Contact Conductivity Detection Research Articles

A Study on Double Inputs Direct Contact and Single Output Capacitively Coupled Conductivity Detector.

In this paper, an improved double inputs direct contact and single output capacitively coupled conductivity detector (DISODCD) based on traditional contactless capacitively coupled conductivity detector (C4D) is developed. The sensor uses double inputs of the contact electrode and capacitively coupled output of the contactless electrode and a lock-in amplifier to reduce interfering noise signals and amplify gain. Parallel circuit counteracts the part of the adverse capacitance reactance introduced by electrode polarization and reduces the effect of the impedance caused by the coupled wall capacitance to measure the resistance of solution. The sensor reduces limit of detection (LOD) of analyte and improves the sensitivity of the device. The LOD of the potassium chloride solution is 1 nM, and the detection range is 0.01 μM to 10 mM in actual testing for a single sample. The ratio of the response of potassium chloride solution to background ultrapure water at low concentrations is better than that of double input capacitively coupled contactless conductivity detector (DIC4D) and direct contact conductivity detection (DCD) under the same condition. In the case that the test cell is contaminated with impurities, pollution of impurities has little effect on the response of DISODCD. In practical application, it has a good service life.

Determination of Commonly Used Excipients in Pharmaceutical Preparations by Microchip Electrophoresis with Conductivity Detection

In this study, a microchip electrophoresis method for simultaneous determination of three frequently used pharmaceutical excipients (methylparaben, propylparaben and erythrosine) was described. Anionic zone electrophoresis (ZE) separations were performed on the microchip with contact conductivity detection using a high pH buffer (9.8). Sufficient resolution of the analytes (≥ 2.6) was achieved by 1 mmol L−1 β-cyclodextrin added to the buffer. Adsorption of the analytes on the walls of a poly(methylmethacrylate) microchip was suppressed by adding 1 mmol L− 1 sulfate to the sample. The LOD values for the excipients ranged from 0.5 to 11.1 µmol L− 1. High repeatability of the migration times of the analytes in model (< 2.9% RSD) and real pharmaceutical (< 4.1% RSD) samples was reached on the microchip. Peak areas of the analytes in all analyzed samples were characterized by RSD values ranging from 0.4 to 5.7%. The ZE method was successfully applied to the analysis of pharmaceutical syrups after a simple pretreatment (centrifugation and dilution), and gave recoveries of the analytes in the range 86.1–96.6%. The results showed a good agreement with those obtained by CZE with UV detection (254 nm) at 95% confidence level.

Capillary Scale Admittance and Conductance Detection.

Admittance detection, more commonly called capacitively coupled contactless conductivity detection, is widely used. While the true conductance of a solution is linear with concentration up to ∼1 mequiv/L, the admittance signal is nonlinear. In small-bore capillaries and highly resistive solutions, such as in suppressed open tubular ion chromatography (SOTIC), the admittance signal is exponentially related to concentration. Solution contact conductivity detection is common in microfluidics, but no true conductivity measurement efforts have been made with conventional capillaries in the last two decades. We examine five solution contact cell geometries: (A) wire/disk electrodes perpendicular to the flow direction, (B) annular tubular electrodes facing the flow (that exits through the center tube), (C) ring-disk electrodes facing the flow that exits through the annulus, (D) coplanar parallel wire/disk electrodes facing the flow that exits around the electrodes, and (E) planar electrodes separated by a thin insulating layer with a through-hole in which the liquid flows. Present limitations of the available components as well as the designs themselves do not allow type A and B cells to reach low enough dispersion levels. Types C-E all produce the same efficiency for chloride in a SOTIC setup (12000 ± 200 plates/m), limited by dispersion in the suppressor. Further choice and refinement will be dictated by the availability of a lower dispersion suppressor. All such contact conductance results were linear with concentration, and initial results suggest that attainable LODs will be competitive with those from benchtop ICs.

A Microchip Electrophoresis Device Integrated with the Top-bottom Antiparallel Electrodes of Indium Tin Oxide to Detect Inorganic Ions by Contact Conductivity.

