Electroosmotic Flow Pump Research Articles

Electrokinetic control of fluid transport in gold-coated nanocapillary array membranes in hybrid nanofluidic–microfluidic devices

The introduction of metallic elements into microfluidic devices that support electrokinetic transport creates several fundamental issues relative to the high conductivity of the metal, which can act as a current shunt, causing profound effects on the transport process. Here we examine the use of Au-coated nanocapillary array membranes (Au NCAMs) as electrically addressable fluid control elements in multi-layer microfluidic architectures. Three alternative methods for fluid injection across Au NCAMs are presented: electrokinetic injection across NCAMs with Au coated on one side (asymmetric NCAM), electrokinetic injection across NCAMs with an embedded Au layer (symmetric NCAM), and field-free electroosmotic flow (EOF) pumping across either type of Au NCAM. Injection efficiency across asymmetric NCAMs depends on the orientation of the asymmetric membrane relative to the driving potential. Efficient injections are enabled when the Au coating is on the receiving side of the membrane, however, some distortion of the injected volume element is observed, especially with large injection potentials. These results for asymmetric membranes agree qualitatively with two-dimensional numerical simulations of injections across a single slit pore, which suggest that the direction-selective transport behavior is related to electrophoretic transport of the anionic fluorescein probe. Reproducible, high quality injections are also achieved in symmetric Au NCAMs having an embedded gold nanoband region within the nanopores. Nanoband Au NCAMs are excellent candidates for a range of applications, including high efficiency electrochemical sensing, electrochemically catalyzed conversion or pretreatment and label free sensing utilizing extraordinary optical transmission. EOF pumping could be an alternative to electrokinetic injections in some applications, however, this approach is only useful for relatively large pore sizes (>400 nm) and presents considerably worse sample spreading via Taylor dispersion.

In-line coupling of two-phase single drop microextraction and large volume stacking using an electroosmotic flow pump in nonaqueous capillary electrophoresis

In order to improve the concentration sensitivity of capillary electrophoresis (CE), two sample preconcentration techniques, single drop microextraction (SDME) and large volume stacking using an electroosmotic flow pump (LVSEP), were coupled in-line in a commercial CE instrument. By simple programming of liquid handling sequences, a pentanol drop was prepared at the tip of a fused silica capillary over which a Teflon tube had been sleeved to serve as a hydrophobic support. After extraction of the analytes from an aqueous donor solution into the drop, the entire capillary column was filled with enriched pentanol extract. LVSEP, in which the sample matrix is automatically removed by the EOF, was then carried out using a methanolic run buffer. The overall enrichment factors for the analytes pentachlorophenol (PCP), 3-bromobenzoic acid (3-BBA), and 4-iodobenzoic acid (4-IBA), from a combination of 30 min SDME and LVSEP on a 27 cm capillary, were about 7000, even without agitation of the donor solution. The resulting limits of detection for PCP, 3-BBA, and 4-IBA were 0.7, 0.3 and 0.7 nM, respectively. Since no modification of the existing CE instrument is necessary and a bare capillary is used for LVSEP, this scheme can be adapted quite easily for many CE applications that require high concentration sensitivity.

Determination of nerve agent degradation products by capillary electrophoresis using field-amplified sample stacking injection with the electroosmotic flow pump and contactless conductivity detection

In the present study, field-amplified sample stacking injection using the electroosmotic flow pump (FAEP) was developed for the capillary electrophoretic separation of the four nerve agent degradation products methylphosphonic acid (MPA), ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA) and cyclohexyl methylphosphonic acid (CMPA). Coupled to contactless conductivity detection, direct quantification of these non-UV active compounds could be achieved. Sensitivity enhancement of up to 500 to 750-fold could be obtained. The newly established approach was applied to the determination of the analytes in river water and aqueous extracts of soil. Detection limits of 0.5, 0.7, 1.4 and 2.7 ng/mL were obtained for MPA, EMPA, IMPA and CMPA, respectively, in river water and 0.09, 0.14, 0.44 and 0.22 μg/g, respectively, in soil.

