Overlap Of Electrical Double Layers Research Articles

Preconcentration-enhanced immunosensing for whole human cancer cell lysate based on a nanofluidic preconcentrator

Sample preconcentration is an important step that increases the accuracy of subsequent detection, especially for samples with extremely low concentrations. Due to the overlap of electrical double layers in a nanofluidic channel, the concentration polarization effect can be generated by applying an electric field. A nonlinear electrokinetic flow is induced, which results in the fast accumulation of proteins in front of the induced ionic depletion zone, the so-called exclusion- enrichment effect. In this way, a protein sample can be driven by electroosmotic flow and accumulated at a specific location. In the present study, a nanofluidic preconcentrator fabricated with the help of junction gap electric breakdown was integrated with microelectrodes for immunoassay. The preconcentration chip for proteins was fabricated using simple standard soft lithography with a polydimethylsiloxane replica. Human galectin-1 proteins from the cell lysate of T24 cells were concentrated and immunoassayed in the proposed microchip. The capability of the proposed microchip for concentrating multiple proteins from cell lysates and immunoassays after preconcentration was demonstrated. Immunosensing was evaluated by measurements of both fluorescence intensities and impedance, which proved the enhancement of preconcentration for immunoassay.

Influence of ionic strength and polyelectrolyte concentration on the electrical conductivity of suspensions of soft colloidal polysaccharides

The electrokinetic properties of carboxymethyldextran, a soft and anionic polysaccharide, were analysed in aqueous NaNO3 solutions through measurements of the electrical conductivity of the suspensions. The results, which furnish new experimental support for the structure of soft polysaccharides in electrolyte solution show that the polyion concentration governs the conductance behavior of the suspension as the ionic strength decreases. This is particularly evident for large polymer concentrations, for which electrical double layer overlap is more likely. In contrast, the electrical conductivity of the suspension at high ionic strength reduces to the contribution of the ions in solution, as screening of the polyion charges is more efficient in such conditions. The applicability of Ohshima’s general conductivity expression to these electrical conductivity measurements was examined, and a major discrepancy against the theory was observed. The calculated values of the electrical conductivity deduced on the basis of this theory were found to be lower than the experimental ones. Possible reasons for this discrepancy are discussed and a numerical model, based on the use of a cell approach to account for hydrodynamic and electrical interactions between particles, has shown to be a good description of the experimental electrokinetic data.

Electric Field-Controlled Ion Transport In TiO2 Nanochannel.

On the basis of biological ion channels, we constructed TiO2 membranes with rigid channels of 2.3 nm to mimic biomembranes with flexible channels; an external electric field was employed to regulate ion transport in the confined channels at a high ionic strength in the absence of electrical double layer overlap. Results show that transport rates for both Na+ and Mg2+ were decreased irrespective of the direction of the electric field. Furthermore, a voltage-gated selective ion channel was formed, the Mg2+ channel closed at -2 V, and a reversed relative electric field gradient was at the same order of the concentration gradient, whereas the Na+ with smaller Stokes radius and lower valence was less sensitive to the electric field and thus preferentially occupied and passed the channel. Thus, when an external electric field is applied, membranes with larger nanochannels have promising applications in selective separation of mixture salts at a high concentration.

Sample preconcentration utilizing nanofractures generated by junction gap breakdown assisted by self-assembled monolayer of gold nanoparticles.

The preconcentration of proteins with low concentrations can be used to increase the sensitivity and accuracy of detection. A nonlinear electrokinetic flow is induced in a nanofluidic channel due to the overlap of electrical double layers, resulting in the fast accumulation of proteins, referred to as the exclusion-enrichment effect. The proposed chip for protein preconcentration was fabricated using simple standard soft lithography with a polydimethylsiloxane replica. This study extends our previous paper, in which gold nanoparticles were manually deposited onto the surface of a protein preconcentrator. In the present work, nanofractures were formed by utilizing the self-assembly of gold-nanoparticle-assisted electric breakdown. This reliable method for nanofracture formation, involving self-assembled monolayers of nanoparticles at the junction gap between microchannels, also decreases the required electric breakdown voltage. The experimental results reveal that a high concentration factor of 1.5×104 for a protein sample with an extremely low concentration of 1 nM was achieved in 30 min by using the proposed chip, which is faster than our previously proposed chip at the same conditions. Moreover, an immunoassay of bovine serum albumin (BSA) and anti-BSA was carried out to demonstrate the applicability of the proposed chip.