A microchip electrophoresis (ME) device with off-channel contact conductivity detection (C2D) was constructed using top-bottom antiparallel indium tin oxide (ITO) electrodes and a cross-type microchannel. The 500-m wide top-bottom antiparallel decouplers were found to effectively decrease the interference of the electrophoretic current. The cross-type microchannel was formed by bonding the patterned negative photoresist microstructures and the two top-bottom opposed ITO-deposited glass substrates. Five seconds of 150 V/cm injection field and the 100 V/cm separation field equipped with the C2D of AC 200 mV excitation voltage provided adequate ME operational parameters to obtain the K+ and Na+ peaks separation. The ME devices obtained good coefficients in a range of 11000 μM for the K+ and Na+ detection. The calculated limit of detection was 1 μM. This design for off-channel and top-bottom antiparallel electrodes shows that C2D ME devices have great potential for the measurement of inorganic ions.

Sensitive, selective analysis of selenium oxoanions using microchip electrophoresis with contact conductivity detection.

The common selenium oxoanions selenite (SeO32–) and selenate (SeO42–) are toxic at intake levels slightly below 1 mg day–1. These anions are currently monitored by a variety of traditional analytical techniques that are time-consuming, expensive, require large sample volumes, and/or lack portability. To address the need for a fast and inexpensive analysis of selenium oxoanions, we present the first microchip capillary zone electrophoresis (MCE) separation targeting these species in the presence of chloride, sulfate, nitrate, nitrite, chlorate, sulfamate, methanesulfonate, and fluoride, which can be simultaneously monitored. The chemistry was designed to give high selectivity in nonideal matrices. Interference from common weak acids is avoided by operating near pH 4. Separation resolution from chloride was enhanced to improve tolerance of high-salinity matrices. As a result, selenate can be quantified in the presence of up to 1.5 mM NaCl, and selenite analysis is even more robust against chloride. Using contact conductivity detection, detection limits for samples with conductivity equal to the background electrolyte are 53 nM (4.2 ppb Se) and 380 nM (30 ppb) for selenate and selenite, respectively. Analysis time, including injection, is ∼2 min. The MCE method was validated against ion chromatography (IC) using spiked samples of dilute BBL broth and slightly outperformed the IC in accuracy while requiring <10% of the analysis time. The applicability of the technique to real samples was shown by monitoring the consumption of selenite by bacteria incubated in LB broth.

Sequential Determination of Inorganic Cations and Anions in Cerebrospinal Fluid by Microchip Electrophoresis

Analysis of inorganic ions in cerebrospinal fluid (CSF) is used mainly in the diagnostics of central nervous system diseases, such as Alzheimer’s disease or multiple sclerosis. A new analytical method for fast determination of inorganic cations (ammonium, calcium, magnesium, sodium and potassium) and anions (chloride, sulfate, nitrite and nitrate) in CSF on an electrophoretic microchip was developed in this context. Zone electrophoresis (ZE) separations were performed on the microchip with coupled channels (CC) and contact conductivity detection. Two different propionate background electrolytes were used for the sequential determination of cations at pH 3.1 and anions at pH 4.3. ZE was used for the determination of cationic constituents while ZE–ZE approach was employed for the determination of chloride in the first separation channel on the CC microchip and other anionic micro-constituents in the second channel. LOD values were in the range of 0.003–0.012 mg L−1 and 0.019–0.047 mg L−1 for cations and anions, respectively. Repeatability of migration time was up to 1.2 % for both cations and anions. Repeatability of peak area ranged from 0.3 to 5.6 % for cations and from 0.6 to 6.0 % for anions. Recovery of both cations and anions was in the range 90–106 %. CSF samples were only diluted appropriately without other sample pretreatment prior to analysis. Developed sequential method is suitable for fast determination of the studied cations and anions in CSF with total analysis time <15 min.

