Reliable electrophoretic mobilities free from Joule heating effects using CE

Ionic electrophoretic mobilities determined by means of CE experiments are sometimes different when compared to generally accepted values based on limiting ionic conductance measurements. While the effect of ionic strength on electrophoretic mobility has been long understood, the increase in the mobility that results from Joule heating (the resistive heating that occurs when a current passes through an electrolyte) has been largely overlooked. In this work, a simple method for obtaining reliable and reproducible values of electrophoretic mobility is described. The electrophoretic mobility is measured over a range of driving powers and the extrapolation to zero power dissipation is employed to eliminate the effect of Joule heating. These extrapolated values of electrophoretic mobility can then be used to calculate limiting ionic mobilities by making a correction for ionic strength; this somewhat complicated calculation is conveniently performed by using the freeware program PeakMaster 5. These straightforward procedures improve the agreement between experimentally determined and literature values of limiting ionic mobility by at least one order of magnitude. Using Tris-chromate BGE with a value of conductivity 0.34 S/m and ionic strength 59 mM at a modest dissipated power per unit length of 2.0 W/m, values of mobility for inorganic anions were increased by an average of 12.6% relative to their values free from the effects of Joule heating. These increases were accompanied by a reduction in mobilities due to the ionic strength effect, which was 11% for univalent and 28% for divalent inorganic ions compared to their limiting ionic mobilities. Additionally, it was possible to determine the limiting ionic mobility for a number of aromatic anions by using PeakMaster 5 to perform an ionic strength correction. A major significance of this work is in being able to use CE to obtain reliable and accurate values of electrophoretic mobilities with all its benefits, including understanding and interpretation of physicochemical phenomena and the ability to model and simulate such phenomena accurately.     

Joule heating in electrokinetic flow

Electrokinetic flow is an efficient means to manipulate liquids and samples in lab-on-a-chip devices. It has a number of significant advantages over conventional pressure-driven flow. However, there exists inevitable Joule heating in electrokinetic flow, which is known to cause temperature variations in liquids and draw disturbances to electric, flow and concentration fields via temperature-dependent material properties. Therefore, both the throughput and the resolution of analytic studies performed in microfluidic devices are affected. This article reviews the recent progress on the topic of Joule heating and its effect in electrokinetic flow, particularly the theoretical and experimental accomplishments from the aspects of fluid mechanics and heat/mass transfer. The primary focus is placed on the temperature-induced flow variations and the accompanying phenomena at the whole channel or chip level.     

Local and transient structural changes in stratum corneum at high electric fields: contribution of Joule heating

Electroporation of skin is accompanied by local heating, such that thermally induced structural changes of the stratum corneum (SC) accompany the field effect. Comparing on the time scale, the local changes in structure, temperature and conductance of the SC, during and after the pulse, it is seen that Joule heating also facilitates the subsequent molecular transport. It is found that the transport of medium-sized, ionic molecules occurs through localized transport regions (LTR). The size of a LTR increases with the pulse length, whereas the density of the LTRs increases with increasing voltage, for instance at U(SC=)80 V, the LTR cover approximately 0.02--1% of the surface area. The state of low resistance within the LTR is long-lived. During high voltage application, the center of the LTR is heated above the phase transition temperature of the SC lipids (70 degrees C) and the heat front propagates outwards. Inside the SC, the pulse causes aggregates of small-sized vesicles. At a higher temperature, the aggregate formation and their disappearance are delayed. Multiple pulses with the applied voltage of U(appl)=80 V induce the formation of long-lasting vesicle aggregates with a diameter of slashed circle=1--30 microm, covering 0.05--0.5% of the total sample area. The electric energy dissipated within the LTR during high voltage application is apparently sufficient to raise the temperature well above the phase transition temperature of the lipids of the SC, accounting for the conformational changes from the multi-lamella to the vesicular structures.     