Flow characterization of electroconvective micromixer with a nanoporous polymer membrane in-situ fabricated using a laser polymerization technique

Electroconvection is known to cause strong convective mixing in a microchannel near a nanoporous membrane or a nanochannel in contact with an electrolyte solution due to the external electric field. This study addresses micromixer behavior subject to electroconvection occurring near a nanoporous membrane in-situ fabricated by a laser polymerization technique on a microfluidic chip. We found that the micromixer behavior can be categorized into three regimes. Briefly, the weak electroconvection regime is characterized by weak mixing performance at a low applied voltage and KCl concentration, whereas the strong electroconvection regime has a high mixing performance when the applied voltage and KCl concentration are moderately high. Finally, the incomplete electroconvection regime has an incomplete electric double-layer overlap in the nanopores of the membrane when the electrolyte concentration is very high. The mixing index reached 0.92 in the strong electroconvection regime. The detailed fabrication methods for the micromixer and characterization results are discussed in this paper.

PH-regulated ionic conductance in a nanochannel with overlapped electric double layers.

Accurately and rapidly analyzing the ionic current/conductance in a nanochannel, especially under the condition of overlapped electric double layers (EDLs), is of fundamental significance for the design and development of novel nanofluidic devices. To achieve this, an analytical model for the surface charge properties and ionic current/conductance in a pH-regulated nanochannel is developed for the first time. The developed model takes into account the effects of the EDL overlap, electroosmotic flow, Stern layer, multiple ionic species, and the site dissociation/association reactions on the channel walls. In addition to good agreement with the existing experimental data of nanochannel conductance available from the literature, our analytical model is also validated by the full model with the Poisson-Nernst-Planck and Navier-Stokes equations. The EDL overlap effect is significant at small nanochannel height, low salt concentration, and medium low pH. Neglecting the EDL overlap effect could result in a wrong estimation in the zeta potential and conductance of the nanochannel in a single measurement.

Gate manipulation of ionic conductance in a nanochannel with overlapped electric double layers

To improve the development of gated nanofluidic devices for emerging applications, analytical expressions are derived to investigate the gate manipulation of surface charge property and ionic conductance in a pH-regulated nanochannel with overlapped electric double layers (EDLs). Results show that the EDL overlap effect is relatively significant at low pH and salt concentration when a negative gate potential is applied. If pH is low, the EDL overlap effect on the field control of zeta potential of the nanochannel is remarkable at large positive gate voltage, while that effect on ionic conductance is significant at large negative gate voltage.

Nonfaradaic nanoporous electrochemistry for conductometry at high electrolyte concentration.

Nanoporous electrified surfaces create a unique nonfaradaic electrochemical behavior that is sensitively influenced by pore size, morphology, ionic strength, and electric field modulation. Here, we report the contributions of ion concentration and applied ac frequency to the electrode impedance through an electrical double layer overlap and ion transport along the nanopores. Nanoporous Pt with uniform pore size and geometry (L2-ePt) responded more sensitively to conductivity changes in aqueous solutions than Pt black with poor uniformity despite similar real surface areas and enabled the previously difficult quantitative conductometry measurements at high electrolyte concentrations. The nanopores of L2-ePt were more effective in reducing the electrode impedance and exhibited superior linear responses to not only flat Pt but also Pt black, leading to successful conductometric detection in ion chromatography without ion suppressors and at high ionic strengths.

Charge Relaxation Dynamics of an Electrolytic Nanocapacitor.

Understanding ion relaxation dynamics in overlapping electric double layers (EDLs) is critical for the development of efficient nanotechnology-based electrochemical energy storage, electrochemomechanical energy conversion, and bioelectrochemical sensing devices as well as the controlled synthesis of nanostructured materials. Here, a lattice Boltzmann (LB) method is employed to simulate an electrolytic nanocapacitor subjected to a step potential at t = 0 for various degrees of EDL overlap, solvent viscosities, ratios of cation-to-anion diffusivity, and electrode separations. The use of a novel continuously varying and Galilean-invariant molecular-speed-dependent relaxation time (MSDRT) with the LB equation recovers a correct microscopic description of the molecular-collision phenomena and enhances the stability of the LB algorithm. Results for large EDL overlaps indicated oscillatory behavior for the ionic current density, in contrast to monotonic relaxation to equilibrium for low EDL overlaps. Further, at low solvent viscosities and large EDL overlaps, anomalous plasmalike spatial oscillations of the electric field were observed that appeared to be purely an effect of nanoscale confinement. Employing MSDRT in our simulations enabled modeling of the fundamental physics of the transient charge relaxation dynamics in electrochemical systems operating away from equilibrium wherein Nernst–Einstein relation is known to be violated.

