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This work presents a lab-made automatic flow-batch system for headspace single-drop microextraction and on-drop conductometric sensing ammonium. Sample and NaOH solution are simultaneously pumped into a reaction chamber (RC), where ammonium is converted to ammonia by raising pH. The converted ammonia then diffuses into the headspace of the RC, and reacts with a 100 mM boric acid drop. The conductivity of the drop is measured by an on-drop conductivity probe, which is made by two stainless-steel contacting electrodes. The result shows that the increasing rate of conductivity has a linear relationship to the ammonium concentration in sample (R2 = 0.9945). This method has a linear range up to 400 μM, a limit of detection 2.8 μM, a relative standard deviation of 3.0% (200 μM, n = 10) and carryover coefficient 0.028. Measurements of river waters, lake waters and wastewaters have been demonstrated. The recoveries have achieved from 99.0 to 114%. This method avoids using of harmful or odorous reagents and follows the concept of green chemistry.

The aim of this work was to develop an array of biosensors for simultaneous determination of four carbohydrates in solution. Several enzyme systems selective to lactose, maltose, sucrose and glucose were immobilised on the surface of four conductometric transducers and served as bio-recognition elements of the biosensor array. Direct enzyme analysis carried out by the developed biosensors was highly sensitive to the corresponding substrates. The analysis lasted 2 min. The dynamic range of substrate determination extended from 0.001 mM to 1.0–3.0 mM, and strongly depended on the enzyme system used. An effect of the solution pH, ionic strength and buffer capacity on the biosensors responses was investigated; the conditions of simultaneous operation of all biosensors were optimised. The data on cross-impact of the substrates of all biosensors were obtained; the biosensor selectivity towards possible interfering carbohydrates was tested. The developed biosensor array showed good signal reproducibility and storage stability. The biosensor array is suited for simultaneous, quick, simple, and selective determination of maltose, lactose, sucrose and glucose.

In the past decades, many efforts have been made to improve the sensitivity and specificity of electrochemical DNA biosensors. However, it is still strongly required to develop disposable and reliable DNA biosensors for wide and practical application. In this article, we reported superior electrochemical properties of an integrated plastic-gold electrode (PGE) fabricated in-house by chemical plating on polystyrene substrate. PGEs were found having extremely high capacity of DNA immobilization compared with gold electrodes fabricated by standard sputtering based photolithography. Unique nano-structured surface was observed on PGEs through morphology techniques, which would to some extend give an explanation to higher capacity of DNA immobilization on PGEs. A probable mechanism of carboxylic acid produced on polystyrene substrate after exposure to UV irradiation was proposed and discussed for the first time. This biosensor was applied to detection and manipulate of DNA hybridization. Detection limit of 7.2×10(-11) M and 1-500 nM of linearity range was obtained.

International audience; A highly sensitive conductometric biosensor for l-arginine determination was developed by exploiting the unique biorecognition capacities of two enzymes of urea cycle - arginase (E.C. 3.5.3.1) and urease (E.C. 3.5.1.5). The enzymes were co-immobilized in a single bioselective membrane on the working sensor, while a lysine rich bovine serum albumin (BSA) membrane was immobilized on the reference sensor, allowing differential measurements. The optimum percentage ratio of arginase and urease within the bioselective membrane was determined when the biosensor sensitivity to l-arginine and urea was optimum. Analytical characteristics of the conductometric biosensor for l-arginine determination were compared for two types of enzyme immobilization (cross-linking with glutaraldehyde (GA) and entrapment in the polymeric membrane). The optimum features in terms of the sensitivity, the linear range, and the detection limit (4.2 μS/mM, 0.01-4mM, and 5.0 × 10(-7)M, respectively) were found for l-arginine biosensor based on enzyme cross-linking with GA. A quantitative determination of l-arginine in the real sample (a drinkable solution "Arginine Veyron") gave a satisfactory result compared to the data provided by the producer (a relative error was 4.6%). The developed biosensor showed high operational and storage stability.

An improved method for the assay of trifluoroacetic acid (TFA) in a cyclosporin-like drug substance is presented, based on ion chromatography with suppressed conductivity detection. Column fouling by the drug molecule is avoided by use of a sample preparation method in which the drug substance is precipitated at alkaline pH whilst the TFA remains in solution. The new method requires a smaller sample mass than a previous method based on headspace-GC-FID whilst achieving an improvement in sensitivity. During validation, the method's performance was found to be consistent with usual acceptance criteria, and the method was found to be robust in routine use.

Pressure assisted capillary electrophoresis in capillaries with internal diameters of 10 μm was found possible without significant penalty in terms of separation efficiency and sensitivity when using contactless conductivity detection. A sequential injection analysis manifold consisting of a syringe pump and valves was used to impose a hydrodynamic flow in the separation of some inorganic as well as organic cations. It is demonstrated that the approach may be used to optimize analysis time by superimposing a hydrodynamic flow parallel to the electrokinetic motion. It is also possible to improve the separation by using the forced flow to maintain the analytes in the capillary, and thus the separation field, for longer times. The use of the syringe pump allows flexible and precise control of the pressure, so that it is possible to impose pressure steps during the separation. The use of this was demonstrated for the speeding up of late peaks, or forcing repeated passage of the sample plug through the capillary in order to increase separation.

