A method to determine quasi-steady state in constant voltage mode isotachophoresis

Identification of the steady state is very challenging in isotachophoresis (ITP); especially in complex microgeometries, such as dog-leg channels or cross-channel junctions. In this work, an elastic matching method is applied to determine the quasi-steady state in microscale ITP. In the elastic matching method, the similarity between two profiles is calculated by comparing intensity distribution of two images or profiles. To demonstrate this similarity-based analysis technique for ITP, a constant voltage mode ITP model is developed and applied to a five-component ITP system. Hydrochloric acid and caproic acid are used as the leader and terminator, respectively, while histidine is used as the counter-ion. Two sample components, acetic acid and benzoic acid, are separated under the action of an applied electric field in both straight and dog-leg microchannels. This analysis shows that conductivity profiles provide a better measure to determine the quasi-steady state in an ITP process. For a straight microchannel, the quasi-steady state is achieved in less than a minute with a total potential drop of 100?V in a 2?cm long channel. In a straight channel, a true steady state can be achieved for ITP with appropriate countercurrent flow where stationary zones are formed, but the time it takes to reach the steady state is much longer than the without counter flow case. The numerical results indicate that a steady state cannot be reached in a dog-leg microchannel because of sample dispersion and refocusing at and near the intersections and at the branch channels. However, the elastic matching method can be used to determine the quasi-steady state in a dog-leg microchannel.     

Fabrication of Monolithic Silica in Microchannel as an Adsorbent for Preconcentration of VOCs

Abstract

Monolithic silica fabricated in microchannel by adding Methyltrimethoxysilane in starting composition of the sol used for preconcentration of volatile organic compounds was investigated in this study. Fabrication of monolithic silica in microchannel is difficult because of the shrinkage of monolithic silica. By adding Methyltrimethoxysilane in starting composition, the monolithic silica was successfully fabricated in a microchannel of a microchip. The developed microchip was used for preconcentration of VOCs followed by thermal desorption and GC/MS detection. It provides a good preconcentration method for developing an on-site VOCs monitoring micro total analysis system.     

Electroosmotic flow mixing in zigzag microchannels

In this study we performed numerical and experimental investigations into the mixing of EOFs in zigzag microchannels with two different corner geometries, namely sharp corners and flat corners. In the zigzag microchannel with sharp corners, the flow travels more rapidly near the inner wall of the corner than near the outer wall as a result of the higher electric potential drop. The resulting velocity gradient induces a racetrack effect, which enhances diffusion within the fluid and hence improves the mixing performance. The simulation results reveal that the mixing index is approximately 88.83%. However, the sharp-corner geometry causes residual liquid or bubbles to become trapped in the channel at the point where the flow is almost stationary, when the channel is in the process of cleaning. Accordingly, a zigzag microchannel with flat-corner geometry is developed. The flat-corner geometry forms a convergent-divergent type nozzle which not only enhances the mixing performance in the channel, but also prevents the accumulation of residual liquid or bubbles. Scaling analysis reveals that this corner geometry leads to an effective increase in the mixing length. The experimental results reveal that the mixing index is increased to 94.30% in the flat-corner zigzag channel. Hence, the results demonstrate that the mixing index of the flat-corner zigzag channel is better than that of the conventional sharp-corner microchannel. Finally, the results of Taguchi analysis indicate that the attainable mixing index is determined primarily by the number of corners in the microchannel and by the flow passing height at each corner.     

Effect of viscoelasticity on the flow pattern and the volumetric flow rate in electroosmotic flows through a microchannel

Many lab-on-a-chip based microsystems process biofluids such as blood and DNA solutions. These fluids are viscoelastic and show extraordinary flow behaviors, not existing in Newtonian fluids. Adopting appropriate constitutive equations these exotic flow behaviors can be modeled and predicted reasonably using various numerical methods. In the present paper, we investigate viscoelastic electroosmotic flows through a rectangular straight microchannel with and without pressure gradient. It is shown that the volumetric flow rates of viscoelastic fluids are significantly different from those of Newtonian fluids under the same external electric field and pressure gradient. Moreover, when pressure gradient is imposed on the microchannel there appear appreciable secondary flows in the viscoelastic fluids, which is never possible for Newtonian laminar flows through straight microchannels. The retarded or enhanced volumetric flow rates and secondary flows affect dispersion of solutes in the microchannel nontrivially.     