Travelling wave dipolophoresis of ideally polarizable nano-particles with overlapping electric double layers in cylindrical pores

We provide a general integral formulation for the dipolophoretic transport of a polarizable colloid in a likewise polarizable nanochannel which takes into account electric double layer (EDL) overlap between the channel walls and resultant background flow as well as the overlap between the wall EDL and that of the particle. The analysis is based on extension of the Lorentz reciprocal theorem for Stokes flows and necessitates the solving of two auxiliary problems; the background induced-charge electroosmotic flow in the channel and the Stokesian motion of a nanoparticle under confinement. To demonstrate our general methodology, we provide a closed form analytical solution for the specific case of a polarizable spherical colloid, located at the axis of a cylindrical nanopore whose walls are subject to a travelling-wave alternating-current electric signal. We quantify the level of EDL overlap via the introduction of a new parameter, ξ which represents the undefined ionic density at the centerline under Boltzmann distribution and depends on the EDL thickness, λ0. Both the background electroosmotic flow and the phoretic velocity of the particle are found to be a function of the frequency of the applied field, while displaying distinct dispersion characteristics. In the thin EDL limit, maximum velocity and mass transport are obtained in the kilo-Hertz range.

Non-linear streaming conductance in a single nanopore by addition of surfactants

Electrokinetic phenomena in nanofluidic system result in many unique properties and applications due to overlap of electrical double layers. As well known, the streaming current is linear proportional to the pressure gradient of a channel. However, in this Letter, we report a non-linear streaming conductance phenomenon in a single nanopore by addition of ionic surfactants in KCl aqueous solution. The streaming conductance decreases at about 0.8 bar applied pressure in high concentrated surfactant solution that was attributed to the slip of surfactant layer, and the slip length was theoretically estimated.

Electroosmotic flow in nanoporous membranes in the region of electric double layer overlap

This study investigates electroosmotic flow (EOF) with sodium tetraborate buffer in nanoporous anodized alumina membranes. Membranes with pore diameters ranging from 8 to 100 nm have been fabricated with narrow pore size distributions to systematically investigate the effect of pore diameter on the electroosmosis (EO) pumping down to the electric double layer overlap region. EOF was observed in membranes with pore diameters in and below this region, along with evidence of concentration polarization (CP), which resulted in a significant reduction in flux. The initial flux, though, could be fully recovered by temporarily reversing the flow and dislodging the accumulated ion layer from the feed side of the membrane. Stable pumping for up to 2 h was obtained before any flux reduction caused by CP was observed.

Nanofluidic crystal: a facile, high-efficiency and high-power-density scaling up scheme for energy harvesting based on nanofluidic reverse electrodialysis

The great advances in nanotechnology call for advances in miniaturized power sources for micro/nano-scale systems. Nanofluidic channels have received great attention as promising high-power-density substitutes for ion exchange membranes for use in energy harvesting from ambient ionic concentration gradient, namely reverse electrodialysis. This paper proposes the nanofluidic crystal (NFC), of packed nanoparticles in micro-meter-sized confined space, as a facile, high-efficiency and high-power-density scaling-up scheme for energy harvesting by nanofluidic reverse electrodialysis (NRED). Obtained from the self-assembly of nanoparticles in a micropore, the NFC forms an ion-selective network with enormous nanochannels due to electrical double-layer overlap in the nanoparticle interstices. As a proof-of-concept demonstration, a maximum efficiency of 42.3 ± 1.84%, a maximum power density of 2.82 ± 0.22 W m−2, and a maximum output power of 1.17 ± 0.09 nW/unit (nearly three orders of magnitude of amplification compared to other NREDs) were achieved in our prototype cell, which was prepared within 30 min. The current NFC-based prototype cell can be parallelized and cascaded to achieve the desired output power and open circuit voltage. This NFC-based scaling-up scheme for energy harvesting based on NRED is promising for the building of self-powered micro/nano-scale systems.