Poly(glycidyl methacrylate) cation exchange monolithic column was prepared in fused-silica capillaries of 320 μm i.d. by thermally initiated radical polymerization and utilized in capillary ion chromatography. With 15 mM methanesulfonic acid as the mobile phase, the separations of a mixture of inorganic cations (Li + , Na + , NH 4 + , K + ) was tested by using a capacitively coupled contactless conductivity detector (C 4 D) and a low impedance C 4 D (LIC 4 D). The LIC 4 D is the series combination of a C 4 D and a quartz crystal resonator. At the resonant frequency of the series combination, the capacitor impedance from capillary wall was offset by the inductance impedance from the quartz crystal resonator. A minimum impedance was obtained in the impedance–frequency curve of the combination. The responses of the C 4 D and LIC 4 D were analyzed based on an equivalent circuit model. It was shown that the sensitivity of the C 4 D to the change in analyte concentration is rather poor due to the high ratio of the impedance from the capillary wall capacitor to the solution impedance. The LIC 4 D has the similar sensitivity as a contact conductivity detector but a much smaller cell volume. The on-column detection model was realized by LiC 4 D without preparation of optical detection window in monolithic column.

This work presents a flow analysis method for direct quantitation of calcium carbonate in cement without pretreatment of the sample. The method is based on online vaporization of CO 2 gas following acidification of the sample inside a small chamber that has a flow of acceptor solution passing around it. Solubilization of the CO 2 gas into the acceptor stream changes the conductivity of the acceptor solution causing an increase of signal at the capacitively coupled contactless conductivity detection (C 4 D) placed at the outlet of the vaporization chamber. This chamber is an adaption from previous work reported on ‘membraneless vaporization’ (MBL-VP). The method can be used in the quality control of production of mixed cement. These cement materials usually have calcium carbonate contents at high concentration range (e.g., 33–99% (w/w) CaCO 3 ). Analysis of samples by this method is direct and convenient as it requires no sample pretreatment. The method is low-cost with satisfactory accuracy and acceptable precision.

A new conductometric biosensor has been developed for the determination of short chain primary aliphatic alcohols. The biosensor assembly was prepared through immobilization of alcohol oxidase from Hansenula sp. and bovine liver catalase in a photoreticulated poly(vinyl alcohol) membrane at the surface of interdigitated microelectrodes. The local conductivity increased rapidly after alcohol addition, reaching steady-state within 10 min. The sensitivity was maximal for methanol (0.394+/-0.004 microS microM(-1), n=5) and decreased by increasing the alcohol chain length. The response was linear up to 75 microM for methanol, 70 microM for ethanol and 65 microM for 1-propanol and limits of detection were 0.5 microM, 1 microM and 3 microM, respectively (S/N=3). No significant loss of the enzyme activities was observed after 3 months of storage at 4 degrees C in a 20mM phosphate buffer solution pH 7.2 (two or three measurements per week). After 4 months, 95% of the initial signal still remained. The biosensor response to ethanol was not significantly affected by acetic, lactic, ascorbic, malic, oxalic, citric, tartaric acids or glucose. The bi-enzymatic sensor was successfully applied to the determination of ethanol in different alcoholic beverages.

In this study, a cation-exchange resin (CEX) of the K(+)-form, i.e., an enhancer resin, is used as a postcolumn conductimetric enhancer in the ion-exclusion chromatography of aliphatic carboxylic acids. The enhancer resin is filled in the switching valve of an ion chromatograph; this valve is usually used as a suppressor valve in ion-exchange chromatography. An aliphatic carboxylic acid (e.g., CH(3)COOH) separated by a weakly acidic CEX column of the H(+)-form converts into that of the K(+)-form (e.g., CH(3)COOK) by passing through the enhancer resin. In contrast, the background conductivity decreases because a strong acid (e.g., HNO(3)) with a higher conductimetric response in an eluent converts into a salt (e.g., KNO(3)) with a lower conductimetric response. Since the pH of the eluent containing the resin enhancer increases from 3.27 to 5.85, the enhancer accelerates the dissociations of analyte acids. Consequently, peak heights and peak areas of aliphatic carboxylic acids (e.g., acetic acid, propionic acid, butyric acid, and valeric acid) with the enhancer resin are 6.3-8.0 times higher and 7.2-9.2 times larger, respectively, than those without the enhancer resin. Calibrations of peak areas for injected analytes are linear in the concentration range of 0.01-1.0mM. The detection limits (signal-to-noise ratio=3) range from 0.10 microM to 0.39 microM in this system, as opposed to those in the range of 0.24-7.1 microM in the separation column alone. The developed system is successfully applied to the determination of aliphatic carboxylic acids in a chicken droppings sample.

Capillary electrophoresis (CE) with capacitively coupled contactless conductivity detection (C 4 D) was used for rapid, accurate and simultaneous determination of free fluoride and monofluorophosphate (MFP) in six different toothpaste samples. A buffer solution containing 15 mmol L −1 histine, 25 mmol L −1 lactic acid, and 2.5 mmol L −1 tetradecyltrimethylammonium bromide (TTAB) was used as background electrolyte (BGE). A complete separation of the analytes and the internal standard (tartrate) could be attained in less than 2.5 min. The limits of detection (LOD) and quantification (LOQ) were, respectively, 0.17 and 0.57 mg L −1 for free fluoride and 0.70 and 2.33 mg L −1 for MFP. Recoveries ranging from 85 to 107% were obtained for samples spiked with standard solutions of free fluoride or MFP. The CE-C 4 D method was compared to an ion-selective electrode (ISE) method and the results were in good agreement. More importantly, the CE-C 4 D method demonstrates the advantage of being able to determine MFP without a prior hydrolysis step.

