Electrochemiluminescent pH sensor measured by the emission potential of TiO2 nanocrystals and its biosensing application

This work reports for the first time a potential-based nano-electrochemiluminescent (ECL) pH sensor, using anatase TiO2 nanocrystals (NCs) as the ECL probe. The first ECL peak potential of the TiO2 NCs shifted negatively with increasing pH, showing a linear range from −0.47 V (vs Ag/AgCl) at pH 3 to −1.06 V at pH 10. This phenomenon was attributed to the absorption of ‘potential-determining ions’ of OH− on the surface of TiO2 NCs, leading to larger impedance of the electron injection. Other common ‘potential-determining ions’, such as phosphate, induced a slight potential shift of 0.03 V at a concentration of 0.1 M. Using urease as an enzyme model, a urea biosensor was developed by the simultaneous modification of urease and TiO2 NCs on indium–tin oxide (ITO) electrodes. The biosensor, measured on the basis of the pH increase caused by the enzyme catalysis reaction, had a linear range of 0.01–2.0 mM, with a potential shift of 0.175 V. The as-prepared pH sensor, which has simple construction procedures and acceptable sensitivity and selectivity, may provide new avenues for the construction of ECL bioanalytical methodologies. Copyright © 2014 John Wiley & Sons, Ltd.