Band spreading control in electrophoresis microchips by localized zeta-potential variation using field-effect

The paper proposes a new technique, which varies the zeta potential along the channel walls in the vicinity of the microchannel corners in such as a way as to minimize the effects of turn-induced dispersion within U-shaped separation channels. The effects of the separation channel geometry, the fluid velocity profile, and boundary control of the zeta potential on the band distribution in the detection area are all discussed within this paper. The results for the folded square U-shaped separation channel indicate that boundary control of the zeta potential by field-effect significantly reduces the band dispersion induced by the 90[degree] turns. Finally, the results confirm that application of the proposed localized zeta potential variation method results in a correction of the band tilting phenomenon and a reduction in the racetrack effect.     

Analysis of geometry effects on band spreading of microchip electrophoresis

The geometry and the flow field conditions in the separation microchannel of an electrophoresis chip system may have important impact on the system's separation efficiency. Understanding the geometry effect on the flow field physics in the separation microchannel is beneficial to the design or operation of an electrophoresis system. The turns in a microfabricated separation microchannel generally results in degraded separation quality. To avoid this limitation, channels are constructed with different types of turns to determine the optimum design that minimizes turn-induced band broadening. We have designed and tested various geometric bend ratios to greatly reduce this so-called "racetrack" effect. The effects of the separation channel geometry, fluid velocity profile and bend ratio on the band distribution in the detection area are discussed. Results show that the folded square U-shaped channel is better for miniaturization and simplification. The band tilting was corrected and the racetrack effect reduced in the detection area when the bend ratio is 4:1. The detection time obtained from the present numerical solution matches very well with the experimental data.     

Transport of charged samples in fluidic channels with large zeta potentials

In this article, we present an analysis on the transport of charged samples through micro- and nanofluidic channels with large zeta potentials (|zeta| > (kBT)/e). Using the Method of Moments formulation, the diffusion-convection equation has been solved to evaluate the mean velocity and the dispersion of analyte bands in a parallel-plate device under electrokinetically- and pressure-driven flow conditions. The effect of electromigration induced by the lateral electric field within the Debye layer has been quantified in our work using a Peclet number (Pe t) based on the characteristic electrophoretic velocity of the solute molecules in the transverse direction. It has been shown that while the effects of transverse electromigration on analyte transport only depends on the product Pe t zeta* for |zeta*| = (ezeta)/kBT < 1, both these parameters independently affect the flow of charged species in large zeta potential systems. For a given value of Pe t zeta*, the mean velocity and the slug dispersivity can vary by as much as an order of magnitude in going from a small zeta potential system (|zeta*| < 1) to a channel with |zeta*| = 4.     

Peak compression and resolution for electrophoretic separations in diverging microchannels

We report the results of experiments and simulations on electrokinetic flow in diverging microchannels (with cross-sectional area that increases with distance along the channel). Because of conservation of mass and charge, the velocity of an analyte in the channel decreases as the channel cross-section increases. Consequently, the leading edge of a band of sample moves more slowly than the trailing edge and the sample band is compressed. Sample peak widths, rather than increasing diffusively with time, can then be controlled by the geometry of the channel and can even be made to decrease with time. We consider the possibility of using this peak compression effect to improve the resolution of electrophoretic separations. Our results indicate that for typical separations that are dispersion limited, this peak compression effect is more than offset by the decreased distance between peaks, and the separation resolution in diverging channels is worse than that found for straight channels at the same applied voltage. For separations in very short channels or at very high field strengths, however, when the separation efficiency is injection limited, the peak compression effect is dominant and diverging channels can then be used to achieve improved separation resolution.     