Combination of off-line solid-phase extraction and on-column sample stacking for sensitive determination of parabens and p-hydroxybenzoic acid in waters by non-aqueous capillary electrophoresis

For the first time, a procedure based on solid-phase extraction (SPE) for the simultaneous extraction of a group of parabens (methyl, ethyl, propyl, butyl and benzyl p-hydroxybenzoates) and p-hydroxybenzoic acid (PHBA), from environmental water samples has been developed. Analysis of the extracts was performed by non-aqueous capillary electrophoresis (NACE) coupled with diode array detection (DAD), using large-volume sample stacking (LVSS) based on the electroosmotic flow pump as on-column preconcentration technique. Several water samples, such as tap, river, and wastewater samples, were analyzed using both SPE–NACE–DAD and SPE–LVSS–NACE–DAD methods. It has been observed that in addition to SPE parameters such as sorbent material, sample pH, breakthrough volume, addition of an organic solvent and elution solvent, also sample characteristics, such as organic matter content, have influence on SPE extraction yields, especially in the case of PHBA. The presence of PHBA and some parabens was detected at trace levels in surface water samples. Concentrations up to 8.4 ng mL −1 were found in raw wastewater, with the highest levels corresponding to methylparaben, propylparaben, and their main degradation product, PHBA.

A fritless, EOF microchip pump for high pressure pumping of aqueous and organic solvents

A fritless, microchip electroosmotic flow (EOF) pump is microfabricated and demonstrated on a planar soda lime glass substrate to be capable of supplying reasonable flow rates under high back pressures, such as that required for micro-high pressure liquid chromatography (micro-HPLC). The microchip EOF pump is composed of a densely packed microchannel containing 800 nm silica particles and was capable of generating a maximum pressure > 1000 psi ( approximately 7 MPa) and a maximum flow rate of 282 nL/min (aqueous cyclohexylamino alkyl sulfonate (CHES) buffer, 10 mM, pH 9.0, 200 V/cm). Other pumping fluids, such as CHES buffer-acetonitrile mixture (50%, v/v), CHES buffer-methanol mixture (50%, v/v), and pure acetonitrile were also used in a characterization of pump performance that included determinations of the maximum flow rate, maximum pressure, and resulting flow rate against an applied, downstream back pressure. The flow rate under a 200 psi ( approximately 1.4 MPa) back pressure at an applied electric field strength of 250 V/cm ranged from 285 nL/min for aqueous CHES buffer to 44 nL/min for CHES buffer-acetonitrile mixture (50%, v/v), indicating that this EOF pump will meet the future requirements of a micro-HPLC system.

Electroosmotic Flow-Based Pump for Liquid Chromatography on a Planar Microchip

An electroosmotic flow (EOF)-based pump, integrated with a sol-gel stationary phase located in the electric field-free region of a microchip, enabled the separation of six nitroaromatic and nitramine explosives and their degradation products via liquid chromatography (LC). The integrated pump and LC system were fabricated within a single quartz substrate. The pump region consisted of a straight channel (3.0 cm x 230 microm x 100 microm) packed with 5-microm porous silica beads. The sol-gel stationary phase was derived from a precursor mixture of methyltrimethoxy- and phenethyltrimethoxysilanes and was synthesized in the downstream, field-free region of the microchip, resulting in a stationary-phase monolith with dimensions of 2.6 cm x 230 microm x 100 microm. Fluid dynamic design considerations are discussed, especially as they relate to integrating the EOF pump with the LC system. Pump and separation performance, as characterized by flow rate measurements, injection, elution, separation, and detection, point to a viable analytical chemistry platform that encompasses all of the benefits expected of portable, laboratory-on-chip systems, including reduced sample requirements and small packaging.

High pressure electroosmotic pump based on a packed bed planar microchip

Abstract A high pressure electroosmotic flow (EOF) pump was fabricated within a glass substrate and tested to characterize its fluid dynamic performance. The EOF pump was constructed on a compact, planar microchip platform with (L × W × D) dimensions of 10 cm × 3.6 cm × 0.3 cm. The pumping region itself consisted of a straight channel (3 cm × 160 μm × 62 μm) uniformly packed with 3.38 μm silica microspheres held in place by a microfabricated weir structure. Characterization of the microchip EOF pump included pressure and flow rate measurements as a function of voltage and system backpressure for a buffered aqueous fluid containing 10 mM cyclohexylamino alkyl sulfonate CHES. Measurements indicate a maximum pressure of 25 atm and a maximum measured flow rate of 85 nL/min. Linear relationships of pressure and flow rate with voltage were confirmed. Current measurements show linear profiles with voltage for flow rate and maximum pressure measurements, indicating minimal effects due to Joule heating under either test condition. Design and performance considerations relating to fluid dynamic considerations are discussed. The large pressures generated electrokinetically by the microchip EOF pump show the potential for a compact motive source that allows for easy integration with applications requiring high pressures.