Effect of Joule heating on electrokinetic transport

The Joule heating (JH) is a ubiquitous phenomenon in electrokinetic flow due to the presence of electrical potential gradient and electrical current. JH may become pronounced for applications with high electrical potential gradients or with high ionic concentration buffer solutions. In this review, an in-depth look at the effect of JH on electrokinetic processes is provided. Theoretical modeling of EOF and electrophoresis (EP) with the presence of JH is presented and the important findings from the previous studies are examined. A numerical study of a fused-silica capillary PCR reactor powered by JH is also presented to extend the discussion of favorable usage of JH.     

Joule heating in packed capillaries used in capillary electrochromatography

Effective heat dissipation is critical for reproducible and efficient separations in electrically driven separation systems. Flow rate, retention kinetics, and analyte diffusion rates are some of the characteristics that are affected by variation in the temperature of the mobile phase inside the column. In this study, we examine the issue of Joule heating in packed capillary columns used in capillary electrochromatography (CEC). As almost all commonly used CEC packings are poor thermal conductors, it is assumed that the packing particles do not conduct heat and heat transfer is solely through the mobile phase flowing through the system. The electrical conductivity of various mobile phases was measured at different temperatures by a conductivity meter and the temperature coefficient for each mobile phase was calculated. This was followed by measurement of the electrical current at several applied voltages to calculate the conductivity of the solution within the column as a function of the applied voltage. An overall increase in the conductivity is attributed to Joule heating within the column, while a constant conductivity means good heat dissipation. A plot of conductivity versus applied voltage was used as the indicator of poor heat dissipation. Using theories that have been proposed earlier for modeling of Joule heating effects in capillary electrophoresis (CE), we estimated the temperature within CEC columns. Under mobile and stationary phase conditions typically used in CEC, heat dissipation was found to be not always efficient. Elevated temperatures within the columns in excess of 23 degrees C above ambient temperature were calculated for packed columns, and about 35 degrees C for an open column, under a given set of conditions. The results agree with recently published experimental findings with nuclear magnetic resonance (NMR) thermometry, and Raman spectroscopic measurements.     

Quantification and evaluation of Joule heating in on-chip capillary electrophoresis

We present the use of a novel, picoliter volume interferometer to measure, for the first time, the extent of Joule heating in chip-scale capillary electrophoresis (CE). The simple optical configuration for the on-chip interferometric backscatter detector (OCIBD) consists of an unfocused laser, an unaltered silica chip with a half-cylinder channel and a photodetector. Using OCIBD for millidegree-level noninvasive thermometry, temperature changes associated with Joule heating (2.81 degrees C above ambient) in on-chip CE have been observed in 90 microm wide and 40 microm deep separation channels. The temporal response of Joule heating in isotropically etched channels was exponential, with it taking an excess of 2.7 s to reach equilibrium. Buffer viscosity changes have also been derived from empirical on-chip thermometry data, allowing for the determination of diffusion coefficients for solutes when separated in heated buffers. In addition, OCIBD has allowed the reduction in separation efficiency to be estimated in the absence of laminar flow and due to increased molecular diffusion and lower buffer viscosity. A 7% reduction in separation efficiency was determined for a high current drawing buffer such as Tris-boric acid under an applied field of just 400 V/cm. Results indicate that heating effects in on-chip CE have been underestimated and there is a need to readdress the theoretical model.     

Numerical modeling of the Joule heating effect on electrokinetic flow focusing

In electrokinetically driven microfluidic systems, the driving voltage applied during operation tends to induce a Joule heating effect in the buffer solution. This heat source alters the solution's characteristics and changes both the electrical potential field and the velocity field during the transport process. This study performs a series of numerical simulations to investigate the Joule heating effect and analyzes its influence on the electrokinetic focusing performance. The results indicate that the Joule heating effect causes the diffusion coefficient of the sample to increase, the potential distribution to change, and the flow velocity field to adopt a nonuniform profile. These variations are particularly pronounced under tighter focusing conditions and at higher applied electrical intensities. In numerical investigations, it is found that the focused bandwidth broadens because thermal diffusion effect is enhanced by Joule heating. The variation in the potential distribution induces a nonuniform flow field and causes the focused bandwidth to tighten and broaden alternately as a result of the convex and concave velocity flow profiles, respectively. The present results confirm that the Joule heating effect exerts a considerable influence on the electrokinetic focusing ratio.     

