Investigation of heterogeneous electrochemical processes using multi-stream laminar flow in a microchannel

A multi-component microfluidic electrochemical cell is shown to be a useful analytical tool for probing complex coupled processes in electrolytic systems. We recently reported an enzymatic signal amplification phenomenon that may provide increased sensitivity when detecting bio-analytes (M. S. Hasenbank, E. Fu and P. Yager, Langmuir, 2006, 22, 7451-7453), but to fully harness this method requires an improved understanding of the underlying electrochemical and chemical processes. We use spatial control of electrolyte streams on patterned conductive substrates in a microfluidic platform to elucidate the coupling of homogeneous chemical steps to heterogeneous electrochemical charge transfer processes. Because the gold surface was observable using SPR imaging, electrochemical phenomena could be monitored optically in real time. Based on these and additional results, we propose a mechanism for the novel amplification phenomenon that involves direct electron transfer between surface-immobilized enzyme molecules and the gold surface. This improved understanding of the underlying mechanism should enable the future implementation of this phenomenon in signal amplification schemes for highly sensitive lab-on-a-chip biosensors.     

Specific molecule localization in microchannel laminar flow and its application for non-immobilized-probe analysis

Microfluidic systems enable superior control of fluidics. We have developed a novel size-separation method utilizing secondary flow within a microchannel. Using confocal fluorescence microscopy and computer simulation, we confirmed that separation occurred as a result of specific molecular localization in the curving part of the microchannel. Maximum separation efficiency was achieved by optimizing microchannel design and flow rate for individual separation targets. In addition, more effective separation was achieved by use of plural microchannel curves. This method was used for sequence-selective DNA sensing. Double-stranded DNA formed by hybridization between target DNA and a complementary probe had different elution profiles from those of the single-stranded non-complementary sequence. Moreover, the response depends on the length of the DNA molecules. This method does not require immobilization of either probe or target DNA, because all reactions occurred in the solution phase. Such features may reduce experimental error and the difference between data from different operators.     

Glass microchip with three-dimensional microchannel network for 2 x 2 parallel synthesis

An integrated multireactor system for 2 x 2 parallel organic synthesis has been developed on a single glass microchip. Three-dimensional channel circuits in the chip were fabricated by laminating three glass plate layers. The fabrication method is a straightforward extension of the conventional one, and topological equivalence for any three-dimensional circuits can be constructed easily with it. 2 x 2 phase-transfer amide formation reactions, which constitute a simple model for combinatorial synthesis, were successfully carried out on the microchip, and the integrity of the three-dimensional circuits was confirmed. Combinatorial chemistry with multi-microreactors, in conjunction with a high-throughput screening method based on micro-TAS technologies, is expected to provide an efficient tool for drug discovery.     

Frequency-dependent laminar electroosmotic flow in a closed-end rectangular microchannel

This article presents an analysis of the frequency- and time-dependent electroosmotic flow in a closed-end rectangular microchannel. An exact solution to the modified Navier-Stokes equation governing the ac electroosmotic flow field is obtained by using the Green's function formulation in combination with a complex variable approach. An analytical expression for the induced backpressure gradient is derived. With the Debye-Hückel approximation, the electrical double-layer potential distribution in the channel is obtained by analytically solving the linearized two-dimensional Poisson-Boltzmann equation. Since the counterparts of the flow rate and the electrical current are shown to be linearly proportional to the applied electric field and the pressure gradient, Onsager's principle of reciprocity is demonstrated for transient and ac electroosmotic flows. The time evolution of the electroosmotic flow and the effect of a frequency-dependent ac electric field on the oscillating electroosmotic flow in a closed-end rectangular microchannel are examined. Specifically, the induced pressure gradient is analyzed under effects of the channel dimension and the frequency of electric field. In addition, based on the Stokes second problem, the solution of the slip velocity approximation is presented for comparison with the results obtained from the analytical scheme developed in this study.     

Compact model for multi-phase liquid-liquid flows in micro-fluidic devices

We present a compact model describing the laminar flow of viscous multiphase fluids in micro-channel networks. We apply this model to the flow of 2 immiscible fluids representing typically oil and water, in a network of micro-channels comprising one inlet for each fluid splitting into 2 branches meeting at a T-junction, where the 2 phases are combined before exiting the network through two outlets. This network is akin to an electrical "Wheatstone bridge" and represents a simplified interdigital micro-reactor, where the fluids to be mixed are separated into smaller branches and later re-combined together. We show from an analytical solution and a computational modelling that fluid flow inside this network is very sensitive to small differences in fluid resistance between the various branches of the network, which may lead to catastrophic error in fluid distribution between the various branches that can have a profound effect on mixing. These errors depend on the viscosity difference between the fluids, on the processing conditions, and also on the geometric resistance parameters of the various channels. Increasing the resistance of the distribution channels upstream of the fluid junctions allows minimisation of the distribution errors. Interaction between the fluids can also lead to transients that are orders of magnitude longer than the flooding time of the channels. This may be exploited to provide impedance-like terms in flui-logic operations.     