Direct prediction of the desalination performance of porous carbon electrodes for capacitive deionization

Desalination by capacitive deionization (CDI) is an emerging technology for the energy- and cost-efficient removal of ions from water by electrosorption in charged porous carbon electrodes. A variety of carbon materials, including activated carbons, templated carbons, carbon aerogels, and carbon nanotubes, have been studied as electrode materials for CDI. Using carbide-derived carbons (CDCs) with precisely tailored pore size distributions (PSD) of micro- and mesopores, we studied experimentally and theoretically the effect of pore architecture on salt electrosorption capacity and salt removal rate. Of the reported CDC-materials, ordered mesoporous silicon carbide-derived carbon (OM SiC-CDC), with a bimodal distribution of pore sizes at 1 and 4 nm, shows the highest salt electrosorption capacity per unit mass, namely 15.0 mg of NaCl per 1 g of porous carbon in both electrodes at a cell voltage of 1.2 V (12.8 mg per 1 g of total electrode mass). We present a method to quantify the influence of each pore size increment on desalination performance in CDI by correlating the PSD with desalination performance. We obtain a high correlation when assuming the ion adsorption capacity to increase sharply for pore sizes below one nanometer, in line with previous observations for CDI and for electrical double layer capacitors, but in contrast to the commonly held view about CDI that mesopores are required to avoid electrical double layer overlap. To quantify the dynamics of CDI, we develop a two-dimensional porous electrode modified Donnan model. For two of the tested materials, both containing a fair degree of mesopores (while the total electrode porosity is ∼95 vol%), the model describes data for the accumulation rate of charge (current) and salt accumulation very well, and also accurately reproduces the effect of an increase in electrode thickness. However, for TiC-CDC with hardly any mesopores, and with a lower total porosity, the current is underestimated. Calculation results show that a material with higher electrode porosity is not necessarily responding faster, as more porosity also implies longer transport pathways across the electrode. Our work highlights that a direct prediction of CDI performance both for equilibrium and dynamics can be achieved based on the PSD and knowledge of the geometrical structure of the electrodes.

Liquid flow retardation in nanospaces due to electroviscosity: Electrical double layer overlap, hydrodynamic slippage, and ambient atmospheric CO2 dissolution

A theoretical investigation is performed into the electroviscous-induced retardation of liquid flows through finitely long nanochannels or nanotubes with large wells at either end. Given the assumption of equilibrium conditions between the ionic solution in the wells and that within the nanochannel or nanotube, an exact solution is derived for the overlapped electrical double layer (EDL) for the case where the concentrations of the positive and negative ions in the wells may be unequal. The ion concentrations in the wells are determined by the conditions of global electroneutrality and mass conservation. It is shown that the overlapped EDL model proposed by Baldessari and Santiago [J. Colloid Interface Sci. 325, 526 (2008)10.1016/j.jcis.2008.06.007] is in fact the same as the “thick EDL model” (i.e., the traditional Poisson-Boltzmann model) when the positive and negative ion concentrations in the large enough wells are both equal to the bulk concentration of the salt solution. Utilizing the proposed overlapped EDL analytical model, an investigation is performed to evaluate the effects of hydrodynamic slippage on the flow retardation caused by electroviscosity in nanochannels or nanotubes. Furthermore, exact and approximate solutions are derived for the electroviscosity in ion-selective nanochannels and nanotubes. It is shown that in the absence of slip, the maximum electroviscosity in nanochannels and nanotubes containing a unipolar solution of simple monovalent counter-ions occurs at surface charge densities of h|σ| = 0.32 nm × C/m2 and a|σ| ≈ 0.4 nm × C/m2, respectively. In addition, it is shown that the electroviscosity in a nanotube is smaller than that in a nanochannel. For example, given a LiCl solution, the maximum electroviscosites in a non-slip nanochannel and non-slip nanotube are ηa/η ≈ 1.6 and 1.47, respectively. For both nanospaces, the electroviscosity is greatly increased when the liquid slip effect is taken into account. Significantly, under slip conditions, the electroviscosity in the nanotube is greater than that in the nanochannel. Finally, an investigation is performed into the effects of ambient atmospheric CO2 dissolution on the electroviscosities of salt/buffer solution and deionized (DI) water in silica nanochannels. The results show that the electroviscosity of CO2-saturated DI water (pH = 5.6) can be reasonably neglected in silica nanochannels with a height of less than 100 nm.