A fast ion chromatographic method with suppressed conductivity detection has been developed for the simultaneous determination of methane-, ethane-, 1-propane-, 1-butane-, 1-pentane-, 1-hexane-, 1-heptane-, 1-octane-, 1-nonane-, 1-decane-, 1-dodecane-, dodecylbenzene-, p -toluene-, benzenesulfonic acids, octylsulfate and dodecylsulfate in water samples. Due to the high number of analytes and their heterogeneity, the effect of the mobile phase parameters (NaOH, CH 3 OH and CH 3 CN concentration) on the retention factors has been studied in detail, so achieving, for the first time, the separation among 15 of these analytes by a gradient elution. Detection limits included within 0.06–0.16 μM have been obtained. Interferences from Cl − , NO 3 − and SO 4 2− , possible anions present in water samples, have been considered and a SPE procedure has been developed for analytes enrichment and matrix removal in a seawater sample. This is the first application of an ion-exchange chromatographic method to a seawater sample for this kind of analytes.

Complex matrices and rather high acidity in environmental samples are often the impelling challenges for the used running buffers of capillary electrophoresis. Twelve binary acid-base buffers were evaluated for separation of Cr(VI)/Cr(III), Co(2+) and Zn(2+) in a sample containing various salts by capillary electrophoresis with contactless conductivity detector. The malic acid (MA) systems including MA-His (histidine), MA-Arg (arginine) and MA-Tris (tris(hydroxymethyl)aminomethane) were selected as the candidates with powerful separation efficiency and good response sensitivity. In the MA-Tris buffer, optimization were further carried out in terms of the pH value and the concentration of MA, and the optimal conditions were obtained as 6mM MA-Tris and 2mM 18-crown-6 at pH 3.5. Furthermore, a real application was demonstrated by analyzing the plating rinse water (pH 0.8), in which the Ca(2+), Na(+), Cr(VI)/Cr(III), Co(2+) and Zn(2+) were all detected by adjusting at pH 3.5 with 5% (v/v) diluent ammonia. Both the cations, e.g., K(+), Ca(2+), Na(+), Mg(2+), and the common high concentration anions in the sample, e.g., Cl(-), SO(4)(2-) and NO(3)(-) did not cause any disturbance to the concerned analytes.

A cost effective flow injection (FI) conductometric system has been developed for determination of total inorganic nitrogen (TIN). The system is aimed for evaluation of nitrogen nutrient in soil for agricultural application. Inorganic nitrogen compounds were extracted from soil according to the standard method by using potassium chloride solution as an extractant, and the extracted solution was then injected into the FI system. Nitrate and nitrite are converted to ammonium ion by an in-line reduction column packed with a Devarda's alloy. A gas diffusion unit was incorporated into the FI system to separate ammonium ion from other ions in a donor stream by forming ammonia gas that can diffuse through a PTFE membrane to re-dissolve in an acceptor stream. Conductance of the acceptor stream was directly proportional to ammonium ion concentration. Various parameters affecting reduction efficiency of the column, e.g., column diameter, column packing procedure, and column length was investigated and optimized. A linear calibration graph in the range of 2.00-60.00 mg L(-1) N-NH4(+) (y=0.123x+0.039, R(2) =0.997) was obtained with a limit of detection of 0.47 mg L(-1). Sample throughput of 20 samples h(-1) was achieved. The result of developed method was correlated with total Kjeldahl nitrogen (TKN) obtained from the Kjeldahl digestion method. The proposed method could be used as an alternative method to the Kjeldahl method for determination of TIN in soil.

Ion-exclusion/adsorption chromatography of dimethylsulfoxide (DMSO) and its derivatives, i.e., methanesulfinic acid (MSI), methanesulfonic acid (MSA) and sulfuric acid (SA), was developed in order to clear the decomposition mechanism of DMSO on quality-test of TiO2-photocatalyst in water. The separation was achieved by the adsorption effect for DMSO and ion-exclusion effect for MSI, MSA and SA under optimum conditions, using a weakly acidic cation-exchange resin column with 20 mM succinic acid as the eluent. In this system, DMSO and MSI with UV at 195 nm and MSA and SA with conductivity detection were consecutively determined by single injection and single separation column. This method was used to monitor the artificial decomposition of DMSO induced by a photocatalyst. The concentration of DMSO by active oxygens (e.g., OH radical) generated from surface of photocatalyst was found to be decreased through the stoichiometric reaction in the order of MSI, MSA and SA.

A highly sensitive, fast and stable conductometric enzyme biosensor for determination of nitrate in water is reported for the first time. The biosensor electrodes were modified by methyl viologen mediator mixed with nitrate reductase (NR) from Aspergillus niger by cross-linking with glutaraldehyde in the presence of bovine serum albumin and Nafion((R)) cation-exchange polymer. The process parameters for the fabrication of the enzyme electrode and various experimental variables such as pH, the enzyme loading and time of immobilization in glutaralaldehyde vapor were investigated with regard to their influence on sensitivity, limit of detection, dynamic range and operational and storage stability. The biosensor can reach 95% of steady-state conductance value in about 15s. Linear calibration in the range of 0.02 and 0.25 mM with detection limits of 0.005 mM nitrate was obtained with a signal-to-noise ratio of 3. When stored in 5 mM phosphate buffer (pH 7.5) at 4 degrees C, the sensor showed good stability over 2 weeks.

