Electrokinetic particle trapping in microfluidic wells using conductive nanofiber mats.

The frequency dependence of electrokinetic particle trapping using large-area (>mm2) conductive carbon nanofiber (CNF) mat electrodes is investigated. The fibers provide nanoscale geometric features for the generation of high electric field gradients, which is necessary for particle trapping via dielectrophoresis (DEP). A device was fabricated with an array of microfluidic wells for repeated experiments; each well included a CNF mat electrode opposing an aluminum electrode. Fluorescent microspheres (1 µm) were trapped at various electric field frequencies between 30 kHz and 1 MHz. Digital images of each well were analyzed to quantify particle trapping. DEP trapping by the CNF mats was greater at all tested frequencies than that of the control of no applied field, and the greatest trapping was observed at a frequency of 600 kHz, where electrothermal flow is more significantly weakened than DEP. Theoretical analysis and measured impedance spectra indicate that this result was due to a combination of the frequency dependence of DEP and capacitive behavior of the well-based device.

Energy harvesting from water streaming at charged surface.

Water flowing at a charged surface may produce electricity, known as streaming current/potentials, which may be traced back to the 19th century. However, due to the low gained power and efficiencies, the energy conversion from streaming current was far from usable. The emergence of micro/nanofluidic technology and nanomaterials significantly increases the power (density) and energy conversion efficiency. In this review, we conclude the fundamentals and recent progress in electrical double layers at the charged surface. We estimate the generated power by hydrodynamic energy dissipation in multi-scaling flows considering the viscous systems with slipping boundary and inertia systems. Then, we review the coupling of volume flow and current flow by the Onsager relation, as well as the figure of merits and efficiency. We summarize the state-of-the-art of electrokinetic energy conversions, including critical performance metrics such as efficiencies, power densities, and generated voltages in various systems. We discuss the advantages and possible constraints by the figure of merits, including single-phase flow and flying droplets.

Streaming electric field, electroviscous effect, and electrokinetic liquid flows in the induced pressure-driven transport of active liquids in narrow capillaries.

In this paper, we develop a theory for studying the electrokinetic effects in a charged nanocapillary filled with active liquid. The active particles present within the active liquid are self-driven, demonstrate vortex defects, and enforce a circumferentially arranged polarization field. Under such circumstances, there is the development of an induced pressure-gradient-driven transport dictated (similar to diffusioosmotic transport) by the presence of an axial gradient in the activity (or the concentration of the active particles). This pressure-driven transport has a profile different from the standard Hagen-Poiseuille flow in a nanocapillary. Also, this induced pressure-driven flow drives electrokinetic effects, which are characterized by the generation of a streaming electric field, associated electroosmotic (EOS) transport opposing pressure-driven flow, and electroviscous effect. We quantify these effects as functions of dimensionless parameters that vary inversely as the strength of the activity-induced pressure-driven flow and salt concentrations. Overall, we anticipate that this paper will draw immense attention toward a new type of activity-induced pressure-driven flow and associated electrokinetic phenomena in charged nanoconfinements.

Numerical and experimental investigation of the deviation of microparticles inside the microchannel using the vortices caused by the ICEK phenomenon.

One field of study in microfluidics is the control, trapping, and separation of microparticles suspended in fluid. Some of its applications are related to cell handling, virus detection, and so on. One of the new methods in this field is using ICEK phenomena and dielectrophoresis forces. In the present study, considering the ICEK phenomena, the microparticles inside the fluid are deviated in the desired ratio using a novel ICEK microchip. The deviation is such that after the microparticles reach the floating electrode, they are trapped in the ICEK flow vortex and deviated through a secondary channel that was placed crosswise and noncoplanar above the main channel. For simulation verification, an experimental test is done. The method used for making two noncoplanar channels and separating the particles in the desired ratio with a simple ICEK microchip is an innovation of the present study. Moreover, the adjustment of the percentage of separation of microparticles by adjusting the parameters of the applied voltage and fluid inlet velocity is one of the other innovations of the present experimental study. We observed that for input velocities of 150-1200 µm/s with applied voltages of 10-33 V, 100% of the particles can be directed toward the secondary-channel.

