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.     

Investigating protein translocation in the presence of an electrolyte concentration gradient across a solid-state nanopore

Electrolyte chemistry plays an important role in the transport properties of analytes through nanopores. Here, we report the translocation properties of the protein human serum transferrin (hSTf) in asymmetric LiCl salt concentrations with either positive (C_trans/C_cis < 1) or negative chemical gradients (C_trans/C_cis > 1). The cis side concentration was fixed at 4 M for positive chemical gradients and at 0.5 M LiCl for negative chemical gradients, while the trans side concentration varied between 0.5 to 4 M which resulted in six different configurations, respectively, for both positive and negative gradient types. For positive chemical gradient conditions, translocations were observed in all six configurations for at least one voltage polarity whereas with negative gradient conditions, dead concentrations where no events at either polarity were observed. The flux of Li⁺ and Cl⁻ ions and their resultant cation or anion enrichment zones, as well as the interplay of electrophoretic and electroosmotic transport directions, would determine whether hSTf can traverse across the pore.     

Electrokinetic flow in an elliptic microchannel covered by ion-penetrable membrane

The electrokinetic flow of an electrolyte solution in an elliptical microchannel covered by an ion-penetrable, charged membrane layer is examined theoretically. The present analysis extends previous results in that a two-dimensional problem is considered, and the system under consideration simulates the flow of a fluid, for example, in a microchannel of biological nature such as vein. The electroosmostic volumetric flow rate, the total electric current, the streaming potential, and the electroviscous effect of the system under consideration are evaluated. We show that, for a constant hydraulic diameter, the variations of these quantities as a function of the aspect ratio of a microchannel may have a local minimum or a local maximum at a medium level of ionic strength, which depends on the thickness of the membrane layer. For a constant cross-sectional area, the electroosmostic volumetric flow rate, the total electric current, and the streaming potential increase monotonically with the increase in the aspect ratio, but the reverse is true for the electroviscous effect.     

Continuous-Flow Nanoparticle Trapping Driven by Hybrid Electrokinetics in Microfluidics

We introduce herein an efficient microfluidic approach for continuous transport and localized collection of nanoparticles via hybrid electrokinetics, which delicately combines linear and nonlinear electrokinetics driven by a composite DC-biased AC voltage signal. The proposed technique utilizes a simple geometrical structure, in which one or a series of metal strips serving as floating electrode (FE) are attached to the substrate surface and arranged in parallel between a pair of coplanar driving electrodes (DE) in a straight microchannel. On application of a DC-biased AC electric field across the channel, nanoparticles can be transported continuously by DC bulk electroosmotic flow, and then trapped selectively onto the metal strips due to AC-field induced-charge electrokinetic (ICEK) phenomenon, which behaves as counter-rotating micro-vortices around the ideally polarizable surfaces of FE. Finite-element simulation is carried out by coupling the dual-frequency electric field, flow field and sample mass transfer in sequence, for guiding a practical design of the microfluidic nanoparticle concentrator. With the optimal device geometry, the actual performance of the technique is investigated with respect to DC bias, AC voltage amplitude, and field frequency by using both latex nanospheres (∼500 nm) and BSA molecules (∼10 nm). Our experimental observation indicates nanoparticles are always enriched into a narrow bright band on the surface of each FE, and a horizontal concentration gradient even emerges in the presence of multiple metal strips, which therefore permits localized analyte enrichment. The proposed trapping method is supposed to guide an elaborate design of flexible electrokinetic frameworks embedding FE for continuous-flow analyte manipulation in modern microfluidic systems.     

Influence of boundary on the effect of double-layer polarization and the electrophoretic behavior of soft biocolloids

The electrophoresis of a soft particle comprising a rigid core and a charged porous membrane layer in a narrow space is modeled. This simulates, for example, the capillary electrophoresis of biocolloids such as cells and microorganisms, and biosensor types of device. We show that, in addition to the boundary effect, the effects of double-layer polarization (DLP) and the electroosmotic retardation flow can be significant, yielding interesting electrophoretic behaviors. For example, if the friction coefficient of the membrane layer and/or the boundary is large, then the DLP effect can be offset by the electroosmotic retardation flow, making the particle mobility to decrease with increasing double layer thickness, which is qualitatively consistent with many experimental observations in the literature, but has not been explained clearly in previous analyses. In addition, depending upon the thickness of double layer, the friction of the membrane layer of a particle can either retard or accelerate its movement, an interesting result which has not been reported previously. This work is the first attempt to show solid evidence for the influence of a boundary on the effect of DLP and the electrophoretic behavior of soft particles. The model proposed is verified by the experimental data in the literature. The results of numerical simulation provide valuable information for the design of bio-analytical apparatus such as nanopore-based sensing applications and for the interpretation of relevant experimental data.     