A chemometric method for analysis of conductometric titration data was introduced to extend its applicability to lower concentrations and more complex acid-base systems. Auxiliary pH measurements were made during the titration to assist the calculation of the distribution of protonable species on base of known or guessed equilibrium constants. Conductivity values of each ionized or ionizable species possibly present in the sample were introduced in a general equation where the only unknown parameters were the total concentrations of (conjugated) bases and of strong electrolytes not involved in acid-base equilibria. All these concentrations were adjusted by a multiparametric nonlinear regression (NLR) method, based on the Levenberg-Marquardt algorithm. This first conductometric titration method with NLR analysis (CT-NLR) was successfully applied to simulated conductometric titration data and to synthetic samples with multiple components at concentrations as low as those found in rainwater (approximately 10 micromol L(-1)). It was possible to resolve and quantify mixtures containing a strong acid, formic acid, acetic acid, ammonium ion, bicarbonate and inert electrolyte with accuracy of 5% or better.

The determination of diuron, atrazine, desisopropylatrazine (DIA) and desethylatrazine (DEA) were investigated using conductometric tyrosinase biosensor. Tyrosinase was immobilised on the biosensor sensitive part by allowing it to mix with bovine serum albumin (BSA) and then cross-linking in saturated glutaraldehyde (GA) vapour for 30min. The determination of pollutants in a solution was performed by comparison of the output signal (i.e percentage of the enzymatic activity) of the biosensor before and after contact with pollutants. The measurement of the enzymatic activity was performed using 4-chlorophenol, phenol and catechol substrates and response times ranging from 1 to 5min were observed. A 4-chlorophenol substrate was used to detect pesticides. A 30min contact time of the biosensor in the pollutant solution was used. Under the experimental conditions employed, detection limits for diuron and atrazine were about 1ppb and dynamic range of 2.3-2330 and 2.15-2150ppb were obtained for diuron and atrazine, respectively. A relative standard deviation (n=3) of the output signal was estimated to be 5% and a slight drift of 1.5muSh(-1) was observed. The 90% of the enzyme activity was still maintained after 23 days of storage in a buffer solution at 4 degrees C.

A mobile drop based approach was utilized for the conductometric determination of aqueous ammonium ion. A liquid drop was manipulated by gravity to remain or move out of a conductivity measurement zone located on a hydrophobic path. A dilute sulfuric acid drop functioned as a micro gas absorber. Gaseous NH3 was liberated from a sample containing NH4(+) by adding NaOH and purged to flow over the absorber drop. As H(+) in the absorber drop was converted to NH4(+), the conductivity decreased. The rate of the conductivity decrease thus ultimately depended on the NH4(+) concentration in the sample. While the sample could be complex, the liberation of NH3 gas essentially freed the analyte of interest from the matrix and allowed the use of an otherwise nonselective detector. The system was applied to the determination of NH4(+) in some natural waters without prior filtration; the results agreed well with those from a manual indophenol blue method. The approach exhibited a limit of detection (LOD) of 5 μM and a relative standard deviation (RSD) of5%. The mobile drop gave a constant volume of the gas absorbing solution and provided a cost-effective and simple analytical platform.

The aggregation of teicoplanin was studied in four solutions: 0.06 M phosphate buffers pH 4.3 and 6.3, both with and without 10% (v/v) of acetonitrile. Conductometry, capillary electrophoresis, cyclic voltammetry, and static light scattering were employed to determine the critical micelle concentration (CMC) of teicoplanin. Dynamic light scattering was used to give an additional information on the size and the size distribution of the particles formed. While the CMC was found in solutions without acetonitrile, attempts to detect any CMC failed in solutions containing acetonitrile. The results point out to different solvating mechanism in solutions with and without acetonitrile, leading to two different schemes of association.

A simple, rapid and accurate method for the determination of iodate in iodized common salts has been developed. The quantitative determination of iodate was accomplished by anion exchange chromatography with conductimetric detection. The method requires a sample pretreatment for the removal of large excess of chloride from the sample matrix. Onguard silver cartridges were found most suitable for this purpose. The sulphate content in the salt was simultaneously determined. The lower limits for the determination of iodate and sulphate in solution are 0.5 and 0.05 μg ml−1, respectively. Quantitative recovery of the anions in synthetic samples has been obtained and the interferences from different cations and anions have been studied. The method has been successfully applied to the determination of iodate and sulphate in the commercially available salts. The concentrations of iodate measured by this method are in good agreement with those claimed by the manufacturer.

A simple method for simultaneous determination of three catecholamines using ion chromatography (IC) with direct conductivity detection (CD) based on the ionization of catecholamines in acidic medium without chemical suppression is developed in the present paper. The method could be used for the determination of these catecholamines in pharmaceutical preparations for the purpose of drug quality control. The recovery of catecholamines was more than 97% (n=3) and the relative standard deviation (R.S.D.) (n=11) was less than 2.1%. In a single chromatographic run, norepinephrine (NE), epinephrine (E) and dopamine (DA) can be determined in less than 10 min. The detection limits were found to be 0.001 microg/ml for NE, 0.01 microg/ml for E and DA respectively. Linear ranges were 0.01-50 microg/ml for NE (r(2)=0.9998), 0.1-50 microg/ml for E (r(2)=0.9995) and DA (r(2)=0.9999), respectively.

