Kjeld G. H. Janssen

Solution titration by wall deprotonation during capillary filling of silicon oxide nanochannels

This paper describes a fundamental challenge when using silicon oxide nanochannels for analytical systems, namely the occurrence of a strong proton release or proton uptake from the walls in any transient situation such as channel filling. Experimentally, when fluorescein solutions were introduced into silicon oxide nanochannels through capillary pressure, a distinct bisection of the fluorescence was observed, the zone of the fluid near the entrance fluoresced, while the zone near the meniscus, was dark. The ratio between the zones was found to be constant in time and to depend on ionic strength, pH, and the presence of a buffer and its characteristics. Theoretically, using the Gouy-Chapman-Stern model of the electrochemical double layer, we demonstrate that this phenomenon can be effectively modeled as a titration of the solution by protons released from silanol groups on the walls, as a function of the pH and ionic strength of the introduced solution. The results demonstrate the dominant influence of the surface on the fluid composition in nanofluidic experiments, in transient situations such as filling, and changes in solvent properties such as the pH or ionic strength. The implications of these fundamental properties of silicon oxide nanochannels are important for analytical strategies and in particular the analysis of complex biological samples.

Single-Electrolyte Isotachophoresis Using a Nanochannel-Induced Depletion Zone

Isotachophoretic separations are triggered at the border of a nanochannel-induced ion-depleted zone. This depletion zone acts as a terminating electrolyte and is created by concentration polarization over the nanochannel. We show both continuous and discrete sample injections as well as separation of up to four analytes. Continuous injection of a spacer compound was used for selective analyte elution. Zones were kept focused for over one hour, while shifting less than 700 μm. Moreover, zones could be deliberately positioned in the separation channel and focusing strength could be precisely tuned employing a three-point voltage actuation scheme. This makes depletion zone isotachophoresis (dzITP) a fully controllable single-electrolyte focusing and separation technique. For on-chip electrokinetic methods, dzITP sets a new standard in terms of versatility and operational simplicity.

Almost) Stationary Isotachophoretic Concentration Boundary in a Nanofluidic Channel Using Charge Inversion

The present work is an experimental study of a new means to induce a quasi-stationary boundary for concentration or separation in a nanochannel induced by charge inversion. Instead of using pressure-driven counter-flow to keep the front stationary, we exploit charge inversion by a highly charged electrolyte, Ru(bpy)3Cl2, that changes the sign of the zeta potential in part of the channel from negative to positive. Having a non-charge inverting electrolyte (MgCl2) in the other part of the channel and applying an electric field can create a standing front at the interface between them without added dispersion due to an externally applied pressure-driven counterflow. The resulting slow moving front position can be easily imaged optically since Ru(bpy)3Cl2 is fluorescent. A simple analytical model for the velocity field and front axial position that reproduces the experimental location of the front shows that the location can be tuned by changing the concentration of the electrolytes (and thus local zeta potential). Both of these give the charge inversion-mediated boundary significant advantages over current methods of concentration and separation and the method is, therefore, of particular importance to chemical and biochemical analysis systems such as chromatography and separations and for enhancing the stacking performance of field amplified sample injection and isotachophoresis. By choosing a non-charge inverting electrolyte other than MgCl2, either this electrolyte or the Ru(bpy)3Cl2 solution can be made to be the leading or trailing electrolyte.

Electrocavitation in Nanochannels

A novel method has been developed to cavitate aqueous solutions, which is called electrocavitation. An axial voltage is applied in a nanochannel containing an aqueous solution with a stepwise conductivity gradient. A combination of electrical and viscous forces then generates a tension in the solution which, at sufficiently low pressures, causes it to cavitate. Measurement of the current during the experiment as well as optical observation provides knowledge on the time and axial position of cavitation, after which the pressure at the cavitation position can be calculated from a theoretical model in which also the ζ-potential is inserted, which is separately determined from electroosmotic flow experiments. It is found that generally the cavitation position coincides with the position of the conductivity step. In several experiments the cavitation pressure in successive experiments on the same channel became increasingly lower, suggesting a gradual removal of cavitation nuclei from the system. We calculated that pressures as low as −1630 bar ±10 % have been reached, close to theoretically predicted pressures for homogeneous cavitation. The platform performs reliably and can be easily controlled.