Effect of electric field during gel-layer controlled ultrafiltration of synthetic and fruit juice

Electric field enhanced ultrafiltration of pectin–sucrose mixture (synthetic juice) and mosambi (Citrus sinensis (L.) Osbeck) fruit juice using 50,000 (MWCO) polyerthersulfon membrane is studied in a cross-flow cell. Pectin, completely rejected by the membrane, forms a gel type layer over the membrane surface. Under the application of an external dc electric field across the membrane, gel-layer formation is restricted leading to an enhancement of permeate flux. During ultrafiltration of synthetic juice, application of dc electric field (800 V/m) increases the permeate flux to almost threefold compared to that with zero electric field. A theoretical model based on integral method assuming suitable concentration profile in the boundary layer is developed. The proposed model is used to predict the permeate flux in gel-layer governed electric field enhanced ultrafiltration. Predictions of the model are successfully compared with the experimental results under a wide range of operating conditions. Experiments with fruit juice also demonstrated significant increase in flux with the application of a suitable electric field.     

Study on the electrochemical behavior and differential pulse voltammetric determination of rhein using a nanoparticle composite film-modified electrode

A sensitive electrochemical method was developed for the differential pulse voltammetric determination of rhein at a glassy carbon electrode (GCE) modified with a nanoparticle composite film. In the present paper, multi-wall carbon nanotube (MWNT) was dispersed into dihexadecyl phosphate (DHP) to give a homogeneous suspension. After the solvent evaporation, a uniform film of MWNT-DHP composite film was obtained on the GCE surface. The MWNT-DHP composite film-modified GCE exhibited excellent electrocatalytic behavior toward the redox of rhein. Compared with an irreversible reduction of rhein at the bare GCE, a reversible redox behavior of rhein was observed at the MWNT-DHP composite film-modified GCE and the redox current was also enhanced greatly. Based on this, a cathodic differential pulse voltammetry (DPV) was applied for the determination of rhein. The experimental parameters, which influence the current of rhein, were optimized. Under optimal conditions, the cathodic DPV measurements were performed and a linear response of rhein was obtained in the range from 1.0 x 10(-8) to 5.0 x 10(-6) mol L(-1) and with a limit of detect (LOD) of 5.0 x 10(-9) mol L(-1). The proposed procedure was successfully applied to assay rhein in real samples with satisfactory results.     

Effect of magnetic field on electroosmotic flow of viscoelastic fluids in a microchannel

Electroosmotic flow is an efficient transportation technology driven by applying an external electric field across the microchannel, which has a great potential for future application. This work is presented to study the unsteady electroosmotic flow of viscoelastic fluids combined with a constant pressure gradient and a vertical magnetic field through a parallel plate microchannel. For the reason that the upper and bottom walls of the parallel plate microchannel in microfluidic devices can be made of different materials, this leads to different hydrophobic properties, asymmetric zeta wall potentials, and different slip boundary conditions. The Navier slip model with different slip coefficients at walls is considered. The generalized Maxwell fluid with fractional derivative is adopted for the constitutive equation of the fluid. The analytical and numerical solutions of velocity are derived by employing the integral transform method and finite difference method, respectively. Excellent agreement is found between the numerical solutions and analytical solutions. Finally, the effects of fractional parameter , relaxation time , slip coefficients and , the ratio of wall zeta potentials , Hartmann number , and electrical field strength parameter on velocity profiles are interpreted graphically in detail.     