Two simple flow injection (FI) procedures for the determination of ascorbic acid content in a vitamin C tablet are proposed: spectrophotometric involving injection into a stream of acidic potassium permanganate solution and monitoring its color change due to the redox reaction; FI conductometry based on the neutralization of ascorbic acid injected into a flowing ammonia solution yielding a change in conductivity. The procedures have been applied to the analysis of locally commercial vitamin C tablet samples. A through-put of at least 90 injections h(-1) can be achieved. The relative standard deviation was found to be 2.5% (for a 50 mg vitamin C tablet; n=7) for both. Results obtained by either procedure agree with a standard titrimetric method.

Sensors for determining humidity in air have been described and investigated. Sensing film of the devices was prepared from polyvinylalcohol and graphitized carbon black disperse phase. The composition, thermal treatment and design of sensing films were investigated and optimized. An optimized humidity sensor has better metrological parameters as compared with its prototype (response time approximately 45 s, detection limit 0.17%, slope 6.25 +/- 0.05 Theta/R.H., standard deviation of measurement 0.15%, standard deviation of analytical signal in the graduation equation 8.29Theta). Such construction of sensors have prospects in analytical practice.

The complexation reaction between a macrocyclic polyether, 18-crown-6 (18C6), and potassium ion was studied in methanol (MeOH)-acetonitrile (AN), dimethylformamide (DMF)-AN and propylecarbonate (PC)-DMF binary solvent systems at different temperatures using a conductometric method. It was found that the stability of the 1:1 complex formed between K(+) ion and this ligand increases with decreasing temperature. Standard enthalpies and standard entropies of the complex formation were obtained from the temperature dependence of the stability constant. In all cases negative DeltaH(o)(c) and DeltaS(o)(c) values characterize the formation of 18C6-K(+) complex. The results obtained show that the stability of the complex is governed by the solvent medium and the thermodynamic parameters DeltaH(o)(c), DeltaS(o)(c) and DeltaG(o)(c) are sensitive to the composition of the mixed solvents. In addition, it was found that the stability constant of the resulting 1:1 complex among various neat solvents used varies in the order PCMeOHANDMF.

The isohydricity property, referred to systems composed of acids or bases, is presented. The related isohydricity conditions are formulated for different pairs of solutions. The pH titrations in the system of isohydric solutions are put in context with conductometric titrations. The differences between pK1 values obtained according to both methods are not too significant and the conductometric titration can be perceived, in some instances, as a reasonable alternative to the pH titration.

A FIA system using a pH-sensitive detector based on a graphite/quinhydrone/silicone composite electrode was applied to determine sequentially the titratable acidity and the pH of wine, as well as the sum of calcium and magnesium ions. For all measurements the same FIA configuration was used employing different carrier solutions. The results for the determination of acidity and pH are in good agreement with those obtained by classical potentiometric titrations and by pH measurements using a conventional glass electrode. The standard deviation was less than 1.5% for both kinds of measurements and the sample volume was 150 μL. The method allows about 40 determinations of titratable acidity per hour and 30 pH measurements per hour. The titration method can be adjusted to the legal requirements in USA and Europe.

An analytical method for the determination of the composition of renal stones by capillary isotachophoresis with conductometric detection was developed. Using different leading/terminating electrolyte systems, the qualitative and quantitative analysis of organic compounds (urate, xanthate, oxalate) and inorganic ions (phosphate, Ca(2+), Mg(2+), Na(+), NH(4)(+)) species commonly present in mixed renal stones in three separate steps can be carried out with limits of detection about 10 μmol/L. The developed method was validated by the analysis of real samples and can be used for urinary calculi classification. In addition, it was verified that this method can also be employed for the determination of the above mentioned analytes in some other samples (bones, teeth) concerning apatite biominerals (fluoro-, carbonate-, chloro-apatite).

A new approach was developed for urea determination where a thin film of silicalite and zeolite Beta deposited onto gold electrodes of a conductometric biosensor was used to immobilize the enzyme. Biosensor responses, operational and storage stabilities were compared with results obtained from the standard membrane methods for the same measurements. For this purpose, different surface modification techniques, which are simply named as Zeolite Membrane Transducers (ZMTs) and Zeolite Coated Transducers (ZCTs) were compared with Standard Membrane Transducers (SMTs). Silicalite and zeolite Beta with Si/Al ratios 40, 50 and 60 were used to modify the conductometric electrodes and to study the biosensor responses as a function of changing zeolitic parameters. During the measurements using ZCT electrodes, there was no need for any cross-linker to immobilize urease, which allowed the direct evaluation of the effect of changing Si/Al ratio for the same type of zeolite on the biosensor responses for the first time. It was seen that silicalite and zeolite Beta added electrodes in all cases lead to increased responses with respect to SMTs. The responses obtained from ZCTs were always higher than ZMTs as well. The responses obtained from zeolite Beta modified ZMTs and ZCTs increased as a function of increasing Si/Al ratio, which might be due to the increased hydrophobicity and/or the acid strength of the medium.

