The methodology of continuous feedback-based flow titrations and the principle of compensating er... more The methodology of continuous feedback-based flow titrations and the principle of compensating errors [Anal. Chem. 72 (2000) 4713; Anal. Chim. Acta 435 (2001) 289] were applied to the determination of calcium and magnesium ions with EDTA. The flow of the titrant, EDTA, varied linearly in response to a controller output voltage while the total flow (F(T), the sum of the metal ion sample flow and the titrant flow) was held constant. The sample was pre-doped with a metal ion indicator; the status of the indicator color in the mixed stream was monitored by an optical detector and was used for governing the controller output as well as for interpreting the results of the titrations. The titrant flow initially ramped upward linearly. As a change in the color corresponding to the equivalence point was sensed by the detector, the controller output (instantaneous value V(H)) reversed its ramp direction, thus decreasing the titrant flow linearly at the same ramp rate. When the predefined abso...
A microfluidic traveling-wave electrophoresis (TWE) system is reported that uses a locally define... more A microfluidic traveling-wave electrophoresis (TWE) system is reported that uses a locally defined traveling electric field wave within a microfluidic channel to achieve band transport and separation. Low voltages, over a range of -0.5 to +0.5 V, are used to avoid electrolysis and other detrimental redox reactions while the short distance between electrodes, ∼25 μm, provides high electric fields of ∼200 V cm(-1). It is expected that the low voltage requirements will simplify the future development of smaller portable devices. The TWE device uses four interdigitated electrode arrays: one interdigitated electrode array pair is on the top of the microchannel and the other interdigitated electrode array pair is on the microchannel bottom. The top and bottom substrates are joined by a PDMS spacer that has a nominal height of 15 μm. A pinched injection scheme is used to define a narrow sample band within an injection cross either electrokinetically or hydrodynamically. Separation of two dyes, fluorescein and FLCA, with baseline resolution is achieved in less than 3 min and separation of two proteins, insulin and casein is demonstrated. Investigation of band broadening with fluorescein reveals that sample band widths equivalent to the diffusion limit can be achieved within the microfluidic channel, yielding highly efficient separations. This low level of band broadening can be achieved with capillary electrophoresis, but is not routinely observed in microchannel electrophoresis. Sample enrichment can be achieved very easily with TWE using a device with converging electric field waves controlled by two sets of independently controlled interdigitated electrodes arrays positioned serially along the microchannel. Sample enrichment of 40-fold is achieved without heterogeneous buffer/solvent systems, sorptive, or permselective materials. While there is much room for improvement in device fabrication, and many capabilities are yet to be demonstrated, it is anticipated that the capabilities and performance demonstrated herein will enable new lab-on-a-chip processes and systems.
Models and microfluidic experiments are presented of an electrophoretic separation technique in w... more Models and microfluidic experiments are presented of an electrophoretic separation technique in which charged particles whose mobilities exceed a tunable threshold are trapped between the crests of a longitudinal electric wave traveling through a stationary viscous fluid. The wave is created by applying periodic potentials to electrode arrays above and below a microchannel. Predicted average velocities agree with experiments and feature chaotic attractors for intermediate mobilities.
We describe the use of electrogenerated titrants in continuous feedback-based flow titrations. In... more We describe the use of electrogenerated titrants in continuous feedback-based flow titrations. In previous studies from this laboratory (Anal. Chem. 2000, 72, 4713; Anal. Chim. Acta. 2001, 435, 289) the flow rate of a titrant was varied linearly in response to a controller output voltage (V c ). In the present article, the status of the controller output (positive or negative ramping) is governed in a binary fashion by a sensor output and the controller output voltage linearly controls the electrical current applied to an electrochemical titrant generator. The volumetric flow rate of the generated titrant remains constant, but its concentration varies linearly with V c . The ultimate titration accuracy and precision in previous studies where flow was varied depended on flow accuracy and reproducibility, here they depend on more easily controlled/accurately known parameters, electrical current and coulometric reagent generation efficiency at a constant flow rate. The system has been tested by applying it to titrations of As(III), thiosulfate, sulfite, metabibisulfite and sulfide using electrogenerated iodine. The titration mixture is monitored optically (as well as potentiometrically, for sulfide). This principle permitted continuous true titrations with good precision and speed (typ. < 1.5% relative standard deviation (RSD) with less than 30 s/titration with photometric detection, typ. 1.25% RSD with under 60 s/titration with potentiometric detection for sulfide).