Mobility-based selective on-line preconcentration of proteins in capillary electrophoresis by controlling electroosmotic flow

A simple method to perform selective on-line preconcentration of protein samples in capillary electrophoresis (CE) is described. The selectivity, based on protein electrophoretic mobility, was achieved by controlling electroosmotic flow (EOF). A short section of dialysis hollow fiber, serving as a porous joint, was connected between two lengths of fused silica capillary. High voltage was applied separately to each capillary, and the EOF in the system was controlled independently of the local electric field intensity by controlling the total voltage drop. An equation relating the EOF with the total voltage drop was derived and evaluated experimentally. On-line preconcentration of both positively charged and negatively charged model proteins was demonstrated without using discontinuous background electrolytes, and protein analytes were concentrated by approximately 60-200-fold under various conditions. For positively charged proteins, positive voltages of the same magnitude were applied at the free ends of the connected capillaries while the porous joint was grounded. This provided a zero EOF in the system and a non-zero local electric field in each capillary to drive the positively charged analytes to the porous joint. CE separation was then initiated by switching the polarity of the high voltage over the second capillary. For negatively charged proteins, the procedure was the same except negative voltages were applied at the free ends of the capillaries. Mobility-based selective on-line preconcentration was also demonstrated with two negatively charged proteins, i.e. beta-lactoglobulin B and myoglobin. In this case, negative voltages of different values were applied at the free ends of the capillaries with different values, which provided a non-zero EOF in the system. The direction of EOF was the same as that of the electrophoretic migration velocities of the protein analytes in the first capillary and opposite in the second capillary. By controlling the EOF, beta-lactoglobulin B, which has a higher mobility, could be concentrated over 150-fold with a 15 min injection while myoglobin, which has a lower mobility, was eliminated from the system.     

微流控芯片中的流体驱动和控制方式

随着微流控芯片分析技术的发展,微流控芯片中的关键技术之一流体的驱动和控制技术逐步成为人们关注和研究的热点。本文主要综述了微流控芯片上的压力驱动、电驱动和其他驱动方式,着重介绍了电驱动方式,并讨论了各种驱动方式的优缺点以及发展前景。     

Separation of basic proteins by capillary zone electrophoresis with coatings of a copolymer of vinylpyrrolidone and vinylimidazole

Capillary zone electrophoretic (CZE) separation of basic proteins has been achieved with capillary columns modified with copolymers of vinylpyrrolidone (VP) and vinylimidazole (VI). The copolymerization reaction is performed inside the capillary column and involves chemical bonding of the polymer to silica. The electroosmotic flow (EOF) is greatly decreased by this surface modification. The presence of positive charges on the coating surface, due to the cationic property of vinylimidazole at pH below 7, reduces the adsorption of basic proteins onto the silanol groups of the capillary surface. Acidic proteins are irreversibly adsorbed, but rapid separation and good performance reproducibility are obtained with basic proteins. In the case of capillaries modified with VP, the acidic and basic proteins are eluted within 10 min. In this work, we studied the effects of pH and buffer concentration on the magnitude of the EOF, as well as the effect of copolymer composition on the separation efficiency.     

Electrophoretic motion of a soft spherical particle in a nanopore

Many biocolloids, biological cells and micro-organisms are soft particles, consisted with a rigid inner core covered by an ion-permeable porous membrane layer. The electrophoretic motion of a soft spherical nanoparticle in a nanopore filled with an electrolyte solution has been investigated using a continuum mathematical model. The model includes the Poisson-Nernst-Planck (PNP) equations for the ionic mass transport and the modified Stokes and Brinkman equations for the hydrodynamic fields outside and inside the porous membrane layer, respectively. The effects of the “softness” of the nanoparticle on its electrophoretic velocity along the axis of a nanopore are examined with changes in the ratio of the radius of the rigid core to the double layer thickness, the ratio of the thickness of the porous membrane layer to the radius of the rigid core, the friction coefficient of the porous membrane layer, the fixed charge inside the porous membrane layer of the particle and the ratio of the radius of the nanopore to that of the rigid core. The presence of the soft membrane layer significantly affects the particle electrophoretic mobility.     

电动流动分析-胶束电动毛细管色谱联用测定食品防腐剂

采用电动流动分析(EFA)和胶束电动毛细管色谱(MEKC)联用系统测定了食品中的防腐剂.EFA系统设备简单便携、易于实现自动化.EFA由一台自制电渗泵、5个电磁切换阀(由计算机通过自制接口卡和自编VC语言程序控制)和一个固相萃取微柱组成,采用EFA-MEKC低试剂消耗接口,可减少含贵重试剂的缓冲液消耗.MEKC缓冲溶液为100 mmol/L十二烷基硫酸钠(SDS) 20 mmol/L Na2B4O7(pH 9.3).使用对羟基苯甲酸(PBA)为内标物,方法可在15 min内分离测定6种防腐剂,峰面积相对标准偏差小于3.4%;检出限范围为0.04～0.1 mg/L;实际样品的回收率为91.4%～104%.     