The experimental system involves the permeative preconcentration of CO2 from an acidified sample through a tubular silicone rubber membrane into a suitable receptor. Procedures for measuring the CO2 collected in the receptor by the absorbance change of an acid—base indicator incorporated in the receptor or by the conductance change of the receptor are compared. Previous theoretical considerations of the photometric system are augmented for numerical modeling and the theoretical behavior of the conductometric system is considered in detail. Experimental data generally conform to theoretical expectations. Based on either reproducibility or sensitivity, the conductometric measurement method using a solution of 1–10mM tris(hydroxymethylamino)methane as receptor is recommended. The interference from sulfite or sulfide can be eliminated by adding acidic permanganate to the sample; considerably more involved arrangements are necessary to eliminate interferences from cyanide.

This work describes the characterization and potential applications of a silica-based anion-exchange phase prepared by a two-step modification process that incorporates a propylpyridinium group. The effects of pH and eluent concentration on anion separation were examined using 150 mm × 3.9 mm HPLC columns packed with the new phase. The mobile phase pH values ranged from 3.8 to 6.6 using phthalic acid/Tris solutions. The best separation was achieved using 2.5 mmol L(-1) phthalate/2.4 mmol L(-1) Tris solution at pH 4.2 as mobile phase with non-suppressed conductivity detection. The new stationary phase was used for the separation of some inorganic and organic anions showing good resolution. The stability of the silica-based anion exchange phase was also evaluated. Analytical curves, for concentrations ranging from 0.25 to 10 mg L(-1) for the inorganic anions chloride, nitrite, bromide and nitrate, showed good linear correlations (r>0.998). The method was tested with certified rainwater samples. The measured and certified values were in good agreement, indicating that the new phase holds significant promise for the analysis of these anions in environmental samples.

A novel long drop time mercury electrode has been constructed from common fused-silica capillary (50 μm I.D., 360 μm E.D.). Proposed device provides reproducible mercury drops with typical lifetime 40–120 s. The electrode was used for a set of electrocapillary measurements aimed at determination of critical micelle concentration of anionic surfactants by a convection controlled drop-time technique. A critical micelle concentration of sodium dodecyl sulfate 5.6 ± 0.4 mmol L −1 and 4.3 ± 0.4 mmol L −1 were obtained in 1 mmol L −1 and 5 mmol L −1 phosphate buffer (pH 7.0), respectively. The values were comparable to those obtained from conductometric measurements under the same conditions (7.0 ± 0.1 mmol L −1 and 5.2 ± 0.1 mmol L −1 , respectively) and the difference was explained in accordance with theory of hemi-micelle formation.

A method was developed to determine traces of trifluoroacetic acid as impurity in synthetic or semi-synthetic drugs as antibiotics, macropeptides, etc. Capillary electrophoresis in combination with capacitively coupled contactless conductivity detection (CE-C(4)D) was used due to lack of UV absorbance property of trifluoroacetic acid (TFA). The optimized method took less than 1 min with good linearity (R(2)=0.9995) for trifluoroacetic acid concentration from 2 to 100 ppm. It also has a good repeatability expressed by the relative standard deviation (% RSD) which is 1.2 and 2.1% for intraday and interday precision, respectively, at 50 ppm TFA, and good sensitivity with 0.34 ppm, 1.2 ppm LOD and LOQ, respectively. In addition, the content of TFA in synthetic drug, was determined using the validated method which gave good linearity (R(2)=0.9996) for trifluoroacetic acid spiked into drug in a concentration range of 2-80 ppm, with good intraday repeatability of 2.0%. The analysis is performed in a background electrolyte composed of 20mM morpholinoethane-sulfonic acid (Mes) and 20mM L-histidine (L-His) pH 6.1. Cetyltrimethylammonium bromide (CTAB) was added as flow modifier in a concentration (0.2mM) lower than the critical micellar concentration. Ammonium formate 6 ppm was used as internal standard. The applied voltage was 30 kV in reverse polarity. A fused silica capillary with 75 μm internal diameter and total length 47 cm (31 cm to C(4)D detector and 37 cm to DAD detector) was used.

Potassium cyanide was used as a model toxicant to determine the feasibility of using anionic impurities as a forensic signature for matching cyanide salts back to their source. In this study, portions of eight KCN stocks originating from four countries were separately dissolved in water and analyzed by high performance ion chromatography (HPIC) using an anion exchange column and conductivity detection. Sixty KCN aqueous samples were produced from the eight stocks and analyzed for 11 anionic impurities. Hierarchal cluster analysis and principal component analysis were used to demonstrate that KCN samples cluster according to source based on the concentrations of their anionic impurities. The Fisher-ratio method and degree-of-class separation (DCS) were used for feature selection on a training set of KCN samples in order to optimize sample clustering. The optimal subset of anions needed for sample classification was determined to be sulfate, oxalate, phosphate, and an unknown anion named unk5. Using K-nearest neighbors (KNN) and the optimal subset of anions, KCN test samples from different KCN stocks were correctly determined to be manufactured in the United States. In addition, KCN samples from stocks manufactured in Belgium, Germany, and the Czech Republic were all correctly matched back to their original stocks because each stock had a unique anionic impurity profile. The application of the Fisher-ratio method and DCS for feature selection improved the accuracy and confidence of sample classification by KNN.

