Mingkan Zhang

Ion Transport in a pH-Regulated Nanopore

Fundamental understanding of ion transport phenomena in nanopores is crucial for designing the next-generation nanofluidic devices. Due to surface reactions of dissociable functional groups on the nanopore wall, the surface charge density highly depends upon the proton concentration on the nanopore wall, which in turn affects the electrokinetic transport of ions, fluid, and particles within the nanopore. Electrokinetic ion transport in a pH-regulated nanopore, taking into account both multiple ionic species and charge regulation on the nanopore wall, is theoretically investigated for the first time. The model is verified by the experimental data of nanopore conductance available in the literature. The results demonstrate that the spatial distribution of the surface charge density at the nanopore wall and the resulting ion transport phenomena, such as ion concentration polarization (ICP), ion selectivity, and conductance, are significantly affected by the background solution properties, such as the pH and salt concentration.

Regulating DNA translocation through functionalized soft nanopores

Nanopores have emerged as promising next-generation devices for DNA sequencing technology. The two major challenges in such devices are: (i) find an efficient way to raise the DNA capture rate prior to funnelling a nanopore, and (ii) reduce the translocation velocity inside it so that single base resolution can be attained efficiently. To achieve these, a novel soft nanopore comprising a solid-state nanopore and a functionalized soft layer is proposed to regulate the DNA electrokinetic translocation. We show that, in addition to the presence of an electroosmotic flow (EOF), which reduces the DNA translocation velocity, counterion concentration polarization (CP) occurs near the entrance of the nanopore. The latter establishes an enrichment of the counterion concentration field, thereby electrostatically enhancing the capture rate. The dependence of the ionic current on the bulk salt concentration, the soft layer properties, and the length of the nanopore are investigated. We show that if the salt concentration is low, the ionic current depends largely upon the length of the nanopore, and the density of the fixed charge of the soft layer, but not upon its degree of softness. On the other hand, if it is high, ionic current blockade always occurs, regardless of the levels of the other parameters. The proposed soft nanopore is capable of enhancing the performance of DNA translocation while maintaining its basic signature of the ionic current at high salt concentration. The results gathered provide the necessary information for designing devices used in DNA sequencing.

Electrokinetic ion and fluid transport in nanopores functionalized by polyelectrolyte brushes

Chemically functionalized nanopores in solid-state membranes have recently emerged as versatile tools for regulating ion transport and sensing single biomolecules. This study theoretically investigated the importance of the bulk salt concentration, the geometries of the nanopore, and both the thickness and the grafting density of the polyelectrolyte (PE) brushes on the electrokinetic ion and fluid transport in two types of PE brush functionalized nanopore: PE brushes are end-grafted to the entire membrane surface (system I), and to its inner surface only (nanopore wall) (system II). Due to a more significant ion concentration polarization (CP), the enhanced local electric field inside the nanopore, the conductance, and the electroosmotic flow (EOF) velocity in system II are remarkably smaller than those in system I. In addition to a significantly enhanced EOF inside the nanopore, the direction of the flow field near both nanopore openings in system I is opposite to that of EOF inside the nanopore. This feature can be applied to regulate the electrokinetic translocation of biomolecules through a nanopore in the nanopore-based DNA sequencing platform.

Controlling pH-Regulated Bionanoparticles Translocation through Nanopores with Polyelectrolyte Brushes

A novel polyelectrolyte (PE)-modified nanopore, comprising a solid-state nanopore functionalized by a nonregulated PE brush layer connecting two large reservoirs, is proposed to regulate the electrokinetic translocation of a soft nanoparticle (NP), comprising a rigid core covered by a pH-regulated, zwitterionic, soft layer, through it. The type of NP considered mimics bionanoparticles such as proteins and biomolecules. We find that a significant enrichment of H(+) occurs near the inlet of a charged solid-state nanopore, appreciably reducing the charge density of the NP as it approaches there, thereby lowering the NP translocation velocity and making it harder to thread the nanopore. This difficulty can be resolved by the proposed PE-modified nanopore, which raises effectively both the capture rate and the capture velocity of the soft NP and simultaneously reduces its translocation velocity through the nanopore so that both the sensing efficiency and the resolution are enhanced. The results gathered provide a conceptual framework for the interpretation of relevant experimental data and for the design of nanopore-based devices used in single biomolecules sensing and DNA sequencing.

Electrokinetic particle translocation through a nanopore containing a floating electrode

Electrokinetic particle translocation through a nanopore containing a floating electrode is investigated by solving a continuum model, composed of the coupled Poisson–Nernst–Planck (PNP) equations for the ionic mass transport and the modified Stokes equations for the flow field. Two effects due to the presence of the floating electrode, the induced‐charge electroosmosis (ICEO) and the particle‐floating electrode electrostatic interaction, could significantly affect the electrokinetic mobility of DNA nanoparticles. When the electrical double layers (EDLs) of the DNA nanoparticle and the floating electrode are not overlapped, the particle‐floating electrode electrostatic interaction becomes negligible. As a result, the DNA nanoparticle could be trapped near the floating electrode arising from the induced‐charge electroosmosis when the applied electric field is relatively high. The presence of the floating electrode attracts more ions inside the nanopore resulting in an increase in the ionic current flowing through the nanopore; however, it has a limited effect on the deviation of the current from its base current when the particle is far from the pore.

Slowing down DNA translocation through a nanopore by lowering fluid temperature

In the next‐generation nanopore‐based DNA sequencing technique, the DNA nanoparticles are electrophoretically driven through a nanopore by an external electric field, and the ionic current through the nanopore is simultaneously altered and recorded during the DNA translocation process. The change in the ionic current through the nanopore as the DNA molecule passes through the nanopore represents a direct reading of the DNA sequence. Due to the large mismatch of the cross‐sectional areas of the nanopore and the microfluidic reservoirs, the electric field inside the nanopore is significantly higher than that in the fluid reservoirs. This results in high‐speed DNA translocation through the nanopore and consequently low read‐out accuracy on the DNA sequences. Slowing down DNA translocation through the nanopore thus is one of the challenges in the nanopore‐based DNA sequencing technique. Slowing down DNA translocation by lowering the fluid temperature is theoretically investigated for the first time using a continuum model, composed of the coupled Poisson–Nernst–Planck equations for the ionic mass transport and the Navier–Stokes equations for the hydrodynamic field. The results qualitatively agree with the existing experimental results. Lowering the fluid temperature from 25 to 0°C reduces the translocation speed by a magnitude of about 6.21 to 2.50 mm/sK (i.e. 49.82 to 49.71%) for the salt concentration at 200 and 2000 mM, respectively, improving the read‐out accuracy considerably. As the fluid temperature decreases, the magnitude of the ionic current signal decreases (increases) when the salt concentration is high (sufficiently low).