Estimation of zeta potential by electrokinetic analysis of ionic fluid flows through a divergent microchannel

The streaming potential is generated by the electrokinetic flow effect within the electrical double layer of a charged solid surface. Surface charge properties are commonly quantified in terms of the zeta potential obtained by computation with the Helmholtz-Smoluchowski (H-S) equation following experimental measurement of streaming potential. In order to estimate a rigorous zeta potential for cone-shaped microchannel, the correct H-S equation is derived by applying the Debye-Hückel approximation and the fluid velocity of diverging flow on the specified position. The present computation provides a correction ratio relative to the H-S equation for straight cylindrical channel and enables us to interpret the effects of the channel geometry and the electrostatic interaction. The correction ratio decreases with increasing of diverging angle, which implies that smaller zeta potential is generated for larger diverging angle. The increase of Debye length also reduces the correction ratio due to the overlapping of the Debye length inside of the channel. It is evident that as the diverging angle of the channel goes to nearly zero, the correction ratio converges to the previous results for straight cylindrical channel.     

Lattice Poisson-Boltzmann simulations of electro-osmotic flows in microchannels

This paper presents the numerical results of electro-osmotic flows in micro- and nanofluidics using a lattice Poisson-Boltzmann method (LPBM) which combines a potential evolution method on discrete lattices to solve the nonlinear Poisson equation (lattice Poisson method) with a density evolution method on discrete lattices to solve the Boltzmann-BGK equation (lattice Boltzmann method). In an electrically driven osmotic flow field, the flow velocity increases with both the external electrical field strength and the surface zeta potential for flows in a homogeneous channel. However, for a given electrical field strength and zeta potential, electrically driven flows have an optimal ionic concentration and an optimum width that maximize the flow velocity. For pressure-driven flows, the electro-viscosity effect increases with the surface zeta potential, but has an ionic concentration that yields the largest electro-viscosity effect. The zeta potential arrangement has little effect on the electro-viscosity for heterogeneous channels. For flows driven by both an electrical force and a pressure gradient, various zeta potential arrangements were considered for maximize the mixing enhancement with a less energy dissipation.     

Characterization of voltage degradation in dynamic field gradient focusing

Dynamic field gradient focusing (DFGF) is an equilibrium gradient method that utilizes an electric field gradient to simultaneously separate and concentrate charged analytes based on their individual electrophoretic mobilities. This work describes the use of a 2-D nonlinear, numerical simulation to examine the impact of voltage loss from the electrodes to the separation channel, termed voltage degradation, and distortions in the electric field on the performance of DFGF. One of the design parameters that has a large impact on the degree of voltage degradation is the placement of the electrodes in relation to the separation channel. The simulation shows that a distance of about 3 mm from the electrodes to the separation channel gives the electric field profile with least amount of voltage degradation. The simulation was also used to describe the elution of focused protein peaks. The simulation shows that elution under constant electric field gradient gives better performance than elution through shallowing of the electric field. Qualitative agreement between the numerical simulation and experimental results is shown. The simulation also illustrates that the presence of a defocusing region at the cathodic end of the separation channel causes peak dispersion during elution. The numerical model is then used to design a system that does not suffer from a defocusing region. Peaks eluted under this design experienced no band broadening in our simulations. Preliminary experimental results using the redesigned chamber are shown.     

Effect of dispersants on dispersion stability of collophane and quartz fines in aqueous suspensions

A stable dispersion of fine mineral particles in an aqueous system facilitated by dispersants is an essential prerequisite for their successful separation. We investigated the dispersion stability and mechanism of suspensions of aqueous collophane and quartz fines (10?µm) in the presence of sodium hexametaphosphate (SHMP), sodium silicate or sodium carbonate using the sedimentation balance method, zeta potential measurements, contact angle measurements, micro-flotation tests and theoretical calculation of Extended-DLVO (Derjaguin-Landau-Verwey-Overbeek). The results showed that three dispersants significantly enhanced the dispersion stability of collophane in the following descending order SHMP?>?sodium silicate?>?sodium carbonate. This is because they increased the zeta potential of collophane in the same order; meanwhile, the SHMP made the collophane more hydrophilic compared to two other dispersants. These results illustrated that the dispersion stability was attributed to electrostatic repulsion and hydration repulsion and that the hydration repulsion had a greater influence on the stability than electrostatic repulsion based on the calculation of Extended-DLVO. However, the quartz suspension always maintained a stable dispersion in the absence or presence of dispersants, since there was a higher zeta potential and stronger hydrophilicity for natural quartz. These provide a theoretical direction for the dispersion of fine-disseminated siliceous phosphorites and phosphate slimes in separations.     