CZE study on adsorption processes of aliphatic and aromatic amines on PMMA chip

Adsorption processes on a PMMA chip linked with CZE separations of a group of 13 aliphatic and aromatic mono- and di-amines were studied. Due to the lack of chromophores within aliphatic amines, contact conductivity detection implemented directly onto the chip was used for monitoring of cationic CZE separations. To prevent an adsorption of studied amines to the chip channels, the surface of PMMA chip was modified by dynamic coating. Different surface modifiers, such as aliphatic oligoamines (diethylenetriamine and triethylenetetramine), were added to the BGE solutions filling the chip channels. The effect of various concentrations of surface modifiers on peak profiles and separation parameters of amines was monitored. Of these, mainly, aliphatic di-amines and aromatic mono-amines adversely affected the CZE resolution of a whole group of analytes by their strong adsorption to the chip channels. A propionate BGE with pH 3.2 containing 100 μM triethylenetetramine and 25 mM 18-crown-6-ether was found suitable for CZE resolution of 12 from a total of 13 amines studied. Simple dynamic modification of the surface of PMMA chip enabled fast (analysis time lasted 9 min), sensitive (sub-μM LODs reached) and reproducible (1-3% RSD of the peak areas) CZE analysis of the aliphatic and aromatic amines.

A low-cost, label-free DNA detection method in lab-on-chip format based on electrohydrodynamic instabilities, with application to long-range PCR

In order to evolve from a "chip in the lab" to a "lab on a chip" paradigm, there is still a strong demand for low-cost, portable detection technologies, notably for analytes at low concentrations. Here we report a new label-free DNA detection method with direct electronic read, and apply it to long-range PCR. This method uses a nonlinear electrohydrodynamic phenomenon: when subjected to high electric fields (typically above 100 V cm(-1)), suspensions of large polyelectrolytes, such as long DNA molecules, create "giant" dynamic concentration fluctuations. These fluctuations are associated with large conductivity inhomogeneities, and we use here a contact-mode local conductivity detector to detect these fluctuations. In order to decouple the detection electronics from the high voltage excitation one, an original "doubly symmetric" floating mode battery-operated detection scheme was developed. A wavelet analysis was then applied, to unravel from the chaotic character of the electohydrodynamic instabilities a scalar signal robustly reflecting the amplification of DNA. As a first proof of concept, we measured the products of the off-chip amplification of 10 kbp DNA from lambda phage DNA, achieving a sensitivity better than 100 fg DNA in the original 50 μl sample. This corresponds to the amplification products of less than 100 initial copies of target DNA. The companion enabling technologies developed to implement this new concept, i.e. the doubly symmetric contact conductivity detection and wavelet analysis, may also find various other applications in lab-on-chips.

Rapid Analysis of Perchlorate in Drinking Water at Parts per Billion Levels Using Microchip Electrophoresis

A microchip capillary electrophoresis (MCE) system has been developed for the determination of perchlorate in drinking water. The United States Environmental Protection Agency (USEPA) recently proposed a health advisory limit for perchlorate in drinking water of 15 parts per billion (ppb), a level requiring large, sophisticated instrumentation, such as ion chromatography coupled with mass spectrometry (IC-MS), for detection. An inexpensive, portable system is desired for routine online monitoring applications of perchlorate in drinking water. Here, we present an MCE method using contact conductivity detection for perchlorate determination. The method has several advantages, including reduced analysis times relative to IC, inherent portability, high selectivity, and minimal sample pretreatment. Resolution of perchlorate from more abundant ions was achieved using zwitterionic, sulfobetaine surfactants, N-hexadecyl-N,N-dimethyl-3-ammonio-1-propane sulfonate (HDAPS) and N-tetradecyl-N,N-dimethyl-3-ammonio-1-propane sulfonate (TDAPS). The system performance and the optimization of the separation chemistry, including the use of these surfactants to resolve perchlorate from other anions, are discussed in this work. The system is capable of detection limits of 3.4 +/- 1.8 ppb (n = 6) in standards and 5.6 +/- 1.7 ppb (n = 6) in drinking water.

