectrochemical sensors (similar to1-5 muM); markedly shorter analysis times also result. We report the dependence of the measured absorbance on sample flow rate and Nafion film thickness, and also provide calibration curves that illustrate the linear range and detection limits of the sensor using a 24 nm film at a constant sample flow rate of 0.07 mL/min.