Online Sample Stacking for Determination of Carnosine-Related Peptides by Capillary Electrophoresis

Recent advances and trends in the development of ion exchange monolithic columns are reviewed. Special attention is paid to the preparation methods and their applications in the environment and biology. The problems of ion exchange monolithic columns and its future are discussed. Fifty references are cited.

Electroosmosis-Based Nanopipettor

Decreasing the volume of reagent solutions consumed in each assay is an effective means to reduce the overall cost in high-throughput analysis laboratories. Recently, increasing attention has been paid to investigate the behavior of individual cells. If one wishes to transfer solution to or from a single cell, a picoliter pipettor is needed since the entire cell volume is commonly less than 1 nL. While pressure ejection and iontophoresis have been used to deliver picoliter volumes of solutions, these techniques cannot yield routine pipettors which perform both solution "picking up" and "dispensing" functions. The state-of-the-art pipettors can handle liquids down to approximately 100 nL, although the pipetting accuracy and precision deteriorate considerably from microliters to nanoliters. If one wishes to pipet reagents of less than 100 nL, new pipettors need to be developed. Electroosmosis has been utilized to pump solutions at flow rates of nanoliters to approximately picoliters per second, which is ideal for nanopipettors. The issue is how to arrange fluidic/electrical connections so that pipetting functions can be performed conveniently. In this paper, we present the results of our initial attempt to develop an electroosmosis-based nanopipettor. The first version of this pipettor consists of a microfabricated electroosmotic (EO) flow pump, a polyacrylamide grounding interface, and a nanoliter-to-picoliter pipet tip. The detailed configuration and fabrication process of the pipettor are discussed. An excellent feature of an EO-driven pipettor is that it has no moving parts. Good reproducibilities (RSD = 6% at 140 pL, 2% at 950 pL, and 2% at 13 nL) and accuracies (9% at 0.13 nL, 4% at 1.0 nL, and 3% at 10 nL) of this pipettor have been demonstrated to aliquot/transport nanoliter-to-picoliter solutions.

Integrated multilayer microfluidic device with a nanoporous membrane interconnect for online coupling of solid-phase extraction to microchip electrophoresis

An integrated microfluidic device was developed for online coupling of solid-phase extraction to microchip electrophoresis (chip SPE-CE). With a nanoporous membrane sandwiched between two PDMS substrates, SPE preconcentration and electrophoretic separation can be carried out in upper and lower fluidic layers, separately and sequentially. During the SPE process, the thin membrane can act as a fluid isolator to prevent intermixing between two fluidic channels. However, when a pulse voltage is applied, the membrane becomes a gateable interconnect so that a small plug of concentrated analytes can be online injected into the lower channel for subsequent separations. This multilayer design provides a universal solution to online SPE-CE hyphenation. Both electroosmotic flow and hydrodynamic pumps have been adopted for SPE operation. SPE was performed on a 2.5 mm long microcolumn, with two weirs on both sides to retain the C(18)-coated silica beads. Rhodamine 123 and FITC-labelled ephedrine were used to test the operational performance of the hyphenation system. High separation efficiency and thousand-fold signal enhancement were achieved.

Thin film electro-osmotic pumps for biomicrofluidic applications.

Electro-osmotic flow (EOF) pumps are attractive for fluid manipulation in microfluidic channels. Open channel EOF pumps can produce high pressures and flow rates, and are relatively easy to fabricate on-chip or integrate with other microfluidic or electrical components. An EOF pump design that is conducive to on-chip fabrication consists of multiple small channel arms feeding into a larger flow channel. We have fabricated this type of pump design using a thin film deposition process that avoids wafer bonding. We have evaluated pumps fabricated on both silicon and glass substrates. Consistent flow rate versus electric field were obtained. For the range of 40-400 V, flow rates of 0.19-2.30 muLmin were measured. Theoretical calculations of pump efficiency were made, as well as calculations of the mechanical power generated by various pump shapes, to investigate design parameters that should improve future pumps.