The role of Joule heating in dispersive mixing effects in electrophoretic cells: hydrodynamic considerations

The analysis described in this contribution is focused on the effect of Joule heating generation on the hydrodynamics of batch electrophoretic cells (i.e., cells that do not display a forced convective term in the motion equation). The hydrodynamics of these cells is controlled by the viscous forces and by the buoyancy force caused by the temperature gradients due to the Joule heating generation. The analysis is based on differential models that lead to analytical and/or asymptotic solutions for the temperature and velocity profiles of the cell. The results are useful in determining the characteristics of the temperature and velocity profiles inside the cell. Furthermore, the results are excellent tools to be used in the analysis of the dispersive-mixing of solute when Joule heating generation must be accounted for. The analysis is performed by identifying two sequentially coupled problems. Thus, the "carrier fluid problem" and the "solute problem" are outlined. The former is associated with all the factors affecting the velocity profile and the latter is related to the convective-diffusion aspects that control the spreading of the solute inside the cell. The analysis of this contribution is centered on the discussion of the "carrier fluid problem" only. For the boundary conditions selected in the contribution, the study leads to the derivation of an analytical temperature and a "universal" velocity profile that feature the Joule heating number. The Grashof number is a scaling factor of the actual velocity profile. Several characteristics of these profiles are studied and some numerical illustrations have been included.     

Role of Joule heating in dispersive mixing effects in electrophoretic cells: convective-diffusive transport aspects

This contribution addresses the problem of solute dispersion in a free convection electrophoretic cell for the batch mode of operation, caused by the Joule heating generation. The problem is analyzed by using the two-problem approach originally proposed by Bosse and Arce (Electrophoresis 2000, 21, 1018-1025). The approach identifies the carrier fluid problem and the solute problem. This contribution is focused on the latter. The strategy uses a sequential coupling between the energy, momentum and mass conservation equations and, based on geometrical and physical assumptions for the system, leads to the derivation of analytical temperature and velocity profiles inside the cell. These results are subsequently used in the derivation of the effective dispersion coefficient for the cell by using the method of area averaging. The result shows the first design equation that relates the Joule heating effect directly to the solute dispersion in the cell. Some illustrative results are presented and discussed and their implication to the operation and design of the device is addressed. Due to the assumptions made, the equation may be viewed as an upper boundary for applications such as free flow electrophoresis.     

Accelerated SDS depletion from proteins by transmembrane electrophoresis: Impacts of Joule heating

SDS plays a key role in proteomics workflows, including protein extraction, solubilization and mass‐based separations (e.g. SDS‐PAGE, GELFrEE). However, SDS interferes with mass spectrometry and so it must be removed prior to analysis. We recently introduced an electrophoretic platform, termed transmembrane electrophoresis (TME), enabling extensive depletion of SDS from proteins in solution with exceptional protein yields. However, our prior TME runs required 1 h to complete, being limited by Joule heating which causes protein aggregation at higher operating currents. Here, we demonstrate effective strategies to maintain lower TME sample temperatures, permitting accelerated SDS depletion. Among these strategies, the use of a magnetic stir bar to continuously agitate a model protein system (BSA) allows SDS to be depleted below 100 ppm (>98% removal) within 10 min of TME operations, while maintaining exceptional protein recovery (>95%). Moreover, these modifications allow TME to operate without any user intervention, improving throughput and robustness of the approach. Through fits of our time‐course SDS depletion curves to an exponential model, we calculate SDS depletion half‐lives as low as 1.2 min. This promising electrophoretic platform should provide proteomics researchers with an effective purification strategy to enable MS characterization of SDS‐containing proteins.     