Influence of varying electroosmotic flow on the effective diffusion in electric field gradient separations

Recently the use electric field gradient focusing (EFGF) to enhance focusing of proteins has been proposed and explored to provide significant improvement in separation resolution. The objective of EFGF is to focus proteins of specific electrophoretic mobilities at distinct stationary locations in a column or channel. This can be accomplished in a capillary by allowing the electric potential to vary in the streamwise direction. Because the electric field is varying, so also is the electrokinetic force exerted on the proteins and the electroosmotic velocity of the buffer solution. Due to the varying electric field, the Taylor diffusion characteristics will also vary along the column, causing a degradation of peak widths of some proteins, dependent on their equilibrium positions and local velocity distributions. The focus of this paper is an analysis that allows characterization of the local Taylor diffusion and resulting protein band peak width as a function of the local magnitude of the EOF relative to the average fluid velocity for both cylindrical and rectangular channels. In general the analysis shows that as the ratio of the local electroosmotic velocity to the average velocity deviates from unity, the effective diffusion increases significantly. The effectiveness of EFGF devices over a range of protein diffusivities, capillary diameters, flow velocities, and electric field gradient is discussed.     

Rational strategy for characterization of nanoscale particles by asymmetric-flow field flow fractionation: A tutorial

This tutorial proposes a comprehensive and rational measurement strategy that provides specific guidance for the application of asymmetric-flow field flow fractionation (A4F) to the size-dependent separation and characterization of nanoscale particles (NPs) dispersed in aqueous media. A range of fractionation conditions are considered, and challenging applications, including industrially relevant materials (e.g., metal NPs, asymmetric NPs), are utilized in order to validate and illustrate this approach. We demonstrate that optimization is material dependent and that polystyrene NPs, widely used as a reference standard for retention calibration in A4F, in fact represent a class of materials with unique selectivity, recovery and optimal conditions for fractionation; thus use of these standards to calibrate retention for other materials must be validated a posteriori. We discuss the use and relevance of different detection modalities that can potentially yield multi-dimensional and complementary information on NP systems. We illustrate the fractionation of atomically precise nanoclusters, which are the lower limit of the nanoscale regime. Conversely, we address the upper size limit for normal mode elution in A4F. The protocol for A4F fractionation, including the methods described in the present work is proposed as a standardized strategy to realize interlaboratory comparability and to facilitate the selection and validation of material-specific measurement parameters and conditions. It is intended for both novice and advanced users of this measurement technology.     

The effect of water on separations in non-aqueous capillary electrophoresis systems

Summary Water, in concentrations up to 10%, has been added to organic solvents (dimethylsulphoxide,N-methylformamide, acetonitrile and methanol) used as the buffer solvents in electrophoresis media for non-aqueous capillary electrophoresis. Anionic and cationic test substances have been used to study the effect on separation selectivity and efficiency. The effect on the electroosmotic flow has also been studied. Water added in concentrations up to 0.5% had only a minor effect on the separation selectivity, efficiency or electroosmotic flow in the systems studied. These results indicate that small variations in the water-content of organic solvents are of only minor importance to the reproducibility of non-aqueous capillary electrophoresis systems. The reproducibility of selectivity might, however, be slightly improved by adding 0.1–0.5% water, because true non-aqueous solvents are likely to cause problems as a result of the variable absorption of water.     

Electrokinetic injection of samples into a short electrophoretic capillary controlled by piezoelectric micropumps

Electrokinetic sample injection using two piezoelectric micropumps has been proposed for electrophoresis in short capillaries. The sample is brought to the injection end of the capillary using one of them. Then, the high‐voltage source is turned on and the sample is injected electrokinetically for a defined time. The injection is terminated by removal of the sample zone by the flowing separation electrolyte pumped by the second piezoelectric micropump. The RSD value, expressing the repeatability of the injection, does not exceed 4%. The injection apparatus does not contain any mobile mechanical components, there is no movement of the capillary and both its ends remain constantly in the solution during both the sample injection and separation. Thus, the micropumps replace the six‐way injection valve and linear pump in similar types of injection apparatuses. The injection was tested in the separation and determination of ammonium and potassium ions in two samples of mineral fertilizers. The separation was performed in background electrolyte containing 500 mM of acetic acid + 20 mM Tris + 2 mM 18‐crown‐6 (pH 3.3) in a capillary with id 50 μm and total length/length to the contactless conductivity detector of 10.5/8 cm. The injection and separation took place at a voltage of 5 kV and the separation time equaled 20 s. The measured values of the analyte contents corresponded to the value declared by the manufacturer within the reliability interval, where RSD equaled between 3.5 and 4.7%.     