Modulating selective ionic enrichment and depletion zones in straight nanochannels via the interplay of surface charge modulation and electric field mediated fluid-thickening.

We report the possibilities of achieving highly controlled segregation of ion-enriched and ion-depleted regions in straight nanochannels. This is achieved via harnessing the interplay of an axial gradient of the induced transverse electric field on account of electrical double layer phenomenon and the localized thickening of the fluid because of intensified electric fields due to the large spatial gradients of the electrical potential in extreme confinements. By considering alternate surface patches of different charge densities over pre-designed axial spans, we illustrate how these effects can be exploited to realize selectively ion-enriched and ion-depleted zones. Physically, this is attributed to setting up of an axial concentration gradient that delves on the ionic advection due to the combined effect of an externally applied electric field and induced back-pressure gradient along the channel axis and electro-migration due to the combinatorial influences of the applied and the induced electrostatic fields. With an explicit handle on the pertinent parameters, our results offer insights on the possible means of imposing delicate controls on the solute-enrichment and depletion phenomena, a paradigm that remained unexplored thus far.

Zeta Potentials of Cotton Membranes in Acetonitrile Solutions.

Solid surfaces in contact with nonaqueous solvents play a key role in electrochemistry, analytical chemistry, and industrial chemistry. In this work, the zeta potentials of cotton membranes in acetonitrile solutions were determined by streaming potential and bulk conductivity measurements. By applying the Gouy-Chapman theory and the Langmuir adsorption isotherm of ions to the experimental data, the mechanism of the electrification at the cotton/acetonitrile interface is revealed for the first time to be solely due to ion adsorption on the surface, rather than proton dissociation at the interface. Different salts were found to produce opposite signs of the zeta potentials. This behavior can be attributed to ion solvation effects and the strong ordering of acetonitrile molecules at the interface. Furthermore, a trend of the electroviscous effect was observed, in agreement with the standard electrokinetic theory. These findings demonstrate that electrokinetics in acetonitrile, a polar aprotic solvent, can be treated in the same manner as in water.

DC Electric Fields Promote Biodegradation of Waterborne Naphthalene in Biofilter Systems.

Biofiltration is a simple and low-cost method for the cleanup of contaminated water. However, the reduced availability of dissolved chemicals to surface-attached degrader bacteria may limit its efficient use at certain hydraulic loadings. When a direct current (DC) electric field is applied to an immersed packed bed, it invokes electrokinetic processes, such as electroosmotic water flow (EOF). EOF is a surface-charge-induced plug-flow-shaped movement of pore fluids. It acts at a nanometer distance above surfaces and allows the change of microscale pressure-driven flow profiles and, hence, the availability of dissolved contaminants to microbial degraders. In laboratory percolation columns, we assessed the effects of a weak DC electric field (E = 0.5 V·cm-1) on the biodegradation of waterborne naphthalene (NAH) by surface-attached Pseudomonas fluorescens LP6a. To vary NAH bioavailability, we used different NAH concentrations (C0 = 2.7, 5.1, or 7.8 × 10-5 mol·L-1) and Darcy velocities typical for biofiltration (U¯ = 0.2-1.2 × 10-4 m·s-1). In DC-free controls, we observed higher specific degradation rates (qc) at higher NAH concentrations. The qc depended on U¯, suggesting bioavailability restrictions depending on the hydraulic residence times. DC fields consistently increased qc and resulted in linearly increasing benefits up to 55% with rising hydraulic loadings relative to controls. We explain these biodegradation benefits by EOF-altered microscale flow profiles allowing for better NAH provision to bacteria attached to the collectors even though the EOF was calculated to be 100-800 times smaller than bulk water flow. Our data suggest that electrokinetic approaches may give rise to future technical applications that allow regulating biodegradation, for example, in response to fluctuating hydraulic loadings.