We introduce a new concept for continuous on-line titrations based on feedback-controlled flow ra... more We introduce a new concept for continuous on-line titrations based on feedback-controlled flow ratiometry and the principle of compensating errors. The system has been thoroughly tested by applying it to acid-base neutralization titrations with indicator-based end point detection. In a typical case, the total flow (FT, consisting of the sample and the titrant flows) is held constant while the titrant (e.g., a standard base containing an indicator) flow FB varies linearly in response to a controller output voltage. The sample (e.g., an acidic solution to be titrated) flow FA constitutes the makeup and thus also varies (FA = FT - FB). The status of the indicator color in the mixed stream is monitored by an optical detector and used either for governing the controller output or for interpreting the results of the titration. Three methods (PID based control, fixed triangular wave control, and feedback-based triangular wave control implemented on a PC) were examined. In the last and the most successful approach, the titrant flow is initially ramped upward linearly. At the instant a change in the color is sensed by the detector, the titrant flow rate FH is higher than the true equivalence flow rate FE because of the lag time between the first compositional change and its detection. The sensing of the change in color causes the system output to immediately reverse its ramp direction such that the titrant flow now goes down linearly at the same rate. At the instant a change in color, in the opposite direction this time, is again sensed, the titrant flow rate FL is lower than FE by exactly the same amount that FH was higher than FE. This principle of compensating errors (FE = (FH + FL)/2) allows true titrations with excellent reproducibility and speed (0.6% RSD at 3 s/titration and 0.2% RSD at 10 s/titration) and titrant volume consumption as little as 12 microL/titration and solves an old conceptual problem in flow based titrations.
The current rectification factor can be tailored by changing the degree of asymmetry between the ... more The current rectification factor can be tailored by changing the degree of asymmetry between the fluid baths on opposite sides of a nanocapillary membrane (NCM). A symmetric device with symmetric fluid baths connected to opposite sides of the NCM did not rectify ionic current; while a NCM connected between fluid baths with a 32-fold difference in cross-sectional area produced a rectification factor of 75. The data suggests that the primary mechanism for the current rectification is the change in cross-sectional area of the fluid baths and the polarity dependent propagation of the enriched and depleted concentration polarization (CP) zones into these regions. An additional contribution to the increasing rectification factor with increasing bath asymmetry appears to be a result of electroconvection in the macropore, with inside diameters (IDs) of 625 and 850μm. Power spectral density (PSD) analysis reveals chaotic oscillations that are consistent with electroconvection in the I-t data of the 625 and 850-μm ID macropore devices. In the ON state, current rectification keeps ionic transport toward the NCM high, increasing the speed of processes like sample enrichment. A simple means is provided to fabricate fluidic diodes with tailored current rectification factors.
The methodology of continuous feedback-based flow titrations and the principle of compensating er... more The methodology of continuous feedback-based flow titrations and the principle of compensating errors [Anal. Chem. 72 (2000) 4713; Anal. Chim. Acta 435 (2001) 289] were applied to the determination of calcium and magnesium ions with EDTA. The flow of the titrant, EDTA, varied linearly in response to a controller output voltage while the total flow (F(T), the sum of the metal ion sample flow and the titrant flow) was held constant. The sample was pre-doped with a metal ion indicator; the status of the indicator color in the mixed stream was monitored by an optical detector and was used for governing the controller output as well as for interpreting the results of the titrations. The titrant flow initially ramped upward linearly. As a change in the color corresponding to the equivalence point was sensed by the detector, the controller output (instantaneous value V(H)) reversed its ramp direction, thus decreasing the titrant flow linearly at the same ramp rate. When the predefined abso...
A microfluidic traveling-wave electrophoresis (TWE) system is reported that uses a locally define... more A microfluidic traveling-wave electrophoresis (TWE) system is reported that uses a locally defined traveling electric field wave within a microfluidic channel to achieve band transport and separation. Low voltages, over a range of -0.5 to +0.5 V, are used to avoid electrolysis and other detrimental redox reactions while the short distance between electrodes, ∼25 μm, provides high electric fields of ∼200 V cm(-1). It is expected that the low voltage requirements will simplify the future development of smaller portable devices. The TWE device uses four interdigitated electrode arrays: one interdigitated electrode array pair is on the top of the microchannel and the other interdigitated electrode array pair is on the microchannel bottom. The top and bottom substrates are joined by a PDMS spacer that has a nominal height of 15 μm. A pinched injection scheme is used to define a narrow sample band within an injection cross either electrokinetically or hydrodynamically. Separation of two dyes, fluorescein and FLCA, with baseline resolution is achieved in less than 3 min and separation of two proteins, insulin and casein is demonstrated. Investigation of band broadening with fluorescein reveals that sample band widths equivalent to the diffusion limit can be achieved within the microfluidic channel, yielding highly efficient separations. This low level of band broadening can be achieved with capillary electrophoresis, but is not routinely observed in microchannel electrophoresis. Sample enrichment can be achieved very easily with TWE using a device with converging electric field waves controlled by two sets of independently controlled interdigitated electrodes arrays positioned serially along the microchannel. Sample enrichment of 40-fold is achieved without heterogeneous buffer/solvent systems, sorptive, or permselective materials. While there is much room for improvement in device fabrication, and many capabilities are yet to be demonstrated, it is anticipated that the capabilities and performance demonstrated herein will enable new lab-on-a-chip processes and systems.