Solid‐phase extraction and large‐volume sample stacking with an electroosmotic flow pump in capillary electrophoresis for determination of methotrexate and its metabolites in human plasma

This paper describes approaches for large-volume sample stacking (LVSS) with an EOF pumpin CE for the determination of methotrexate (MTX) and its metabolites in human plasma. After pretreatment of plasma through a SPE cartridge, a large sample volume was loaded by hydrodynamic injection (3 psi, 70 s) into the capillary filled with phosphate buffer (70 mM, pH 6.0) containing 0.01% polyethylene oxide. Following removal of a large plug of sample matrix from the capillary using polarity switching (-25 kV), the separation of anionic analytes was subsequently performed without changing polarity again, achieving an improvement of sensitivity of around a 100-fold. The method was applied to therapeutic drug monitoring of MTX in one acute lymphoblastic leukemia patient. This study is one of very few applications showing the feasibility of LVSS in analysis of biological samples by CE.

Approaches for the Simultaneous Extraction of Tetrabromobisphenol A, Tetrachlorobisphenol A, and Related Phenolic Compounds from Sewage Sludge and Sediment Samples Based on Matrix Solid-Phase Dispersion

A procedure based on matrix solid-phase dispersion (MSPD) for sample preparation in the analysis of some bromophenols and halogenated bisphenols in sediments and sludges has been developed. For the first time ever, MSPD was applied for the extraction of organic contaminants from sediment and sewage sludge samples. The influence of experimental conditions on the yield of the extraction process and on the efficiency of the built-in cleanup step was thoroughly evaluated. Analysis of the extracts was performed by nonaqueous capillary electrophoresis coupled with photodiode array ultraviolet detection, using large-volume sample stacking injection based on the electroosmotic flow pump as an on-column preconcentration technique. The method was applied to the analysis of real sludges from urban sewage treatment plants, as well as river and marine sediment samples.

Improving sensitivity in simultaneous determination of copper carboxylates by nonaqueous capillary electrophoresis

A new method of nonaqueous capillary electrophoresis (NACE) with UV spectrophotometric detection was developed and optimized for the simultaneous determination of seven carboxylates (trans-1,2-diaminocyclohexane- N, N, N′, N′-tetraacetic acid (CDTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenediamine- N, N′, N′-triacetic acid (HEDTA), nitrilotriacetic acid (NTA), 1,3-diaminopropane- N, N, N′, N′-tetraacetic acid (PDTA) and triethylenetetraaminehexaacetic acid (TTHA)) as copper complexes. The method development was carried out by using a fused silica capillary. Background electrolyte (BGE) was optimized and the best separation achieved by using 30 mmol L −1 potassium bromide in N-methylformamide (NMF) at apparent pH (pH app) 10.2. A voltage of +30 kV and direct UV detection at 280 nm were used in all measurements. Large-volume sample stacking using the electroosmotic flow pump (LVSEP) was tested in addition to basic capillary electrophoresis (CE) and observed to improve the separation of the analyte zones in the capillary. All the peaks in the electropherograms were properly separated, the calibration plots gave excellent correlation coefficients ( R 2 ≥ 0.994) and all seven copper carboxylate complexes were detected in less than 20 min using both the basic measurements and the large-volume sample stacking method. The new NACE method was tested with lake water and proved to be reliable.

Comparative study of aqueous and non-aqueous capillary electrophoresis in the separation of halogenated phenolic and bisphenolic compounds in water samples

Capillary zone electrophoresis methods, based on either aqueous and non-aqueous solutions as running buffers and UV spectrophotometric detection, have been developed and optimized for the separation of several halogenated phenolic and bisphenolic compounds, suspected or proved to exhibit hormonal disrupting effects. Both aqueous capillary electrophoresis (CE) and non-aqueous capillary electrophoresis (NACE) methods were suitable for the analysis of compounds under study. The separation of the analytes from other 25 potentially interfering phenolic derivatives was achieved with NACE method. Large-volume sample stacking using the electroosmotic flow pump (LVSEP) was assayed as on-column preconcentration technique for sensitivity enhancement. LVSEP–CE and LVSEP–NACE improved peak heights by 5–26 and 16–330 folds, respectively. To evaluate their applicability, the capillary electrophoresis methods developed were applied to the analysis of water samples, using solid-phase extraction as sample pre-treatment process.

Large‐volume stacking in capillary electrophoresis using pH hysteresis of the electroosmotic flow in a bare fused‐silica capillary

For large-volume stacking with the electroosmotic flow pump (LVSEP) in capillary electrophoresis of anionic analytes it is required that the electroosmotic mobility (EOM) should be smaller than the magnitudes of the effective mobilities of the analytes. When a fused-silica capillary is treated with an acidic solution, the silanoate group on the silica surface is neutralized to silanol and the EOM is suppressed. Due to the slow deprotonation equilibrium of the silanol group at an intermediate pH, this reduced EOM can be retained during a number of electrophoresis runs. Using a bare fused-silica capillary preconditioned with 0.01 M HCl, successful LVSEP at pH 6.0 was achieved for weakly acidic compounds with two orders of magnitude enhancements in the concentration sensitivity. The repeatability in migration times of ten analytes stacked by LVSEP in a single day was excellent with the relative standard deviation (RSD) less than 1% (n = 6). The day-to-day repeatability was also excellent with RSD less than 3% (n = 3 x 6) when the capillary was preconditioned each day.