Electrokinetic-vortex formation near a two-part cylinder with same-sign zeta potentials in a straight microchannel

Vortex formation near a two-part cylinder with zeta potentials of different values but the same sign under an external DC electric field is numerically investigated in this paper. The cylinder, inserted in a straight microchannel filled with an aqueous solution, is composed of an upstream part and a downstream part. When a DC electric field is applied in the channel, under certain conditions, the vortex will form near the cylinder due to the different velocities of electroosmotic flow generated on the cylinder surface. The numerical results reveal that the larger the velocity difference of electroosmotic flow generated on the two-part cylinder and the smaller the channel width, the more conducive to vortex formation in the channel. In addition, if the zeta potential ratios of cylinder downstream part to upstream part and channel wall to cylinder upstream part are unchanged, the DC electric field strength and the zeta potential value do not affect the pattern of vortices formed in the channel. This study provides a way for vortex formation in microchannels and has the potential application in microfluidic devices.     

System-oriented dispersion models of general-shaped electrophoresis microchannels

This paper presents a system-oriented model for analyzing the dispersion of electrophoretic transport of charged analyte molecules in a general-shaped microchannel, which is represented as a system of serially connected elemental channels of simple geometry. Parameterized analytical models that hold for analyte bands of virtually arbitrary initial shape are derived to describe analyte dispersion, including both the skew and broadening of the band, in elemental channels. These models are then integrated to describe dispersion in the general-shaped channel using appropriate parameters to represent interfaces of adjacent elements. This lumped-parameter system model offers orders-of-magnitude improvement in computational efficiency over full numerical simulations, and is verified by results from experiments and numerical simulations. The model is used to perform a systematic parametric study of serpentine channels consisting of a pair of complementary turn microchannels, and the results indicate that dispersion in a particular turn can contribute to either an increase or decrease of the overall band broadening. The efficiency and accuracy of the system model is further demonstrated by its application to general-shaped channels that occur in practice, including a serpentine channel with multiple complementary turns and a multi-turn spiral-shaped channel. The results indicate that our model is an accurate and efficient simulation tool useful for designing optimal electrophoretic separation microchips.     

Effects of surface heterogeneity on flow circulation in electroosmotic flow in microchannels

The characteristics of electroosmotic flow in a cylindrical microchannel with non-uniform zeta potential distribution are investigated in this paper. Two-dimensional full Navier–Stokes equation is used to model the flow field and the pressure field. The numerical results show the distorted electroosmotic velocity profiles and various kinds of flow circulation resulting from the axial variation of the zeta potential. The influences of heterogeneous patterns of zeta potential on the velocity profile, the induced pressure distribution and the volumetric flow rate are discussed in this paper. This work shows that using either heterogeneous patterns of zeta potential or a combination of a heterogeneous zeta potential distribution and an applied pressure difference over the channel can generate local flow circulations and hence provide effective means to improve the mixing between different solutions in microchannels.     

Diffusiophoresis of concentrated suspensions of spherical particles with distinct ionic diffusion velocities

The diffusiophoresis of a concentrated spherical dispersion of colloidal particles subject to a small electrolyte gradient is analyzed theoretically for an arbitrary zeta potential and double layer thickness. In particular, the influence of the difference in the diffusivities of cations and anions is discussed. A unit cell model is used to simulate a spherical dispersion, and a pseudospectral method is adopted to solve the equations governing the phenomenon under consideration. We show that, as in the case of an infinitely dilute dispersion, when the diffusivities of cations and anions are different, the diffusiophoretic mobility is no longer an even function of the zeta potential or double layer thickness. In contrast to the case of identical diffusivity of cations and anions, a local electric field is induced in the present case due to an unbalanced charge distribution between higher and lower concentration regions. Depending upon the direction of this induced electric field, the diffusiophoretic mobility can be larger or smaller than that for the case of identical diffusivity. The diffusiophoretic mobility is influenced mainly by the induced electric field arising from the difference in the ionic diffusivities, the concentration gradient, and the effect of double layer polarization.     