Ionic and mass transport in micro-nanofluidic devices: a matter of volumic surface charge

The shape and the surface charge of microchannels are critical parameters for ionic and mass transport in microfluidic systems. A great number of studies and developments have been carried out in order to optimize these features separately. We propose to consider them together within a new fundamental parameter for microfluidics, that we named the Volumic Surface Charge (VSC), which is the ratio of the surface charge to the section height in planar microchannels. The non-linear effects induced by rapid VSC variations can result in selective preconcentration processes, which can be used for a simultaneous preconcentration and separation of biomolecules within simple straight channels. In this review, we first present 3 different techniques that we developed to tune the VSC either by surface chemical patterning, integration of polarisable interfaces or geometrical constrictions. The proof of concept of the selective preconcentration using VSC variations will be presented on the basis of experimental results obtained with fluorescent probes and numerical simulations.     

Ionic separation efficiency of a novel electric-field-assisted membrane module comprising an array of microchannel units

The ionic separation efficiency of a novel membrane module comprising an array of microchannel units is analyzed. Under the Debye-Hückel approximation, we derive a semianalytical expression for the ionic separation efficiency. Analyses reveal that the effects of the size of the microchannel, the fixed charge density in the membrane layer, and the permittivity of the membrane layer on ionic separation efficiency depend strongly on the valence type of electrolyte in treated water. Under the condition of a symmetric electrolyte, the ionic separation efficiency is found to be about unity and unresponsive to variation of system parameters. If the valence of the cation is higher than that of the anion, the ionic separation efficiency is larger than unity, and decreases to unity as the size of the microchannel increases. In contrast, if the valence of the cation is lower than that of the anion, the ionic separation efficiency is smaller than unity and increases to unity as the size of the microchannel increases. Under the latter two conditions, the effects of both fixed charge density in the membrane layer and permittivity of the membrane layer on the ionic separation efficiency are found to be reversed.     

Highly productive droplet formation by anisotropic elongation of a thread flow in a microchannel

We developed a microfluidic device to form monodisperse droplets with high productivity by anisotropic elongation of a thread flow, defined as a threadlike flow of a dispersed liquid phase in a flow of an immiscible, continuous liquid phase. The thread flow was anisotropically elongated in the depth direction in a straight microchannel with a step, where the microchannel depth changed. Consequently, the elongated thread flow was given capillary instability (Rayleigh-Plateau instability) and was continuously transformed into monodisperse droplets at the downstream area of the step in the microchannel. We examined the effects of the flow rates of the dispersed phase and the continuous phase on the droplet formation behavior, including the droplet diameter and droplet formation frequency. The droplet diameter increased as the fraction of the dispersed-phase flow rate relative to the total flow rate increased and was independent of the total flow rate. The droplet formation frequency proportionally increased with the total flow rate at a constant dispersed-phase flow rate fraction. These results are explained in terms of a mechanism similar to that of droplet formation from a cylindrical liquid thread flow by Rayleigh-Plateau instability. The microfluidic device described was capable of forming monodisperse droplets with a 160-microm average diameter and 3-microm standard deviation at a droplet formation frequency of 350 droplets per second from a single thread flow. The highest total flow rate achieved was 6 mL/h using the present device composed of a straight microchannel with a step. We also demonstrated parallel droplet formation by anisotropic elongation of multiple thread flows; the process was applied to form W/O and O/W droplets. The highly productive droplet formation process presented in this study is expected to be useful for future industrial applications.     