Models and microfluidic experiments are presented of an electrophoretic separation technique in w... more Models and microfluidic experiments are presented of an electrophoretic separation technique in which charged particles whose mobilities exceed a tunable threshold are trapped between the crests of a longitudinal electric wave traveling through a stationary viscous fluid. The wave is created by applying periodic potentials to electrode arrays above and below a microchannel. Predicted average velocities agree with experiments and feature chaotic attractors for intermediate mobilities.
We describe the use of electrogenerated titrants in continuous feedback-based flow titrations. In... more We describe the use of electrogenerated titrants in continuous feedback-based flow titrations. In previous studies from this laboratory (Anal. Chem. 2000, 72, 4713; Anal. Chim. Acta. 2001, 435, 289) the flow rate of a titrant was varied linearly in response to a controller output voltage (V c ). In the present article, the status of the controller output (positive or negative ramping) is governed in a binary fashion by a sensor output and the controller output voltage linearly controls the electrical current applied to an electrochemical titrant generator. The volumetric flow rate of the generated titrant remains constant, but its concentration varies linearly with V c . The ultimate titration accuracy and precision in previous studies where flow was varied depended on flow accuracy and reproducibility, here they depend on more easily controlled/accurately known parameters, electrical current and coulometric reagent generation efficiency at a constant flow rate. The system has been tested by applying it to titrations of As(III), thiosulfate, sulfite, metabibisulfite and sulfide using electrogenerated iodine. The titration mixture is monitored optically (as well as potentiometrically, for sulfide). This principle permitted continuous true titrations with good precision and speed (typ. < 1.5% relative standard deviation (RSD) with less than 30 s/titration with photometric detection, typ. 1.25% RSD with under 60 s/titration with potentiometric detection for sulfide).
We introduce a new concept for continuous on-line titrations based on feedback-controlled flow ra... more We introduce a new concept for continuous on-line titrations based on feedback-controlled flow ratiometry and the principle of compensating errors. The system has been thoroughly tested by applying it to acid-base neutralization titrations with indicator-based end point detection. In a typical case, the total flow (FT, consisting of the sample and the titrant flows) is held constant while the titrant (e.g., a standard base containing an indicator) flow FB varies linearly in response to a controller output voltage. The sample (e.g., an acidic solution to be titrated) flow FA constitutes the makeup and thus also varies (FA = FT - FB). The status of the indicator color in the mixed stream is monitored by an optical detector and used either for governing the controller output or for interpreting the results of the titration. Three methods (PID based control, fixed triangular wave control, and feedback-based triangular wave control implemented on a PC) were examined. In the last and the most successful approach, the titrant flow is initially ramped upward linearly. At the instant a change in the color is sensed by the detector, the titrant flow rate FH is higher than the true equivalence flow rate FE because of the lag time between the first compositional change and its detection. The sensing of the change in color causes the system output to immediately reverse its ramp direction such that the titrant flow now goes down linearly at the same rate. At the instant a change in color, in the opposite direction this time, is again sensed, the titrant flow rate FL is lower than FE by exactly the same amount that FH was higher than FE. This principle of compensating errors (FE = (FH + FL)/2) allows true titrations with excellent reproducibility and speed (0.6% RSD at 3 s/titration and 0.2% RSD at 10 s/titration) and titrant volume consumption as little as 12 microL/titration and solves an old conceptual problem in flow based titrations.
The current rectification factor can be tailored by changing the degree of asymmetry between the ... more The current rectification factor can be tailored by changing the degree of asymmetry between the fluid baths on opposite sides of a nanocapillary membrane (NCM). A symmetric device with symmetric fluid baths connected to opposite sides of the NCM did not rectify ionic current; while a NCM connected between fluid baths with a 32-fold difference in cross-sectional area produced a rectification factor of 75. The data suggests that the primary mechanism for the current rectification is the change in cross-sectional area of the fluid baths and the polarity dependent propagation of the enriched and depleted concentration polarization (CP) zones into these regions. An additional contribution to the increasing rectification factor with increasing bath asymmetry appears to be a result of electroconvection in the macropore, with inside diameters (IDs) of 625 and 850μm. Power spectral density (PSD) analysis reveals chaotic oscillations that are consistent with electroconvection in the I-t data of the 625 and 850-μm ID macropore devices. In the ON state, current rectification keeps ionic transport toward the NCM high, increasing the speed of processes like sample enrichment. A simple means is provided to fabricate fluidic diodes with tailored current rectification factors.
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