High-sensitivity microchip electrophoresis determination of inorganic anions and oxalate in atmospheric aerosols with adjustable selectivity and conductivity detection

A sensitive and selective separation of common anionic constituents of atmospheric aerosols, sulfate, nitrate, chloride, and oxalate, is presented using microchip electrophoresis. The optimized separation is achieved in under 1min and at low background electrolyte ionic strength (2.9mM) by combining a metal-binding electrolyte anion (17mM picolinic acid), a sulfate-binding electrolyte cation (19mM HEPBS), a zwitterionic surfactant with affinity towards weakly solvated anions (19mM N-tetradecyl,N,N-dimethyl-3-ammonio-1-propansulfonate), and operation in counter-electroosmotic flow (EOF) mode. The separation is performed at pH 4.7, permitting pH manipulation of oxalate's mobility. The majority of low-concentration organic acids are not observed at these conditions, allowing for rapid subsequent injections without the presence of interfering peaks. Because the mobilities of sulfate, nitrate, and oxalate are independently controlled, other minor constituents of aerosols can be analyzed, including nitrite, fluoride, and formate if desired using similar separation conditions. Contact conductivity detection is utilized, and the limit of detection for oxalate (S/N=3) is 180nM without stacking. Sensitivity can be increased with field-amplified sample stacking by injecting from dilute electrolyte with a detection limit of 19nM achieved. The high-sensitivity, counter-EOF operation, and short analysis time make this separation well-suited to continuous online monitoring of aerosol composition.

Improving the Compatibility of Contact Conductivity Detection with Microchip Electrophoresis Using a Bubble Cell

A new approach for improving the compatibility between contact conductivity detection and microchip electrophoresis was developed. Contact conductivity has traditionally been limited by the interaction of the separation voltage with the detection electrodes because the applied field creates a voltage difference between the electrodes, leading to unwanted electrochemical reactions. To minimize the voltage drop between the conductivity electrodes and therefore improve compatibility, a novel bubble cell detection zone was designed. The bubble cell permitted higher separation field strengths (600 V/cm) and reduced background noise by minimizing unwanted electrochemical reactions. The impact of the bubble cell on separation efficiency was measured by imaging fluorescein during electrophoresis. A bubble cell four times as wide as the separation channel led to a decrease of only 3% in separation efficiency at the point of detection. Increasing the bubble cell width caused larger decreases in separation efficiency, and a 4-fold expansion provided the best compromise between loss of separation efficiency and maintaining higher field strengths. A commercial chromatography conductivity detector (Dionex CD20) was used to evaluate the performance of contact conductivity detection with the bubble cell. Mass detection limits (S/N = 3) were as low as 89 +/- 9 amol, providing concentration detection limits as low as 71 +/- 7 nM with gated injection. The linear range was measured to be greater than 2 orders of magnitude, from 1.3 to 600 microM for sulfamate. The bubble cell improves the compatibility and applicability of contact conductivity detection in microchip electrophoresis, and similar designs may have broader application in electrochemical detection as the expanded detection zone provides increased electrode surface area and reduced analyte velocity in addition to the reduction of separation field effects.

Recent applications of conductivity detection in capillary and chip electrophoresis

The review provides a comprehensive survey of the recent applications of contact and contactless conductivity detection in capillary electrophoretic and chip electrophoretic analyses of a broad scale of compounds, from low-molecular-mass highly mobile small inorganic and organic ions, via medium-molecular-mass peptides and oligo- and polynucleotides up to high-molecular-mass biopolymers, proteins and nucleic acids fragments. The review presents also the recent developments in the construction of different types of conductivity detectors (detectors with galvanic contact of the sensing electrodes with the BGE and sample components, contactless conductivity detectors with capacitively coupled tubular and semitubular electrodes and combined conductivity/optical detectors) applied in the capillary electromigration methods performed in classical fused silica, polytetrafluorethylene, and polyetheretherketone capillaries or on glass and polymethylmethacrylate microchips. In addition, the principle and theoretical bases of conductivity detection in capillary electromigration techniques, zone electrophoresis, ITP, micellar EKC, and electrochromatography are briefly described.