A novel test set up to study three-dimensional electrokinetic dewatering of dredged soil.

The dredged soil obtained from maintenance activities of water bodies has emerged as a potential alternate fill material for infrastructure development. However, dredged soil requires stabilization due to high initial water content, low shear strength and high compressibility. Among several methods, stabilization of dredged soil by using electrokinetics is one of the effective ground improvement techniques that uses electric field to dewater and strengthen the soil. In this context, a series of experiments were conducted on dredged soil by using a combination of electrokinetic treatment with and without 6 kPa seating pressure (viz., low surcharge). A customized and patented electrokinetic dewatering (EKD) test set up was used for the three-dimensional electrokinetic treatment of soil. The potential difference (in the range of 6 V-48 V) within the soil was achieved by inserting stainless steel pipes of 21.4 mm outer diameter, 1.2 mm thickness, and 170 mm length. Two control tests (with and without seating pressure of 6 kPa) also were performed to understand the effectiveness of EKD. From the study, up to 1057% and 427% increase in dewatering was noted in EKD tests due to application of 24 V (optimum voltage noted in EKD tests) as compared to control tests, without and with seating pressure, respectively. Further, seating pressure with EKD resulted in effective control of crack formation in the dredged soil and uniform improvement in shear strength along the depth (up to 95 kPa). The combination of low surcharge with EKD, adopted in the study, is also expected to yield lower differential settlement, and hence better performance of geotechnical structures built on improved dredged soil. The novel 3-dimensional patented EKD test setup with Arduino-programmed automatic water pumping enables collecting and accurately measuring dewatered effluent volume, performing cone penetration tests on undisturbed soil, and collecting soil samples for determination of water content/physiochemical properties from different locations. Overall, the developed EKD setup can be utilized for evaluating the effectiveness and adopting real-time progress management for EKD or other ground improvement methods, and remediation of sludge, mine tailings, dredged sediments, and contaminated soils.

Sedimentation of a Charged Soft Sphere within a Charged Spherical Cavity.

The sedimentation of a soft particle composed of an uncharged hard sphere core and a charged porous surface layer inside a concentric charged spherical cavity full of a symmetric electrolyte solution is analyzed in a quasi-steady state. By using a regular perturbation method with small fixed charge densities of the soft sphere and cavity wall, a set of linearized electrokinetic equations relevant to the fluid velocity field, electrical potential profile, and ionic electrochemical potential energy distributions are solved. A closed-form formula for the sedimentation velocity of the soft sphere is obtained as a function of the ratios of core-to-particle radii, particle-to-cavity radii, particle radius-to-Debye screening length, and particle radius-to-porous layer permeation length. The existence of the surface charge on the cavity wall increases the settling velocity of the charged soft sphere, principally because of the electroosmotic enhancement of fluid recirculation within the cavity induced by the sedimentation potential gradient. When the porous layer space charge and cavity wall surface charge have the same sign, the particle velocity is generally enhanced by the presence of the cavity. When these fixed charges have opposite signs, the particle velocity will be enhanced/reduced by the presence of the cavity if the wall surface charge density is sufficiently large/small relative to the porous layer space charge density in magnitude. The effect of the wall surface charge on the sedimentation of the soft sphere increases with decreases in the ratios of core-to-particle radii, particle-to-cavity radii, and particle radius-to-porous layer permeation length but is not a monotonic function of the ratio of particle radius-to-Debye length.

Nonlinear electrophoresis of dielectric particles in Newtonian fluids.