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the μg m(-3) range) and their variations with sampling site and time. In this work, a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE), a quick separation technique that requires nothing more than some nanoliters of sample and, when combined with capacitively coupled contactless conductometric detection (C(4)D), is particularly favorable for ionic species that do not absorb in the UV-vis region, like the target analytes formaldehyde, formic acid, acetic acid and ammonium. The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry's constant such as formaldehyde and carboxylic acids, or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8.3 nL s(-1)), while the sample was aspirated through the annular gap of the concentric tubes at 2.5 mL s(-1). A second unit, in all similar to the CMDS, was operated as a capillary membrane diffusion emitter (CMDE), generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS. The fluids of the system were driven with inexpensive aquarium air pumps, and the collected samples were stored in vials cooled by a Peltier element. Complete protocols were developed for the analysis, in air, of NH(3), CH(3)COOH, HCOOH and, with a derivatization setup, CH(2)O, by associating the CMDS collection with the determination by CE-C(4)D. The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot's reaction. Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction, solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW). All techniques and methods of this work are in line with the green analytical chemistry trends.

Compared to other volatile carbonylic compounds present in outdoor air, formaldehyde (CH(2)O) is the most toxic, deserving more attention in terms of indoor and outdoor air quality legislation and control. The analytical determination of CH(2)O in air still presents challenges due to the low-level concentration (in the sub-ppb range) and its variation with sampling site and time. Of the many available analytical methods for carbonylic compounds, the most widespread one is the time consuming collection in cartridges impregnated with 2,4-dinitrophenylhydrazine followed by the analysis of the formed hydrazones by HPLC. The present work proposes the use of polypropylene hollow porous capillary fibers to achieve efficient CH(2)O collection. The Oxyphan fiber (designed for blood oxygenation) was chosen for this purpose because it presents good mechanical resistance, high density of very fine pores and high ratio of collection area to volume of the acceptor fluid in the tube, all favorable for the development of air sampling apparatus. The collector device consists of a Teflon pipe inside of which a bundle of polypropylene microporous capillary membranes was introduced. While the acceptor passes at a low flow rate through the capillaries, the sampled air circulates around the fibers, impelled by a low flow membrane pump (of the type used for aquariums ventilation). The coupling of this sampling technique with the selective and quantitative determination of CH(2)O, in the form of hydroxymethanesulfonate (HMS) after derivatization with HSO(3)(-), by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D) enabled the development of a complete analytical protocol for the CH(2)O evaluation in air.

This study describes a new ion chromatography method using a low-capacity anion exchange column with amperometric and absorbance detection for rapid and simultaneous determination of Br(-) and NO(3)(-) in contaminated waters where one of these ions is present in excess compared to other. The use of two detectors overcomes the problem of baseline separation for Br(-) and NO(3)(-) for accurate quantification, which was commonly encountered when using a low-capacity anion exchange column and suppressed conductivity detection mode. The method achieved accurate quantification of these two ions without requirement of baseline separation. The accuracy of 2.8% for NO(3)(-) was determined using a quality control sample obtained from UN GEMS/Water PE Study No. 6. The detection limits for Br(-) and NO(3)(-) were 20 and 6 microg l(-1) (25 microl sample), respectively. Linearity of these two ions was over three orders of magnitude with a correlation coefficient0.998. The influence of potential interfering ions was also studied followed by the determination of Br(-) and NO(3)(-) in seawater, unsaturated zone water, soil extract and groundwater.

A method for determination of metabisulfite and hydrosulfite in poultice and decolorant by isotachophoresis was developed. Metabisulfite and hydrosulfite are ionizable oxoanions of sulfur of similar character that can easily be oxidized to sulfates. To protect the analytes from oxidation the solid samples were dissolved in a 1% (w/v) solution of formaldehyde. Hydrosulfite and metabisulfite present in the samples were transformed by the reaction with formaldehyde to stable compounds, hydroxymethanesulfinate and hydroxymethanesulfonate that were determined isotachophoretically without any pretreatment except for sample filtering and degassing. A capillary of 0.4mm i.d. and 100mm effective length made of fluorinated ethylene-propylene copolymer was filled with an electrolyte system consisting of 10 mmol L(-1) HCl+11 mmol L(-1) imidazole, 0.15% (w/v) hydroxyethylcellulose, pH 6.0 (leading electrolyte) and 5 mmol L(-1) benzoic acid+6 mmol L(-1) imidazole, pH 6.5 (terminating electrolyte). Separation was performed at a driving current of 80 microA and for detection current was decreased to 30 microA. Using contactless conductivity detection, the calibration curves in the tested concentration range up to 2.5 mmol L(-1) were linear for both metabisulfite and hydrosulfite complexes. The concentration detection limits for metabisulfite and hydrosulfite were 2.9 and 3.4 micromol L(-1), respectively. For 1 mmol L(-1) concentration, values of R.S.D. (n=6) were 2.6% for hydrosulfite and 0.8% for metabisulfite. Isotachophoretic determination took about 20 min. The elaborated isotachophoretic procedure is simple to perform, sufficiently sensitive and accurate. In addition to this, low cost of analyses makes the method an alternative procedure to methods used so far for the determination of oxoanions of sulfur.

