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When a direct current (DC) electric field is applied across an ion-selective nanoporous membrane or a nanochannel with an overlapping Debye layer, a surprising microvortex instability occurs on the side of the membrane/channel through which counterions enter. Despite its micro and nano length scales, this instability exhibits all the hallmarks of other classical hydrodynamic instabilities—a subharmonic cascade, a wide-band fluctuation spectrum, and a coherent structure dominated by spatiotemporal dynamics. Moreover, the resulting convection enhances the ion flux into the ion-selective medium and gives rise to an overlimiting-current bifurcation in the current-voltage relationship. This hydrodynamically driven nonequilibrium ion flux does not seem to have any equivalent in cell membrane ion channels. Yet, by introducing asymmetric entrances to provide different polarized regions and/or viscous arrest of the vortex instability, one can fabricate a hydrodynamic nanofluidic diode. With other modifications, hysteretic, excitable, and oscillatory ion flux dynamics could also be elicited—all with strong hydrodynamic features.
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Supplemental Video 1: Movie showing the ion-enrichment (cathodic polarity) ion-depletion (anodic polarity) phenomena at different frequencies (0.01, 0.1, and 1 Hz) and the same voltage difference of 80 V peak to peak for the nanoslot device of Figure 6. Download video file (MP4)
Supplemental Video 2: Movie showing the depletion-layer pattern evolution as a response to a step input of 40 V. In particular, we clearly see the complex process of wavelength selection by small vortices breaking up through fusion and transformation into still larger vortices until a quasi-steady like pattern is formed in the case of the deep (122-µm) microchamber. Download video file (MP4)
Supplemental Video 3: In contrast to the case of the deep (122-µm) microchamber, these patterns do not occur for the shallow (2-µm) microchamber. Instead, a relatively uniform propagating concentration polarization layer front is observed. Download video file (MP4)
Supplemental Video 4: Movie showing the depletion layer and its associated vortex dependence (using 1.2-µm fluorescent microbeads) on the voltage for the widest (2.5-mm) nanoslot. Download or video file (MP4)
Supplemental Video 5 Movie showing the depletion layer and its associated vortex dependence (using 1.2-µm fluorescent microbeads) on the voltage for the narrowest (50-µm) nanoslot. Download video file (MP4)
Supplemental Video 6 Movie showing the evolution of the depletion-enrichment phenomenon under forward and reverse 30-V DC bias for a nanochannel array (consisting of seven channels) with asymmetric channel separation at the entrances. Download video file (MP4)
Supplemental Video 7 Movie showing the evolution of the depletion-enrichment phenomenon under reverse 40-V DC bias for a single nanochannel. Download video file (MP4)
Supplemental Video 8 Movie showing the colloid dynamics for different applied voltages in the case of weak electrolyte (0.1 mM) and 1.2-µm beads without fluorescent dye molecules in the background electrolyte solution. Download video file (MP4)