Analytical study of Joule heating effects on electrokinetic transportation in capillary electrophoresis

Electric fields are often used to transport fluids (by electroosmosis) and separate charged samples (by electrophoresis) in microfluidic devices. However, there exists inevitable Joule heating when electric currents are passing through electrolyte solutions. Joule heating not only increases the fluid temperature, but also produces temperature gradients in cross-stream and axial directions. These temperature effects make fluid properties non-uniform, and hence alter the applied electric potential field and the flow field. The mass species transport is also influenced. In this paper we develop an analytical model to study Joule heating effects on the transport of heat, electricity, momentum and mass species in capillary-based electrophoresis. Close-form formulae are derived for the temperature, applied electrical potential, velocity, and pressure fields at steady state, and the transient concentration field as well. Also available are the compact formulae for the electric current and the volume flow rate through the capillary. It is shown that, due to the thermal end effect, sharp temperature drops appear close to capillary ends, where sharp rises of electric field are required to meet the current continuity. In order to satisfy the mass continuity, pressure gradients have to be induced along the capillary. The resultant curved fluid velocity profile and the increase of molecular diffusion both contribute to the dispersion of samples. However, Joule heating effects enhance the sample transport velocity, reducing the analysis time in capillary electrophoretic separations.     

Precise temperature control in microfluidic devices using Joule heating of ionic liquids

Microfluidic devices for spatially localised heating of microchannel environments were designed, fabricated and tested. The devices are simple to implement, do not require complex manufacturing steps and enable intra-channel temperature control to within +/-0.2 degrees C. Ionic liquids held in co-running channels are Joule heated with an a.c. current. The nature of the devices means that the internal temperature can be directly assessed in a facile manner.     

Joule heating and heat transfer in poly(dimethylsiloxane) microfluidic systems

Joule heating is a significant problem in electrokinetically driven microfluidic chips, particularly polymeric systems where low thermal conductivities amplify the difficulty in rejecting this internally generated heat. In this work, a combined experimental (using a microscale thermometry technique) and numerical (using a 3D "whole-chip" finite element model) approach is used to examine Joule heating and heat transfer at a microchannel intersection in poly(dimethylsiloxane)(PDMS), and hybrid PDMS/Glass microfluidic systems. In general the numerical predictions and the experimental results agree quite well (typically within +/- 3 degree C), both showing dramatic temperature gradients at the intersection. At high potential field strengths a nearly five fold increase in the maximum buffer temperature was observed in the PDMS/PDMS chips over the PDMS/Glass systems. The detailed numerical analysis revealed that the vast majority of steady state heat rejection is through lower substrate of the chip, which was significantly impeded in the former case by the lower thermal conductivity PDMS substrate. The observed higher buffer temperature also lead to a number of significant secondary effects including a near doubling of the volume flow rate. Simple guidelines are proposed for improving polymeric chip design and thereby extend the capabilities of these microfluidic systems.     

Theoretical and numerical analysis of temperature gradient focusing via Joule heating

We present a detailed theoretical and numerical analysis of temperature gradient focusing (TGF) via Joule heating-an analytical species concentration and separation technique relying upon the dependence of an analyte's velocity on temperature due to the temperature dependence of a buffer's ionic strength and viscosity. The governing transport equations are presented, analyzed, and implemented into a quasi-1D numerical model to predict the resulting temperature, velocity, and concentration profiles along a microchannel of varying width under an applied electric field. Numerical results show good agreement with experimental trials presented in previous work. The model is used to analyze the effects of varying certain geometrical and experimental parameters on the focusing performance of the device. Simulations also help depict the separation capability of the device, as well as the effectiveness of different buffer systems used in the technique. The analysis provides rule-of-thumb methodology for implementation of TGF into analytical systems, as well as a fundamental model applicable to any lab-on-a-chip system in which Joule heating and temperature-dependent electrokinetic transport are to be analyzed.     