Electrokinetic flow in connected channels: a comparison of two circuit models

We apply the recently developed ‘ion current model’ (ICM) to investigate mixed pressure-driven/electro-osmotic flow in electrokinetic series circuits. Under the ICM, the local geometric mean ion concentration varies throughout a microfluidic circuit as a consequence of ion conservation. ICM predictions are used to assess the accuracy of the earlier ‘total current model’ (TCM), which is instead based upon the simplifying assumption that the geometric mean ion concentration is uniform in all channels within a circuit. The model comparison is performed over an experimentally relevant range of physical parameters and channel dimensions. When the ratio of total current to flow rate is small, or when the inlet concentration is very low or very high, the ICM and TCM give similar predictions of the total pressure and potential differences across simple three-channel contraction–expansion networks. Otherwise, the errors introduced using the TCM may be very large. Our results demonstrate that the common assumption that the electrolyte concentration throughout a device is equal to the concentration of fluid supplied to the device is not always valid, even if there is little or no electric double layer overlap.

Effect of wall permittivity on electroviscous flow through a contraction.

The electroviscous flow at low Reynolds number through a two-dimensional slit contraction with electric double-layer overlap is investigated numerically for cases where the permittivity of the wall material is significant in comparison with the permittivity of the liquid. The liquid-solid interface is assumed to have uniform surface-charge density. It is demonstrated that a finite wall permittivity has a marked effect on the distribution of ions in and around the contraction, with a significant build-up of counter-ions observed at the back-step. The development length of the flow increases substantially as the wall permittivity becomes significant, meaning that the electric double-layers require a longer distance to develop within the contraction. Consequently, there is a corresponding decrease in the hydrodynamic and electro-potential resistance caused by the contraction. The effect of wall-region width on the flow characteristics is also quantified, demonstrating that the development length increases with increasing wall-region width for widths up to 5 channel widths.

Steric-effect-induced enhancement of electrical-double-layer overlapping phenomena

In this paper, we demonstrate that nontrivial interactions between steric effect and electrical-double-layer (EDL) overlap phenomena may augment the effective extent of EDL overlap in narrow fluidic confinements to a significant extent by virtue of rendering the channel centerline potential tending to the ζ potential in a limiting sense as the steric effect progressively intensifies. Such a behavior may result in a virtually uniform (undiminished) magnitude of the EDL potential across the entire channel height and may cause lowering of the total charge within the EDL.

Thermodynamic Reversibility Analysis of Electrokinetic Energy Conversion in Nanofluidic Channels

The thermodynamic efficiencies of electrokinetic pumping and electrical power generation are investigated numerically using a two-dimensional axisymmetrical model containing a finite-length nanoscale cylindrical capillary and reservoirs connecting at the capillary ends. The Navier-Stokes, Laplace, Poisson, and Nernst-Planck equations are solved simultaneously to obtain the fluid and electric current flows. The main goal of this study is to justify the reversibility of electrokinetic energy conversion resulting from one-dimensional analysis. Based on our numerical results, it is found that the reversible electrokinetic energy conversion between the pump and electric power generation is valid only when the dimensionless Debye length is greater than 2. Because of the electric double layer (EDL) overlap and current due to the electrostatic potential gradient, significant deviation in maximum efficiencies between the numerical and one-dimensional analysis results are found when the dimensionless Debye length is less than 2.

Numerical simulation of probing the electric double layer by scanning electrochemical potential microscopy

Abstract Computational modeling of probing the electric double layer (EDL) by scanning electrochemical potential microscopy (SECPM) was carried out in order to evaluate the applicability of this method. The modeling is based on a continuum approach for the electric double layer in dilute solution using the modified Poisson–Boltzmann equation. This model takes into account the finite ion size and prevents steric effects near the charged surface. The approach of the SECPM probe towards a charged electrode, immersed in electrolyte solution, is simulated obtaining the potential profile in the direction normal to the electrode. The effects of the shape and the size of the metallic protrusion at the apex of the probe were studied. A clear dependence of the probe potential on the apex geometry was observed, and correlated to the apex surface charge density distribution. The overlap of the EDLs located at the probe and the electrode is studied by setting different initial open circuit potentials, i.e., different charging, to the probe. We have found that the obtained potential profiles are consequences of the EDL overlap, characterized by an ionic distribution in the gap separating the probe and electrode. Depending on the strength of both EDLs and their polarity, the Debye screening effect severely influences the probe potential.