Analysis of anions in ambient aerosols by microchip capillary electrophoresis

We describe a microchip capillary electrophoresis method for the analysis of nitrate and sulfate in ambient aerosols. Investigating the chemical composition of ambient aerosol particles is essential for understanding their sources and effects. Significant progress has been made towards developing mass spectrometry-based instrumentation for rapid qualitative analysis of aerosols. Alternative methods for rapid quantification of selected high abundance compounds are needed to augment the capacity for widespread routine analysis. Such methods could provide much higher temporal and spatial resolution than can be achieved currently. Inorganic anions comprise a large percentage of particulate mass, with nitrate and sulfate among the most abundant species. While ion chromatography has proven very useful for analyzing extracts of time-integrated ambient aerosol samples collected on filters and for semi-continuous, on-line particle composition measurements, there is a growing need for development of new compact, inexpensive approaches to routine on-line aerosol ion analysis for deployment in spatially dense, atmospheric measurement networks. Microchip capillary electrophoresis provides the necessary speed and portability to address this need. In this report, on-column contact conductivity detection is used with hydrodynamic injection to create a simple microchip instrument for analysis of nitrate and sulfate. On-column contact conductivity detection was achieved using a Pd decoupler placed upstream from the working electrodes. Microchips containing two Au or Pd working electrodes showed a good linear range (5-500 microM) and low limits-of-detection for sulfate and nitrate, with Au providing the lowest detection limits (1 microM) for both ions. The completed microchip system was used to analyze ambient aerosol filter samples. Nitrate and sulfate concentrations measured by the microchip matched the concentrations measured by ion chromatography.

Capacitively coupled contactless conductivity detection in capillary electrophoresis.

Capacitively coupled contactless conductivity detection (C(4)D) has become an accepted detection method in capillary electrophoresis (CE) for a variety of analytes. Advantages of this technique over optical detection modes and galvanic contact conductivity detection include great flexibility in capillary handling and rather simple mechanical parts and electronics, as it can be performed in an on-capillary mode. Furthermore, the detection principle can be used with capillaries made of other materials than fused silica (PEEK, Teflon), with chip-based separation technologies, or with capillaries having very small inner diameters. This review presents a discussion of the published literature on C(4)D for CE and capillary electrochromatography.

Contact conductivity detection of polymerase chain reaction products analyzed by reverse-phase ion pair microcapillary electrochromatography.

We describe the development of an integrated microelectrophoretic system consisting of a contact conductivity detector mounted on-chip for monitoring the separation of double-stranded (ds) DNA fragments produced via the polymerase chain reaction (PCR) using microcapillary electrochromatography as the separation mode. The separation was carried out in a polymer-based microfluidic device, hot-embossed into poly(methylmethacrylate) (PMMA), whose walls were functionalized to produce a C(18)-terminated surface to act as the stationary phase (open channel format). The carrier electrolyte contained the ion-pairing agent, triethylammonium acetate (TEAA) to allow the separation to be carried out using reverse-phase ion-pair capillary electrochromatography (RP-IPCEC). The microelectrophoretic separations were investigated utilizing various solvent strengths (acetonitrile/water) with 25 mM TEAA to observe the effects on the separation efficiency as well as the chromatographic development time and detector performance. The field strength significantly affected the quality of the separation, with no separation observed at 333 V/cm for a low mass dsDNA sizing ladder, but baseline separation achieved using a field strength of 67 V/cm. It was observed that the solvent strength affected the retention behavior of the polyanionic molecules as well as the electroosmotic mobility. Higher acetonitrile compositions in the run buffer resulted in reduced plate numbers, which produced lower chromatographic resolution. The use of conductivity detection allowed mass detection sensitivities in the range of 10(-21) mol with a separation efficiency of 10(4) plates and the performance of the detector independent of the acetonitrile content used in the carrier electrolyte.

Contact conductivity detection in poly(methyl methacrylate)-based microfluidic devices for analysis of mono- and polyanionic molecules.

An on-column contact conductivity detector was developed for the analysis of various mono- and polyanionic compounds separated by electrophoresis chips fabricated in poly(methyl methacrylate) (PMMA) using hot embossing techniques from Ni electroforms. The detector consisted of a pair of Pt wires (127 microm diameter) with an end-to-end spacing of approximately 20 microm and situated within the fluidic channel. The waveform applied to the electrode pair was a bipolar pulse with a frequency of 5.0 kHz and was used to reduce the charging current from measurement so that the current recorded at the end of one pulse is more representative of the solution conductivity. Using the detector, separations of amino acids, peptides, proteins, and oligonucleotides were demonstrated. For the amino acids and peptides, free-solution zone electrophoresis was performed. A calibration plot for the amino acid alanine was found to be linear from approximately 10 to 100 nM in a carrier electrolyte consisting of 10 mM triethylamonium acetate. The concentration detection limit was found to be 8.0 nM, with the corresponding mass detection limit equal to 3.4 amol (injection volume = 425 pL). The protein separations with conductivity detection were performed using MEKC, in which the carrier electrolyte contained the anionic surfactant sodium dodecyl sulfate (SDS) above its cmc. Near baseline resolution was achieved in the PMMA microchip for a solution containing 8 different proteins. In the case of the DNA fragments, capillary electrochromatography was used with a C18-modified PMMA chip and a carrier electrolyte containing an ion-pairing agent.