Localized chemical stimulation to micropatterned cells using multiple laminar fluid flows

Micropatterns of the electrically conjugating cardiomyocytes were prepared on a single cell level by microcontact printing (microCP), and the localized chemical stimulations were applied to the cellular pattern using multiple laminar flows. The locally delivered 1-octanol inactivated part of the myocyte patterns, while the other areas retained the activity showing spontaneous and synchronous pulsatility. Since both the cells and flows were well defined as micropatterns and each integrated on a chip, the obtained results simply demonstrate the cellular responses in a single-cell network.     

Mixing and reaction fronts in laminar flows

Autocatalytic reaction fronts between unreacted and reacted mixtures in the absence of fluid flow propagate as solitary waves. In the presence of imposed flow, the interplay between diffusion and advection enhances the mixing, leading to Taylor hydrodynamic dispersion. We present asymptotic theories in the two limits of small and large Thiele modulus (slow and fast reaction kinetics, respectively) that incorporate flow, diffusion, and reaction. For the first case, we show that the problem can be handled to leading order by the introduction of the Taylor dispersion replacing the molecular diffusion coefficient by its Taylor counterpart. In the second case, the leading-order behavior satisfies the eikonal equation. Numerical simulations using a lattice gas model show good agreement with the theory. The Taylor model is relevant to microfluidics applications, whereas the eikonal model applies at larger length scales.     

Droplet formation in a microchannel network

A method is given for generating droplets in a microchannel network. With oil as the continuous phase and water as the dispersed phase, pico/nanoliter-sized water droplets can be generated in a continuous phase flow at a -junction. The channel for the dispersed phase is 100 microm wide and 100 microm deep, whereas the channel for the continuous phase is 500 microm wide and 100 microm deep. For given experimental parameters, regular-sized droplets are reproducibly formed at a uniform speed. The diameter of these droplets is controllable in the range from 100-380 microm as the flow velocity of the continuous phase is varied from 0.01 m s(-1) to 0.15 m s(-1).     

Fabrication of complex three-dimensional microchannel systems in PDMS

This paper describes a method for fabricating three-dimensional (3D) microfluidic channel systems in poly(dimethylsiloxane) (PDMS) with complex topologies and geometries that include a knot, a spiral channel, a "basketweave" of channels, a chaotic advective mixer, a system with "braided" channels, and a 3D grid of channels. Pseudo-3D channels, which are topologically equivalent to planar channels, are generated by bending corresponding planar channels in PDMS out of the plane into 3D shapes. True 3D channel systems are formed on the basis of the strategy of decomposing these complex networks into substructures that are planar or pseudo-3D. A methodology is developed that connects these planar and/or pseudo-3D structures to generate PDMS channel systems with the original 3D geometry. This technique of joining separate channel structures can also be used to create channel systems in PDMS over large areas by connecting features on different substrates. The channels can be used as templates to form 3D structures in other materials.     

Membraneless microseparation by asymmetry in curvilinear laminar flows

Membraneless microseparation by asymmetric inertial migration is studied in curvilinear laminar flows and evidence of the microseparation is presented. Along a curvilinear laminar flow, transverse particle migration involves competition between three shear-flow effects; the tubular pinch effect, centrifugal force, and Dean's vortex. Equilibrating control of migration allows for particle separation to different outlets. No filter-media or external force is necessary for the microseparation utilizing only shear-flow characteristics. A double-spiral design effectively controls the migration to optimize microseparation. The concentration ratio of 10 microm beads from the two different outlets was 660 times at 92 mm/s of flow velocity. This new technology has great potential for high-throughput and low cost in bio-agent and particulate separation at both macro and micro scales.     

Electro-osmotic flows in a microchannel with patterned hydrodynamic slip walls

We present an analysis of the electro-osmotic flow of electrolytic solutions in a microchannel with patterned hydrodynamic slippage on channel walls. A set of governing equations is formulated to account for the effects of small variations in hydrodynamic slippage over the microchannel walls on the electro-osmotic flow. These equations are then solved analytically by using the perturbation method. Two frequently encountered surface patterns, (i) cosine wave variation and (ii) square wave variation in slip length, are considered in our analyses. The results show that patterned slippage over microchannel walls can induce complex flow patterns (such as vortical flows) in otherwise plug-like electro-osmotic flows, which suggests potential applications of such flows in microfluidic mixers.     