Electrokinetically-driven flow mixing in microchannels with wavy surface

This paper investigates the mixing characteristics of electrokinetically-driven flow in microchannels with different wavy surface configurations. Numerical simulations are performed to analyze the influence of the wave amplitude and the length of the wavy section on the mixing efficiency within the microchannel. Typically, straight channels have a poor mixing performance because the fluid flow is restricted to the low Reynolds number regime, and hence mixing takes place primarily as a result of diffusion effects. However, the wavy surfaces employed in the current microchannels increase the interfacial contact area between the two species in the microchannel and therefore improve the mixing efficiency. The mixing performance is further enhanced by the application of a heterogeneous charge pattern on the wavy surfaces. The numerical results show that the heterogeneous charge pattern generates flow circulations near the microchannel walls. These circulations are shown to provide an effective enhancement in the mixing performance. Overall, the present results show that the mixing performance is improved by increasing the magnitude of the heterogeneous surface zeta potential upon the wavy surface or by increasing the wave amplitude or the length of the wavy section in the microchannel.     

Experimental and model investigation of the time-dependent 2-dimensional distribution of binding in a herringbone microchannel

A microfluidic device known to mix bulk solutions, the herringbone microchannel, was incorporated into a surface-binding assay to determine if the recirculation of solution altered the binding of a model protein (streptavidin) to the surface. Streptavidin solutions were pumped over surfaces functionalized with its ligand, biotin, and the binding of streptavidin to those surfaces was monitored using surface plasmon resonance imaging. Surface binding was compared between a straight microchannel and herringbone microchannels in which the chevrons were oriented with and against the flow direction. A 3-dimensional finite-element model of the surface binding reaction was developed for each of the geometries and showed strong qualitative agreement with the experimental results. Experimental and model results indicated that the forward and reverse herringbone microchannels substantially altered the distribution of protein binding (2-dimensional binding profile) as a function of time when compared to a straight microchannel. Over short distances (less than 1.5 mm) down the length of the microchannel, the model predicted no additional protein binding in the herringbone microchannel compared to the straight microchannel, consistent with previous findings in the literature.     

Experimental study of asphaltene deposition in transparent microchannels using the light absorption method

This study focuses on an experimental investigation of asphaltene deposition in a vertical transparent microchannel. Heptane-induced asphaltene precipitation is utilized to precipitate dissolved asphaltene in crude oil into asphaltene particles at ambient temperature and standard atmospheric pressure. These asphaltene particles deposit gradually on the surface of microchannels. The key parameters that influence the mechanism of asphaltene deposition are the ratio of crude oil to n-heptane and experimental elapsed time. At a constant flowrate, the amount of asphaltene deposited on a transparent channel wall is quantified using a new flow visualization technique based on reflected light intensity and image analysis. Asphaltene precipitation and deposition strongly affect the reflected light intensity through the change of mixture color in the recorded images. Experimental results show that asphaltene deposition process follows three stages, (i) slow asphaltene particle deposition at the beginning of the experiment, (ii) a rapid and continuous deposition occurring after few hours and (iii) a slower deposition (decreasing deposition rate) at the end of the experimentation. The experimental results for different crude oil to n-heptane ratios illustrate that deposition increases with this ratio, i.e. increasing concentration of n-heptane. An empirical equation is developed to correlate the intensity of the light absorption to the thickness of the deposited asphaltene in a transparent microchannel. Non-uniform deposition along the longitudinal direction of the microchannel is characterized. Deposits decrease with increasing longitudinal distance from the inlet. This non-uniform deposition distribution is due to local mass transport limitations and asphaltene aggregation size effect.     