In classical electrokinetics, the electrophoretic velocity of a dielectric particle is a linear function of the applied electric field. Theoretical studies have predicted the onset of nonlinear electrophoresis at high electric fields because of the nonuniform surface conduction over the curved particle. However, experimental studies have been left behind and are insufficient for a fundamental understanding of the parametric effects on nonlinear electrophoresis. We present in this work a systematic experimental study of the effects of buffer concentration, particle size, and particle zeta potential on the electrophoretic velocity of polystyrene particles in a straight rectangular microchannel for electric fields of up to 3 kV/cm. The measured nonlinear electrophoretic particle velocity is found to exhibit a 2(±0.5)-order dependence on the applied electric field, which appears to be within the theoretically predicted 3- and 3/2-order dependences for low and high electric fields, respectively. Moreover, the obtained nonlinear electrophoretic particle mobility increases with decreasing buffer concentration (for the same particle) and particle size (for particles with similar zeta potentials) or increasing particle zeta potential (for particles with similar sizes). These observations are all consistent with the theoretical predictions for high electric fields.

Electrokinetics in antimicrobial resistance analysis: A review.

Infections caused by antimicrobial resistance are a serious problem in the world. Currently, commercial devices for antimicrobial susceptibility testing and resistant bacteria identification are time-consuming. There is an urgent need to develop fast and accurate methods, especially in the process of sample pretreatment. Electrokinetic (EK) is a family of electric-field-based kinetic phenomena of fluid or embedded objects, and EK applications have been found in various fields. In this paper, EK bacteria manipulation, including enrichment and separation, is reviewed. Focus is given to the rapid electric-based minimum inhibitory concentration measurement. The future directions and major challenges in this field are also outlined.

Electropatterning-Contemporary developments for selective particle arrangements employing electrokinetics.

The selective positioning and arrangement of distinct types of multiscale particles can be used in numerous applications in microfluidics, including integrated circuits, sensors and biochips. Electrokinetic (EK) techniques offer an extensive range of options for label-free manipulation and patterning of colloidal particles by exploiting the intrinsic electrical properties of the target of interest. EK-based techniques have been widely implemented in many recent studies, and various methodologies and microfluidic device designs have been developed to achieve patterning two- and three-dimensional (3D) patterned structures. This review provides an overview of the progress in electropatterning research during the last 5 years in the microfluidics arena. This article discusses the advances in the electropatterning of colloids, droplets, synthetic particles, cells, and gels. Each subsection analyzes the manipulation of the particles of interest via EK techniques such as electrophoresis and dielectrophoresis. The conclusions summarize recent advances and provide an outlook on the future of electropatterning in various fields of application, especially those with 3D arrangements as their end goal.

Electrokinetic transport phenomena in nanofluidics and their applications.

Much progress has been made in the electrokinetic phenomena inside nanochannels in the last decades. As the dimensions of the nanochannels are compatible to that of the electric double layer (EDL), the electrokinetics inside nanochannels indicate many unexpected behaviors, which show great potential in the fields of material science, biology, and chemistry. This review summarizes the recent development of nanofluidic electrokinetics in both fundamental and applied research. First, the techniques for constructing nanochannels are introduced to give a guideline for choosing the optimal fabrication technique based on the specific feature of the nanochannel. Then, the theories and experimental investigations of the EDL, electroosmotic flow, and electrophoresis of nanoparticles inside the nanochannels are discussed. Furthermore, the applications of nanofluidic electrokinetics in iontronics, sensing, and biomolecule separation fields are summarized. In Section 5, some critical challenges and the perspective on the future development of nanofluidic electrokinetics are briefly proposed.

Dielectric polarization-mediated efficient solute mixing: Effect of the geometrical configuration of polarizing blocks.

We propose a novel technique, consistent with the induced charge electrokinetic (ICEK) phenomenon, for the efficient mixing of solute species at a microfluidic scale. A nonuniform bipolar electric double layer develops in the presence of an external electric field over a polarizable object is better known as the ICEK phenomenon. This ICEK is one of the most favorable techniques preferred for enhanced solute mixing in on-chip microfluidic platforms. In the purview of the ICEK phenomenon, instead of using perfectly conducting polarizable objects, for the first time in this study, we employ polarizable dielectric objects of different sizes and shapes for efficient mixing of solute species. We show that different types of vortices developed in the flow pathway adjacent to the polarizable dielectric blocks help in yielding efficient mixing in the proposed configuration. The novelty of our work is embellished in two different perspectives, that is, first, concentrating on the influences of the physical properties of the polarizable dielectric block on the underlying mixing, and, second, focusing on their sizes, shapes, and the arrangements in tuning the underlying mixing phenomena.