Entropy generation analysis in a microchannel Poiseuille flows of nanofluid with nanoparticles injection and variable properties

Journal of Thermal Analysis and Calorimetry - In this study, a more realistic, modified Buongiorno’s nanofluid model is suggested and used to examine the impact of nanoparticle injection and...     

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.     

The change of activation energy in microchannel laminar flow as demonstrated by kinetic analysis of the DNA duplex-coil equilibrium

This paper presents the capability of changing the activation energy of chemical reactions using microchannel laminar flow. Kinetic parameters of the duplex-coil equilibrium of DNA oligomers were studied by measuring the hysteresis between denaturation-renaturation curves using an in-house temperature-controllable microchannel-type flow cell. For this study, DNA oligomers were used because they allow physicochemical analysis and theoretical discussion. Kinetic parameters of the duplex-coil equilibrium of DNA oligomers were obtained by measuring the denaturation-renaturation hysteresis curves. Both cooling and heating curves were shifted to the high-temperature side at higher flow rates. The renaturation reaction was influenced by a slower flow rate. The effect of the slower flow rate was more pronounced for renaturation than denaturation reactions. The magnitude of the activation energies of association decreased as the flow rate increased, but that of the activation energies of the dissociation increased as the flow rate increased. Overall, these results suggest that chemical reactions' change of activation energy depends on the flow rate and the DNA molecular size.     

Off-line integration of CE and MALDI-MS using a closed-open-closed microchannel system

In this work, a new technique for off-line hyphenation between CE and MALDI-MS is presented. Two closed fused-silica capillaries were connected via a silicon chip comprising an open microcanal. The EOF in the system was evaluated using mesityloxide or leucine-enkephalin as a sample and with a running buffer that rendered the analyte neutrally charged. Comparison was made between the EOF in a closed system (first capillary solely included in the electrical circuit) and in a closed-open system (first capillary and microcanal included in the electrical circuit). It was concluded that the experimental values of the EOF agreed with the theory. The influence of the capillary outer diameter on the peak dispersion was investigated using a closed-open-closed system (first capillary, microcanal and second capillary included in the electrical circuit). It was clearly seen that a capillary with 375 microm od induced considerably higher peak dispersion than a 150 microm od capillary, due to a larger liquid dead volume in the connection between the first capillary outlet and the microcanal. Mass spectrometric analysis has also been performed following CE separation runs in a closed-open-closed system with cytochrome c and lysozyme as model proteins. It was demonstrated that a signal distribution profile of the separated analytes could be recorded over a 30 mm long microcanal.     

Inertial deposition of aerosol particles from laminar flows in fibrous filters

The deposition of aerosol particles onto filter fibers under the effect of inertial forces is studied in a wide range of Stokes numbers (St) at Reynolds numbers close to unity (Re ∼ 1). Coefficients η of the capture of inertial particles with finite sizes in model filters composed of parallel rows of identical parallel fibers located normal to the direction of a flow are determined based on the numerical solution of the Navier-Stokes and particle motion equations. It is shown that, at Re < 1 and a constant particle-to-fiber radius ratio, R = r _p/a, number St uniquely characterizes capture coefficients η for particles with different densities, while, at Re ≥ 1, the capture coefficient depends on both St and Re. At constant R and St values, the larger Re the higher the capture coefficient. The influence of the structure of the model filter on pressure drop Δp and η is investigated. A nonuniform arrangement of fibers in rows is shown to increase the Δp/U ratio at lower Re values and to make the η -St dependence more pronounced than that for systems of uniformly ordered fibers. The results of calculations agree with the experimental data.     

Radial basis function interpolation supplemented lattice Boltzmann method for electroosmotic flows in microchannel

Large gradients of physical variables near the channel walls are characteristic of EOF. The previous numerical simulations of EOFs with the lattice Boltzmann method (LBM) utilize uniform lattice and are not efficient, especially when the electric double layer (EDL) thickness is significantly smaller than the channel height. The efficient LBM simulation of EOF in microchannel calls for a nonuniform mesh which is dense in the EDL region and sparse in the bulk region. In this article, we formulate a radial basis function (RBF)-based interpolation supplemented LBM (ISLBM) to solve the governing equations of EOF, that is, the Poisson, Nernst–Planck, and Navier–Stokes equations, in a nonuniform mesh system. Unlike the conventional ISLBM, the RBF-ISLBM determines the prestreaming distribution functions by using the local RBF-based interpolation over circular supporting regions and is particularly suitable for nonuniform meshes. The RBF-ISLBM is validated by the EOFs in infinitely long and finitely long microchannels. The results show that the RBF-ISLBM possesses excellent robustness and accuracy. Finally, we use the RBF-ISLBM to simulate the EOFs with the hitherto highest electrokinetic parameter, κa, defined by the ratio of channel height a to EDL thickness κ⁻¹, in LBM simulations of EOF.