Comparison of different conductivity detector geometries on an isotachophoresis PMMA-microchip

Conductivity detection is one of the most often employed means of detection in isotachophoresis. In microanalytical devices, thin-film platinum electrodes can be used for conductivity detection and for other electrochemical methods of detection. The design and the performance of different electrode geometries for on-column contact conductivity detection with thin-film platinum electrodes integrated on an isotachophoresis PMMA-microchip is described. Three different electrode geometries for direct conductivity detection were used for the investigation of isotachophoretic separations. The influence of the width of the electrodes and their positioning relative to the separation channel was investigated. The performance of the different detectors is compared for the analysis of organic carboxylic acid anions.

Conductivity detection cell for capillary zone electrophoresis with a solution mediated contact of the separated constituents with the detection electrodes

A contact conductivity detection cell for capillary zone electrophoresis (CZE) with an electrolyte solution mediated contact of the separated constituents with the detection electrodes (ESMC cell) was developed in this work. This new approach to the conductivity sensing in CZE is intended to eliminate detection disturbances due to electrode reactions and adsorption of the separated constituents when these are coming into direct contact with the detection electrodes. An optimum detection performance of the cell was achieved when the carrier electrolyte solution mediated the electric contact of the detection electrodes with the separated constituents. Different compositions of the mediator and carrier electrolyte solutions led to large drifts of the detection signals. Isotachophoresis experiments performed in this context with the ESMC cell revealed that origins of these drifts are in transport processes (diffusion and electromigration) between the detection compartment and the detection electrodes in the cell. These processes affected, to some extent, other analytically relevant performance parameters of the ESMC cell of the present construction as well [e.g., concentration limits of detection (LODs), a contribution of the cell to the band broadening]. For example, the ESMC cell gave, under optimum operating conditions, 3–4 times higher concentration LODs for the test analytes than a current on-column conductivity cell employed under identical working conditions. On the other hand, these LOD values (25–150 nmol/l) were still 20–25 times lower than those estimated from reference experiments for a contactless conductivity detector. CZE experiments with iodide, carried out under working conditions leading to electrochemical reactions of this anion on the detection electrodes of current conductivity cells, did not occur in the ESMC cell. In addition, this cell, contrary to a reference contact conductivity cell, required no special care (e.g., cleaning of the surfaces of the detection electrodes by chemical or electrochemical means) to maintain its reliable long-term performance. Anionic CZE analyses of tap and mineral water samples monitored by the conductivity detector provided with the ESMC cell demonstrated a practical applicability and certain limitations of this detection approach in the analysis of ionic constituents present in high ionic strength sample matrices.

A new PMMA-microchip device for isotachophoresis with integrated conductivity detector

This report describes the design, fabrication and use of new microanalytical devices based on polymer substrates for electrophoretic methods, especially isotachophoresis. The devices are fabricated by hot embossing and are sealed with a thin plexiglas cover plate which contains platinum electrodes for contact conductivity detection and power supply. Poly(methylmethacrylat) (PMMA) shows good prospects for the development of low-cost disposable or semi-disposable microanalytical devices. Two different chip-designs are introduced to demonstrate the advantages of the manufacturing procedure and the use of poly(methylmethacrylat) as substrate material. The channel system on the chips is equipped with two sample loops with different volumes to take advantage of the high sample loadability and the enrichment qualities of isotachophoresis. In addition, two separation columns allow two-dimensional on-column ITP–ITP- and CZE–ITP-coupling. Separations of organic acids are used to demonstrate the principle of the isotachophoresis-chips.