Rapid prototyping of polydimethylsiloxane (PDMS) microchips using electrohydrodynamic jet printing: Application to electrokinetic assays.

Polydimethylsiloxane (PDMS) based microfluidic devices have found increasing utility for electrophoretic and electrokinetic assays because of their ease of fabrication using replica molding. However, the fabrication of high-resolution molds for replica molding still requires the resource-intensive and time-consuming photolithography process, which precludes quick design iterations and device optimization. We here demonstrate a low-cost, rapid microfabrication process, based on electrohydrodynamic jet printing (EJP), for fabricating non-sacrificial master molds for replica molding of PDMS microfluidic devices. The method is based on the precise deposition of an electrically stretched polymeric solution of polycaprolactone in acetic acid on a silicon wafer placed on a computer-controlled motion stage. This process offers the high-resolution (order 10  µ $\umu$ m) capability of photolithography and rapid prototyping capability of inkjet printing to print high-resolution templates for elastomeric microfluidic devices within a few minutes. Through proper selection of the operating parameters such as solution flow rate, applied electric field, and stage speed, we demonstrate microfabrication of intricate master molds and corresponding PDMS microfluidic devices for electrokinetic applications. We demonstrate the utility of the fabricated PDMS microchips for nonlinear electrokinetic processes such as electrokinetic instability and controlled sample splitting in ITP. The ability to rapid prototype customized reusable master molds with order 10  µ $\umu$ m resolution within a few minutes can help in designing and optimizing microfluidic devices for various electrokinetic applications.

Catalytic activity of glucose oxidase after dielectrophoretic immobilization on nanoelectrodes.

Dielectrophoresis (DEP) is an AC electrokinetic effect that is proven to be effective for the immobilization of not only cells, but also of macromolecules, for example, antibodies and enzyme molecules. In our previous work, we have already demonstrated the high catalytic activity of immobilized horseradish peroxidase after DEP. To evaluate the suitability of the immobilization method for sensing or research in general, we want to test it for other enzymes, too. In this study, glucose oxidase (GOX) from Aspergillus niger was immobilized on TiN nanoelectrode arrays by DEP. Fluorescence microscopy showed the intrinsic fluorescence of the immobilized enzymes flavin cofactor on the electrodes. The catalytic activity of immobilized GOX was detectable, but a fraction of less than 1.3% of the maximum activity that was expected for a full monolayer of immobilized enzymes on all electrodes was stable for multiple measurement cycles. Therefore, the effect of DEP immobilization on the catalytic activity strongly depends on the used enzyme.

Direct pumping of polar fluids with traveling-wave dielectrophoresis.

Efficiently pumping fluids without moving parts in extremely miniaturized formats is challenging. Here, we propose and numerically explore a new type of fluid pump in which a series of electrodes driven at different phases produce a force directly on the molecules of the fluid. This effect is based on traveling-wave dielectrophoresis (twDEP), which has been observed to drive the motion of colloidal particles. Here, we leverage the time needed for fluid molecules with permanent dipoles to align with the applied field to maintain a phase lag between the applied field and the molecular polarization. While requiring operation in the GHz range, this effect is predicted to be efficient due to its ability to directly drive bulk fluid motion. We begin by establishing the foundational equations for this effect and performing finite element simulations to determine its magnitude in a model geometry. By combining theory and a systematic series of calculations, we validate that twDEP pumps should exhibit a fluid flow that scales as the voltage squared divided by the electrode period and that it should increase with the complex permittivity of the fluid and decrease with increasing viscosity. This results in a general equation that predicts the performance of twDEP pumps. Collectively, these computations provide a blueprint for producing twDEP pumps of polar fluids such as water and ethanol. We conclude by noting that the growing interest in high power microwave technology along with metasurfaces to locally tailor phase could provide a path to realizing twDEP pumps in practice.