Results of determination of selected imidazolium ionic liquids by isotachophoresis (ITP) with conductometric detection was presented. The effects of the molar mass of different ionic liquids on electrophoretic mobility was observed. The presented method was validated and basic validation parameters were determined. Limit of detection (LOD) in a 10 and 25 ng/L for anions and cations, respectively, is very satisfied. Thanks to its low cost and high rate, the presented method can be used in qualitative routine analysis as an alternative technique to liquid chromatography.

A microfabricated thin glass chip for contactless conductivity detection in chip capillary electrophoresis is presented in this contribution. Injection and separation channels were photolithographed and chemically etched on the surface of substrate glass, which was bonded with a thin cover glass (100 μm) to construct a new microchip. The chip was placed over an independent contactless electrode plate. Owing to the thinness between channel and electrodes, comparatively low excitation voltage (20–110 V in V p–p ) and frequency (40–65 kHz) were suitable, and favorable signal could be obtained. This microchip capillary electrophoresis device was used in separation and detection of inorganic ions, amino acids and alkaloids in amoorcorn tree bark and golden thread in different buffer solutions. The detection limit of potassium ion was down to 10 μmol/L. The advantages of this microchip system exist in the relative independence between the microchip and the detection electrodes. It is convenient to the replacement of chip and other operations. Detection in different position of the channel would also be available.

The review focuses on the analysis of small phosphorus-containing compounds by capillary electrophoresis (CE) with different detection modes including UV absorption, laser-induced fluorescence, conductometry, amperometry, atomic spectrometry, and mass spectrometry. Determinations of phosphates, organophosphate, and chemical warfare agents in environmental samples such as water, soil and grains are emphasized. To achieve better sensitivity, high-resolving power, and reproducibility, the optimum separation conditions for various analytes (samples) are different. We compare the merits and demerits of the different detection modes for the detection of the analytes. Although the present methods are successful in many cases, there is still a need to develop high-throughput CE techniques for screening numerous environmental samples and sample stacking techniques in CE for the analysis of trace analytes.

Capillary isotachophoresis (ITP), equipped with the conductivity detection, was tested for the separation of cetyltrimethylamonium (CTMA) bromide. To prevent adsorption of CTMA to the capillary walls, several neutral polymers and ethanol were added into the leading electrolytes. Unlike polymer additives, the CTMA free monomers and micelles, created as a result of the isotachophoretic concentration effect, were recognised in the presence of ethanol from 10 to 25% (v/v). At 30% of ethanol, only a single zone of CTMA monomer was registered because the micellization process did not take place under this condition. Employing an ITP apparatus in the column-coupling configuration, the operational system with 30% of ethanol was tested for the determination of CTMA in hair conditioners. The achieved detection limits were about 0.02 mM. Both model solutions and real samples of hair conditioners were analysed with the precision about R.S.D. = 3%. One analysis in the column-coupled system takes circa 15 min.

The adsorption of DPKSH onto silica gel was investigated, at 25±1 °C and pH 1, 4.7 and 12. For the same DPKSH concentration interval, the minimum required time of contact for adsorption maximum at pH 4.7 was smaller than at pH 1 and the maximum amount of DPKSH adsorbed per gram of silica at pH 1 is smaller than at pH 4.7. At pH 12 the DPKSH adsorption onto silica gel was not significant. The adsorption data followed Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherms. The maximum amount of solute adsorbed ( m ads max ) and the adsorption constant, K L , were derived from Langmuir isotherm. The Freundlich constants 1/ n and K F related, respectively, to the energetic heterogeneity of adsorption sites and an empirical constant were evaluated. The mean sorption free energy ( E ) of DPKSH adsorption onto silica gel was calculated from D–R isotherm indicating a physical adsorption mode. Finally, conductimetric titrations showed the silica particle basicity and acidity as 0.002 and 0.3 mmol g −1 , respectively.

Macrocyclic polyethers are ligands with selectivity for metal ions. In order to understand the interactions between ligand, ion and solvent we resorting to study of magnetic field effect on ion-macrocyclic complexes. Therefore, we studied the complexation between 18-crown-6 and potassium ion in water through the conductometry technique (in 25+0.05 °C) by a nonlinear least-square program (Genplot) under magnetic field. We observed that stability constants of complexes in the presence of the magnetic field, were decreased. Like-wise, we observed that, magnetic field influenced on ion, solvent and ligand one by one.

Conductometric replacement titrations of humic and fulvic acids dissolved in a slight excess of hydroxide were carried out with standard acid. The slope of the titration curve corresponding to the protonation of humate/fulvate was related to the electrophoretic mobility of the polyanions or aggregates, and hence to their dimensions. Promising qualitative agreement was found between sizes of a number of these species and their conductance slopes. Both the separation of humic fractions and size reduction by photolysis and sonication led to the anticipated decrease in slope. The slight reduction in slope observed during the course of the titration was tentatively ascribed to contraction of the expanded (drained) humic aggregates.

An original concept of an enzyme multibiosensor for determination of toxic substances based on enzyme inhibition analysis has been proposed and its main performances have been analysed. For the development of this multibiosensor, two types of transducers such as potentiometric pH-sensitive field-effect transistors and conductometric thin-films interdigitated electrodes, and three enzymes, namely urease, acetylcholinesterase and butyrylcholinesterase have been used. The experimental data have been treated by multivariate correspondence analysis. A complete procedure for a simultaneous determination of some heavy metal ions and pesticides has been proposed and its advantages have been discussed.