Analysis of tetrabromobisphenol A and other phenolic compounds in water samples by non-aqueous capillary electrophoresis coupled to photodiode array ultraviolet detection

Non-aqueous capillary electrophoresis (NACE) with large-volume sample stacking injection using the electroosmotic flow pump (LVSEP) has been developed for the determination of tetrabromobisphenol A (TBBPA) and other phenolic compounds in environmental matrices. Methanol has been used as run buffer solvent to reduce the electroosmotic flow (EOF). Identification and quantification of the analytes was performed by photodiode array ultraviolet detection. LVSEP–NACE improved sensitivity of the peak height by 90–300-fold. The method developed was applied to the analysis of TBBPA in river water and wastewater samples, using solid-phase extraction (SPE) as sample pretreatment process. The average recoveries of the analytes were in the range of 96–106% and 73–103% for 1 L of river water and 0.5 L of wastewater samples, respectively. When the method was based on off line SPE–LVSEP–NACE, sensitivity was improved by 3300–4500-fold and 1600–2200-fold for river water and wastewater samples, respectively.

Large-volume sample stacking-capillary electrophoresis used for the determination of 3-nitrotyrosine in rat urine

Large-volume sample stacking using the electroosmotic flow (EOF) pump technique has been investigated for the quantification of 3-nitrotyrosine in urine of diabetic rats. The best separation conditions for these highly complex samples were obtained using capillary electrophoresis (CE) in the reversed polarity mode (i.e., injecting at the cathode and detecting at the anode) using cetyltrimethylammonium bromide (CTAB) in the running buffer. The optimum CE separation conditions were achieved using a phosphate buffer prepared with 0.15 M phosphoric acid and 0.5 mM CTAB adjusted to pH 6.4 with sodium hydroxide. In such CE conditions, the limit of detection (LOD) was 1.77 μM for 3-nitrotyrosine with normal injection mode, meanwhile with the large-volume sample stacking technique a more than 20-fold improvement was observed (i.e., LOD = 0.08 μM was obtained) without noticeable loss of resolution. This value allowed the detection of 3-nitrotyrosine in urine from diabetic rats. To our knowledge, this work is one of the few applications showing the great possibilities of these stacking procedures to analyse biological samples by CE.

Application of capillary electrophoresis with different sample stacking strategies for the determination of a group of nonsteroidal anti-inflammatory drugs in the low microg x L(-1) concentration range.

Several on-column sample preconcentration modes--large-volume sample stacking using the EOF pump (LVSEP), LVSEP with anion-selective exhaustive injection (LVSEP-ASEI) and field-amplified sample injection with sample matrix removal using the electroosmotic flow (EOF) pump (FAEP)--were used to analyze some nonsteroidal anti-inflammatory drugs (NSAIDs) by capillary electrophoresis, and then compared. Methanol was the background electrolyte solvent to suppress the EOF. The effect of the type and length of the solvent plug, and the sample injection time were investigated in FAEP to determine the conditions that provided the best response. LVSEP, LVSEP-ASEI, and FAEP improved the sensitivity of the peak area by 100-, 1200-, and 1800-fold, respectively. The methodology developed, in combination with solid-phase extraction (SPE), was applied to the analysis of water samples.

Porous glass electroosmotic pumps: theory

This paper presents an analytical study of electroosmotic (EO) pumps with porous pumping structures. We have developed an analytical model to solve for electroosmotic flow rate, pump current, and thermodynamic efficiency as a function of pump pressure load for porous-structure EO pumps. The model uses a symmetric electrolyte approximation valid for the high-zeta-potential regime and numerically solves the Poisson–Boltzmann equation for charge distribution in the idealized pore geometry. Generalized scaling of pumping performance is discussed in the context of a parameterization that includes porosity, tortuosity, pore size, bulk ionic density, and the nonuniform conductivity distribution over charge layers. The model also incorporates an approximate ionic-strength-dependent zeta potential formulation.