Dissolution and nanoparticle generation behavior of Be-associated materials in synthetic lung fluid using inductively coupled plasma mass spectroscopy and flow field-flow fractionation

Various Be-containing micro-particle suspensions were equilibrated with simulated lung fluid (SLF) to examine their dissolution behavior as well as the potential generation of nanoparticles. The motivation for this study was to explore the relationship between dissolution/particle generation behaviors of Be-containing materials relevant to Be-ore processing, and their epidemiologically indicated inhalation toxicities. Limited data suggest that BeO is associated with higher rates of beryllium sensitization (BS) and chronic beryllium disease (CBD) relative to the other five relevant materials studied: bertrandite-containing ore, beryl-containing ore, frit (a processing intermediate), Be(OH)₂ (a processing intermediate), and silica (control). These materials were equilibrated with SLF at two pH values (4.5 and 7.2) to reflect inter- and intra-cellular environments in lung tissue. Concentrations of Be, Al, and Si in SLF increased linearly during the first 20 days of equilibration, and then rose slowly, or in some cases reached a maximum, and subsequently decreased. Relative to the other materials, BeO produced relatively low Be concentration in solution at pH 7.2; and relatively high Be concentration in solution at pH 4.5 during the first 20 days of equilibration. For both pH values, however, the Be concentration in SLF normalized to Be content of the material was lowest for BeO, demonstrating that BeO was distinct among the four other Be-containing materials in terms of its persistence as a source of Be to the SLF solution. Following 149 days of equilibration, the SLF solutions were fractionated using flow-field flow fractionation (FlFFF) with detection via ICP-MS. For all materials, nanoparticles (which were formed during equilibration) were dominantly distributed in the 10–100 nm size range. Notably, BeO produced the least nanoparticle-associated Be mass (other than silica) at both pH values. Furthermore, BeO produced the highest Be concentrations in the size range corresponding to < 3 kDa (determined via centrifugal ultrafiltration), indicating that in addition to persistence, the BeO produced the highest concentrations of truly dissolved (potentially ionic) Be relative to the other materials. Mass balance analysis showed reasonable sample recoveries during FFF fractionation (50–100%), whereas recoveries during ICP-MS (relative to acidified standards) were much lower (5–10%), likely due to inefficiencies in nebulizing and ionizing the nanoparticles.     

Asymmetric flow field flow fractionation of aqueous C60 nanoparticles with size determination by dynamic light scattering and quantification by liquid chromatography atmospheric pressure photo-ionization mass spectrometry

A size separation method was developed for aqueous C₆₀ fullerene aggregates (aqu/C₆₀) using asymmetric flow field flow fractionation (AF4) coupled to a dynamic light scattering detector in flow through mode. Surfactants, which are commonly used in AF4, were avoided as they may alter suspension characteristics. Aqu/C₆₀ aggregates generated by sonication in deionized water ranged in size from 80 to 260 nm in hydrodynamic diameter (D_h) as determined by DLS in flow through mode, which was corroborated by analysis of fractions by DLS in batch mode and by TEM. The mass of C₆₀ in each fraction was determined by LC–APPI–MS. Only 5.2 ± 6.7% of the total aqu/C₆₀ mass had D_h less than 80 nm, while 58 ± 32% of the total aqu/C₆₀ mass had D_h between 80 and 150 nm and 14 ± 9.2% of the total aqu/C₆₀ were between 150 and 260 nm in D_h. With the optimal fractionation parameters, 77 ± 5.8% of the aqu/C₆₀ mass eluted from the AF4 channel, indicating deposition on the AF4 membrane had occurred during fractionation; use of alternative membranes did not reduce deposition. Channel flow splitting increased detector response although channel split ratios greater than 80% of the channel flow led to decreased detector response. This is the first report on the use of AF4 for fractionating a colloidal suspension of aqu/C₆₀.