Joule heating influence on the vitality of fungi in pulsed magnetic fields during magnetic permeabilization

Generation of the pulsed magnetic fields that are 5–6 orders of magnitude higher than the geomagnetic field requires switching of high pulsed currents. As a result, the occurrence of the Joule heating in the inductors limits the possible biological applications of the pulsed magnetic fields. This work is focused on the investigation of the generated Joule heating inside the inductors of different shapes. The analysis of the Joule heating influence on the vitality of biological objects during magnetic permeabilization is presented. The biological objects that are used in the study are the pathogenic fungi Candida albicans and Trichophyton rubrum, which are the common cases for human infections. The finite element method analysis of the pulsed inductors and the experimental results with the selected pathogenic fungi are overviewed. The limitations of the magnetic permeabilization technique due to the generated Joule heating are identified.     

In-line application of electric field in capillary separation systems: Joule heating, pH and conductivity

This study concerns the technique electric field-assisted capillary liquid chromatography. In this technique, an electric field is applied over the separation capillary in order to provide an additional selectivity. In this technique, the electric field is applied in-line in the separation capillary and here the electric current is the factor limiting the magnitude of applied electric field. The influence of Joule heating and other factors on the current in such systems has been investigated. The temperature in the capillary was first measured within a standard CE set-up, as function of effect per unit of length. Then the same cooling system was applied to an in-line set-up, to replicate the conditions between the two systems, and thus the temperature. Thus Joule heating effects could then be calculated within the in-line system. It was found that for systems applying an electric field in line, the direct influence from Joule heating was only relatively small. The pH in the capillary was measured in the in-line set-up using cresol red/TRIS solutions as pH probe. Significant changes in pH were observed and the results suggested that electrolysis of water is the dominant electrode reaction in the in-line system. In summary, the observed conductivity change in in-line systems was found to be mainly due to the pH change by hydrolysis of water, but primarily not due the temperature change in the capillary column.     

Joule heating and determination of temperature in capillary electrophoresis and capillary electrochromatography columns

This article reviews the progress that has taken place in the past decade on the topic of estimation of Joule heating and temperature inside an open or packed capillary in electro-driven separation techniques of capillary electrophoresis (CE) and capillary electrochromatography (CEC), respectively. Developments in theoretical modeling of the heat transfer in the capillary systems have focused on attempts to apply the existing models on newer techniques such as CEC and chip-based CE. However, the advent of novel analytical tools such as pulsed magnetic field gradient nuclear magnetic resonance (NMR), NMR thermometry, and Raman spectroscopy, have led to a revolution in the area of experimental estimation of Joule heating and temperature inside the capillary via the various noninvasive techniques. This review attempts to capture the major findings that have been reported in the past decade.     

Estimation of Joule heating effect on temperature and pressure distribution in electrokinetic-driven microchannel flows

In this study we present simple analytical models that predict the temperature and pressure variations in electrokinetic-driven microchannel flow under the Joule heating effect. For temperature prediction, a simple model shows that the temperature is related to the Joule heating parameter, autothermal Joule heating parameter, external cooling parameter, Peclet number, and the channel length to channel hydraulic diameter ratio. The simple model overpredicted the thermally developed temperature compared with the full numerical simulation, but in good agreement with the experimental measurements. The factors that affect the external cooling parameters, such as the heat transfer coefficient, channel configuration, and channel material are also examined based on this simple model. Based on the mass conservation, a simple model is developed that predicts the pressure variations, including the temperature effect. An adverse pressure gradient is required to satisfy the mass conservation requirement. The temperature effect on the pressure gradient is via the temperature-dependent fluid viscosity and electroosmotic velocity.