Ionic rectifying effect is a unique ion transport phenomenon observed in certain types of nanofluidic devices and cannot be implemented in microfluidics. Analogous to a diode in solid-state electronics, these diode-like nanofluidic devices can be used to turn the ionic flow on and off depending on the polarity of the applied electric-field. In this tutorial review, we summarize recent advances in the experimental and theoretical studies of ion current rectification in several types of nanofluidic devices. We also present a unified model to elucidate the physical mechanism behind the asymmetric ion transport behavior in nanofluidics.

We investigate the ionic rectifying effect through 4 and 20 nm thick silica nanochannels placed between two ionic solutions of different concentrations. The effect was observed when only a single side of the channel has electric double-layer overlap. The calculation based on Poisson-Nernst-Planck (PNP) theory and a simplified model suggests that the phenomenon result from the accumulation and depletion of both cations and anions in the nanochannels responding to different bias polarities. The model also elucidates that the basis of the rectifying effects in the nanofluidic devices reported to date is due to the asymmetric cation/anion ratios or equivalently built-in potentials on the two sides of the nanochannels. The study benefits the design of nanofluidic devices for attoliter-scale chemical delivery.

Selective localization of active proteins to patterns or specific sites is important for development of biosensors, bioMEMS, tissue engineering, and basic proteomic research. We present a flexible technique for selectively patterning bioactive proteins with nanoscale resolution using nanoimprint lithography and fluoropolymer surface passivation, and exploiting the specificity of the biotin/streptavidin linkage. This technique achieves high throughput reproducible nanoscale protein patterns with high selectivity and retained biofunctionality, as demonstrated by interactions between patterned antibodies and their antigen.

We investigate several ion transport behaviors in sub-20 nm nanofluidic channels consisting of heterogeneous oxide materials. By utilizing distinct isoelectric points of SiO2 and Al2O3 surfaces and photolithography to define the charge distribution, nanofluidic channels containing positively and negatively charged surfaces are created to form an abrupt junction. This method provides much more robust surface charges than previous approaches by surface chemical treatment. The fabricated nanofluidic diodes exhibit high rectification of ion current and achieve record-high rectification factors (ratio of forward current to reverse current) of over 300. The current-voltage property of the device follows the theoretical model quantitatively, except that at low ion concentrations the forward current degrades and the reverse current is greater than theoretical prediction, which can be attributed to access resistance and breakdown of water molecules. The breakdown effect characterized by a negative conductance followed by a rapid increase of current is observed in a double junction diode. The occurrence of the breakdown is found to be enhanced by the abruptness of the junction between the heterogeneous nanochannels. Finally, we demonstrate ionic switching in a three-terminal nanofluidic triode in which the ionic flow can be electrically regulated between different channel branches. The study provides insight into the ion transport behavior in nanofluidic devices containing heterogeneous surfaces.

We present a simple, flexible approach for pH regulation in micro-chambers by injecting controllable amounts of protons and hydroxide ions via field-enhanced dissociation of water molecules. Under a DC voltage bias, the polymeric bipolar membranes integrated in microfluidics devices generate and separate H þ and OH À ions without gas production or contaminant generation resulting from electron-transfer reactions. Robust local on-chip pH and pH gradients are sustained with no need of additional acidic/basic solutions that dilute analyte concentrations. The method could provide a better strategy for pH control in microfluidics.