A numerical study on microfluidic devices to maintain the concentration and purity of dielectrophoresis-induced separated fractions of analyte.

Determining the physical and chemical properties of biologically important particles such as cells, organelles, viruses, exosomes, complexes, nucleotides, and proteins is needed to understand their function. These properties are determined with common analytical tools (mass spectrometry, cryo-EM, NMR, various spectroscopies, nucleotide sequencing, etc.) whose function can be improved when samples are pure and concentrated. Separations science plays a central role in conditioning samples, ranging from low-resolution benchtop operations like precipitations or extractions to higher-resolution chromatography and electrophoresis. In the last two decades, gradient insulator-based dielectrophoresis (g-iDEP) has emerged as a high-resolution separation technique capable of highly selective enrichment of cells, viruses, exosomes, and proteins. Specific evidence has been shown that pure homogeneous and concentrated fractions of cells and exosomes can be generated from complex mixtures. However, recovering those fractions for analysis has not been developed, limiting the technique to an analytical rather than a preparative one. Here, a finite element analysis was undertaken to identify geometries and operational parameters to efficiently remove the enriched fraction while retaining maximum concentration and providing total mass transfer. Geometric factors (e.g., side channel width and distance from the gradient-inducing gap) were studied, along with the addition of a second inlet side channel. Two flow-generating mechanisms-electroosmosis and hydrostatic pressure-were evaluated for semi-optimized device designs, including a comparison of the one- and two-inlet designs. Simulations indicate effectively one hundred percent mass transfer and a concentration increase by an order of magnitude for several device configurations and operational parameters.

Electrophoresis-Assisted Multilayer Assembly of Nanoparticles for Sensitive Lateral Flow Immunoassay.

Lateral flow immunoassay (LFIA) is a rapid, simple, and inexpensive point-of-need method. A major limitation of LFIA is a high limit of detection (LOD), which impacts its diagnostic sensitivity. To overcome this limitation, we introduce a signal-enhancement procedure that is performed after completing LFIA and involves controllably moving biotin- and streptavidin-functionalized gold nanoparticles by electrophoresis. The nanoparticles link to immunocomplexes forming multilayer aggregates on the test strip, thus, enhancing the signal. Here, we demonstrate lowering the LOD of hepatitis B surface antigen from approximately 8 to 0.12 ng mL-1 , making it clinically acceptable. Testing 118 clinical samples for hepatitis B showed that signal enhancement increased the diagnostic sensitivity of LFIA from 73 % to 98 % while not affecting its 95 % specificity. Electrophoresis-driven enhancement of LFIA is universal (antigen-independent), takes two minutes, and can be performed by an untrained person.

Activity of AC electrokinetically immobilized horseradish peroxidase.

Dielectrophoresis (DEP) is an AC electrokinetic effect mainly used to manipulate cells. Smaller particles, like virions, antibodies, enzymes, and even dye molecules can be immobilized by DEP as well. In principle, it was shown that enzymes are active after immobilization by DEP, but no quantification of the retained activity was reported so far. In this study, the activity of the enzyme horseradish peroxidase (HRP) is quantified after immobilization by DEP. For this, HRP is immobilized on regular arrays of titanium nitride ring electrodes of 500 nm diameter and 20 nm widths. The activity of HRP on the electrode chip is measured with a limit of detection of 60 fg HRP by observing the enzymatic turnover of Amplex Red and H2 O2 to fluorescent resorufin by fluorescence microscopy. The initial activity of the permanently immobilized HRP equals up to 45% of the activity that can be expected for an ideal monolayer of HRP molecules on all electrodes of the array. Localization of the immobilizate on the electrodes is accomplished by staining with the fluorescent product of the enzyme reaction. The high residual activity of enzymes after AC field induced immobilization shows the method's suitability for biosensing and research applications.