Enzymatic degradation of p-chlorophenol in a two-phase flow microchannel system

Enzymatic degradation of p-chlorophenol was carried out in a two-phase flow in a microchannel (100 microm width, 25 microm depth) fabricated on a glass plate (70 mm x 38 mm). This is the first report on the enzymatic reaction in a two-phase flow on a microfluidic device. The surface of the microchannel was partially modified with octadecylsilane groups to be hydrophobic, thus allowing clear phase separation at the end-junction of the microchannel. The enzyme (laccase), which is surface active, was solubilized in a succinic aqueous buffer and the substrate (p-chlorophenol) was in isooctane. The degradation of p-chlorophenol occurred mainly at the aqueous-organic interface in the microchannel. We investigated the effects of flow velocity and microchannel shape on the enzymatic degradation of p-chlorophenol. Assuming that diffusion of the substrate (p-chlorophenol) is the rate-limiting step in the enzymatic degradation of p-chlorophenol in the microchannel, we proposed a simple theoretical model for the degradation in the microchannel. The calculated degradation values agreed well with the experimental data.     

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.     

Confocal microscopic evaluation of mixing performance for three-dimensional microfluidic mixer

We developed a confocal microscopic method for a quantitative evaluation of the mixing performance of a three-dimensional microfluidic mixer. We fabricated a microfluidic baker's transformation (MBT) mixer as a three-dimensional passive-type mixer for the efficient mixing of solutions. Although the MBT mixer is one type of ideal mixers, it is hard to evaluate its mixing performance, since the MBT mixer is based on several cycles of complicated three-dimensional microchannel structures. We applied the method developed here to evaluate the mixing of water and a fluorescein isothiocyanate (FITC; diffusion coefficient, 4.9 × 10(-10) m(2) s(-1)) solution by the MBT mixer. This method enables us to capture vertical section images for the fluid distributions of FITC and water at different three-dimensional microchannel structures of the MBT device. These images are in good agreement with those of mixing images based on numerical simulations. The mixing ratio could be calculated by the fluorescence intensity at each pixel of the vertical section image; complete mixing is recognized by a mixing ratio of more than 90%. The mixing ratios are measured at different cycles of the MBT mixer by changing the flow rate; the mixing performance is evaluated by comparisons with the mixing ratio of the straight microchannel without the MBT mixer.     

Patterning of a random copolymer of poly[lactide-co-glycotide-co-(epsilon-caprolactone)] by UV embossing for tissue engineering

The random copolymer, poly[lactide-co-glycotide-co-(epsilon-caprolactone)] (PLGACL) diacrylate was prepared by ring-opening polymerization of L-lactide, glycolide, and epsilon-caprolactone initiated with tetra(ethylene glycol). The diacrylated polymers were extensively characterized. With a UV embossing method, these copolymers were successfully fabricated into microchannels separated by microwalls with a high aspect (height/width) ratio. The PLGACL network films showed good cytocompatibility. Varieties of microstructures were fabricated, such as 10 x 40 x 60, 10 x 80 x 60, 25 x 40 x 60, or 25 x 80 x 60 microm(3) structures (microwall width x microchannel width x microwall height). The results demonstrated that smooth muscle cells (SMCs) can grow not only on the microchannel surfaces but also on the surfaces of the microwall and sidewall. The SMCs aligned along the 25 microm wide microwall with an elongated morphology and proliferated very slowly in comparison to those on the smooth surface with a longer cell-culture term. Few cells could attach and spread on the surface of the 40 microm wide microchannel, while the cells flourished on the 80 microm, or more than 80 microm, wide microchannel with a spindle morphology. The biophysical mechanism mediated by the micropattern geometry is discussed. Overall, the present micropattern, consisting of biodegradable and cytocompatible PLGACL, provides a promising scaffold for tissue engineering.     

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.     

10,000-fold concentration increase in proteins in a cascade microchip using anionic ITP by a 3-D numerical simulation with experimental results

