Quantitative visualization of molecular transport through porous membranes: enhanced resolution and contrast using intermittent contact-scanning electrochemical microscopy.

The use of intermittent contact-scanning electrochemical microscopy (IC-SECM) in diffusion-limited amperometric mode to visualize and quantify mass transport through multiporous membranes is described using dentin as a model example. The IC mode of SECM employs the damping of a vertically modulated ultramicroelectrode (UME) to achieve positioning close to the receptor side of a membrane. In this way the UME can detect electroactive species close to the pore exit. A key aspect of IC-SECM is that in addition to the direct current (dc) from the diffusion-limited detection of the analyte, an alternating current (ac) also develops due to the motion of the probe. It demonstrates that this ac signal enhances the spatial resolution of SECM detection and allows the hydrodynamic flow of species to be detected from individual closely spaced pores. The experimental deductions are supported by three-dimensional finite element modeling which allows IC-SECM current maps to be analyzed to reveal transport rates through individual pores. The method described should be widely applicable to multiporous membrane transport.