Electric‐Field Distribution at the End of a Charged Capillary—A Coupling Imaging Study

The electric‐field distribution at the end of a charged capillary system is detected using a scanning electrochemical microscopy (SECM) coupling imaging mode. A theoretical model based on the resistance of solution at the capillary end describes the three‐dimensional distribution of the electric field. The effect of the detection electrode position and separation high voltage on solution potential is observed and analyzed. Results demonstrate that the electric field at the end‐channel shows an isopotential contour changing from a disk shape into a hemispherical shape when leaving the capillary opening. The solution potential decreases along the central axis of the capillary to the detection reservoir. In the same scanning plane, the solution potential decreases along the radial direction. Increase of the separation high voltage results in the increase of the absolute solution potential but does not change the relative spatial electric‐field distribution.     

3-D transient electrophoretic motion of a spherical particle in a T-shaped rectangular microchannel

This paper considers the electrophoretic motion of a spherical particle in an aqueous electrolyte solution in a T-shaped rectangular microchannel, where the size of the channel is close to that of the particle. This is a complicated transient process where the electric field, the flow field, and the particle motion are coupled together. A theoretical model was developed to investigate the influences of the applied electric potentials, the zeta potentials of the channel and the particle, and the size of the particle on the particle motion. A direct numerical simulation method using the finite element method is employed. This method employs a generalized Galerkin finite element formulation that incorporates both equations of the fluid flow and equations of the particle motion into a single variational equation where the hydrodynamic interactions are eliminated. The ALE method is used to track the surface of the particle at each time step. The numerical results show that the electric field in the T-shaped microchannel is influenced by the presence of the particle, and that the particle motion is influenced by the applied electric potentials and the zeta potentials of the channel and the particle. The path of the particle motion is dominated by the local electric field and the ratio of the zeta potential of the channel to that of the particle. The particle's velocity is also dependent on its size in a small channel.     

甲基丙烯酸对聚合物乳胶粉再分散性影响机理

采用半连续种子乳液聚合法,以甲基丙烯酸(MAA)为壳层亲水功能单体,合成了丙烯酸酯原乳液,并通过喷雾干燥法制得具有可再分散性的聚合物乳胶粉.讨论了原乳液粒子粒径随pH值和MAA量的变化关系;重点研究了MAA量对乳胶粉水分散液稳定性、再分散乳液zeta电位、乳胶粒粒径分布及乳胶粉内部微观形貌的影响,并分析其作用机理.研究结果表明:原乳液粒子粒径随pH值的增大逐渐增大,且MAA含量越高,粒径增幅越大;随MAA量增加,再分散液稳定性增强,zeta电位绝对值增大,平均粒径逐渐变小,乳胶粉再分散性显著改善.透射电子显微镜(TEM)结果显示:当MAA含量较高时,乳胶粉内部出现较大孔径的中空微孔结构.中空微孔结构提供水分向乳胶粉内部扩散通道,因而优化其水分散性,再分散乳液的"绒毛结构"与较高的zeta电位赋予其优异的分散稳定性.     