This paper describes both the experimental application and 3-D numerical simulation of isotachophoresis (ITP) in a 3.2 cm long "cascade" poly(methyl methacrylate) (PMMA) microfluidic chip. The microchip includes 10 × reductions in both the width and depth of the microchannel, which decreases the overall cross-sectional area by a factor of 100 between the inlet (cathode) and outlet (anode). A 3-D numerical simulation of ITP is outlined and is a first example of an ITP simulation in three dimensions. The 3-D numerical simulation uses COMSOL Multiphysics v4.0a to concentrate two generic proteins and monitor protein migration through the microchannel. In performing an ITP simulation on this microchip platform, we observe an increase in concentration by over a factor of more than 10,000 due to the combination of ITP stacking and the reduction in cross-sectional area. Two fluorescent proteins, green fluorescent protein and R-phycoerythrin, were used to experimentally visualize ITP through the fabricated microfluidic chip. The initial concentration of each protein in the sample was 1.995 μg/mL and, after preconcentration by ITP, the final concentrations of the two fluorescent proteins were 32.57 ± 3.63 and 22.81 ± 4.61 mg/mL, respectively. Thus, experimentally the two fluorescent proteins were concentrated by over a factor of 10,000 and show good qualitative agreement with our simulation results.     

Focusing particles by induced charge electrokinetic flow in a microchannel

A novel method of sheathless particle focusing by induced charge electrokinetic flow in a microchannel is presented in this paper. By placing a pair of metal plates on the opposite walls of the channel and applying an electrical field, particle focusing is achieved due to the two pairs of vortex that constrain the flow of the particle solution. As an example, the trajectories of particles under different electrical fields with only one metal plate on one side channel wall were numerically simulated and experimentally validated. Other flow focusing effects, such as the focused width ratio (focused width/channel width) and length ratio (focused length/half‐length of metal plate) of the sample solution, were also numerically studied. The results show that the particle firstly passes through the gaps between the upstream vortices and the channel walls. Afterwards, the particle is focused to pass through the gap between the two downstream vortices that determine the focused particle position. Numerical simulations show that the focused particle stream becomes thin with the increases in the applied electrical field and the length of the metal plates. As regards to the focused length ratio of the focused stream, however, it slightly increases with the increase in the applied electrical field and almost keeps constant with the increase in the length of the metal plate. The size of the focused sample solution, therefore, can be easily adjusted by controlling the applied electrical field and the sizes of the metal plates.     

Effect of exposure dose on the replication fidelity and profile of very high aspect ratio microchannels in SU-8

We are interested in using SU-8 dense gratings with very high aspect ratio microchannels as the master mold for fabrication of child molds needed for replication. For such applications, the sidewall taper angle and mask replication fidelity of SU-8 are very important. Increasing the exposure time was experimentally observed to decrease the width of the microchannel and the sidewall angle of SU-8 bars. A new diffraction-refraction-reflection model was also developed. The calculated microchannel width and sidewall angle at high exposure dose agreed well with the experimentally observed values indicating that reflection at the silicon substrate was significant. The larger than calculated actual microchannel width for low exposure dose was shown to be due to leaching of unreacted SU-8 in the developer. Dense gratings of high aspect ratio SU-8 bars separated by high aspect ratio (19.1) microchannels were also demonstrated.     

A simplified method for capillary embedment into microfluidic devices - exemplified by sol-gel-based preconcentration

We here describe an alternative method of embedding functionalized capillaries into microdevices fabricated in PDMS. The capillaries have square-shaped outer dimensions and fit into elastic PDMS channel networks of similar dimensions. By modifying the capillary off-chip, the technique makes it possible to integrate a new chip function without risking contamination of already existing chemically patterned areas because of new reagent solutions. Leak-free insertion of these capillaries has earlier been reported, where a thin layer of uncured PDMS bonded the capillary to the microchannel and the lid structure. In this new approach, oxygen plasma is used to bond the square capillary to the PDMS, eliminating the risk of clogging the microsystem with uncured prepolymer. The new embedding technique was exemplified and evaluated by inserting a square capillary piece containing monolithic sol-gel for sample preconcentration application. The assembled microdevice was run with mass spectrometric detection, showing that peptides were preconcentrated without leakage from either the sol-gel itself or around the inserted capillary. Repeated preconcentration runs showed migration times better than 3% for all peptides. We believe that the presented microchip assembling technique greatly simplifies the insertion of functionalized capillary pieces, e.g., an initial preconcentrator to a PDMS device containing other downstream modules.