Spatiotemporal mapping of concentration polarization induced pH changes at nanoconstrictions

Under an applied electric field, concentration polarization (CP) arises from ion permselectivity of most nanoporous materials and biological ion channels. We present novel methods to quantitatively assess CP-induced spatiotemporal changes of pH that may significantly impact transport dynamics, device functionality, and physicochemical properties of molecular analytes in devices with nanofluidic constrictions. We measured pH fluctuations of >1.5 pH units and changes extending over 100's of micrometers from nanoconstrictions. The degree of change depends on key system parameters including buffer composition, surface charge, and strength of electric field. The results highlight the importance of neglected contributions of pH changes, and the approach can aid characterization and manipulation of mass transport in nanofluidic systems.