A low-leakage sample plug injection scheme for crossform microfluidic capillary electrophoresis devices incorporating a restricted cross-channel intersection

This study develops a crossform CE microfluidic device in which a single-circular barrier or a double-circular barrier is introduced at the cross-channel intersection. Utilizing a conventional crossform injection scheme, it is shown that these barriers reduce sample leakage and deliver a compact sample band into the separation channel, thereby ensuring an enhanced detection performance. A series of numerical and experimental investigations are performed to investigate the effects of the barrier type and the barrier ratio on the flow streamlines within the microchannel and to clarify their respective effects on the sample leakage ratio and sample plug variance during the injection process. The results indicate that a single-circular barrier injector with a barrier ratio greater than 20% and a double-circular barrier injector with a barrier ratio greater than 40% minimize the sample leakage ratio and produce a compact sample plug. As a result, both injectors have an excellent potential for use in high-quality, high-throughput chemical analysis procedures and in many other applications throughout the micro-total analysis systems field.     

Surface decoration and dispersibility of carbon nanofibers in aqueous surfactant solution

As a novel functional nanomaterial, the dispersion effect of carbon nanofibers (CNFs) has a significant influence on the application of CNFs in the composites. Two effective surfactants, methylcellulose (MC) and polycarboxylate superplasticizer, were used to analyze the dispersion of CNFs in aqueous solution. A method utilizing ultrasonic processing was employed to achieve a homogenous CNF suspension, and the dispersion effect was further characterized by the method of measuring ultraviolet absorbency (UV absorbency), zeta potential, surface tension and transmission electron microscopy (TEM) micrographs. The results show that the zeta potential and surface tension reach the saturation plateau at MC concentration and polycarboxylate superplasticizer concentration of about 0.4 and 0.8 g/L, respectively, which reflects that the optimum concentration ratio of MC to CNFs is 2: 1, and the optimum dispersing polycarboxylate superplasticizer to CNFs ratio of 4: 1 is required to achieve dispersions with maximum achievable dispersion of CNFs.     

Electrokinetic mixing vortices due to electrolyte depletion at microchannel junctions

Due to electric field leakage across sharp corners, the irrotational character of Ohmic electroosmotic flow is violated. Instead, we demonstrate experimentally and theoretically evidence of electrolyte depletion and vortex separation in electroosmotic flow around a junction between wide and narrow channels. When the penetration length of the electric field exceeds the width of the narrow channel and if the electric field is directed from the narrow to the wide channel, the electromigration of ions diminishes significantly at the junction end of the narrow channel due to this leakage. Concentration depletion then develops at that location to maintain current balance but it also increases the corner zeta potential and the local electroosmotic slip velocity. A back pressure gradient hence appears to maintain flow balance and, at a sufficient magnitude, generates a pair of vortices.     

One-shot screen-printed thylakoid membrane-based biosensor for the detection of photosynthetic inhibitors in discrete samples

A method is developed to determine the optimal profile of zeta potential around U turns such that the turn-induced spreading of a solute band is minimized. After proposing a velocity profile that eliminates the racetrack effect, a conjugate gradient method is adopted to find the zeta potential profile to induce the required velocity. The optimal profiles of zeta potential seem to be insensitive to the relevant parameters of electroosmotic flows. It is shown that a reduction of variance two orders of magnitude below that of a comparable turn with uniform zeta potential is easily attained by adopting the optimal profile of zeta potential, which can be realized using a UV excimer laser or external voltage control.     

Synchronized cyclic capillary electrophoresis using channels arranged in a triangle and low voltages

Synchronized cyclic capillary electrophoresis (SCCE) makes use of a closed loop separation channel by which the same sample can be separated during many cycles. This enables the repeated use of the same voltage for separations such that a high total voltage, and thus high efficiency, is obtained for the synchronized components. This can be accomplished by using any type of polygon geometry for the separation channel; and calculations of the available field and number of connections needed for polygons from 3 to 5 sides are presented. Triangular designs have the advantage of using the lowest number of wells. Such designs are described, with two additional features compared to that of earlier work: 1. voltage connections that are much shallower than the separation channel, to reduce losses and dispersion at the intersections; and 2. corners that are narrower than the separation channels to reduce dispersion in the turns. Experimental data is presented for the separation of a mixture of amino acids, and for a DNA separation in a polymeric sieving matrix. The DNA separation is most sensitive to the corner dispersion problem, which reduces the observed efficiency for that separation.