Isotachophoresis-capillary Zone Electrophoresis Research Articles

Transient isotachophoresis–Capillary zone electrophoresis–Mass spectrometry method with off-line microscale solid phase extraction pretreatment for quantitation of intact low molecular mass proteins in various biological fluids

Quantification of proteins is still predominantly done by the traditional bottom-up approach. Targeting of intact proteins in complex biological matrices is connected with multiple challenges during the sample pretreatment, separation, and detection step of the analytical workflow. In this work, we focused on the development of an on-line hyphenated capillary zone electrophoresis-mass spectrometry method employing off-line microscale solid-phase extraction based on hydrophilic lipophilic balance (HLB) sorbent as a sample pretreatment step for the analysis of low molecular mass intact proteins (<20 kDa) spiked in various biological fluids (human serum, plasma, urine, and saliva). A detailed optimization process involved the selection of a suitable capillary surface, background electrolyte (BGE), and comparison of two in-capillary preconcentration methods, namely transient isotachophoresis (tITP) and dynamic pH junction (DPJ), to enhance the sensitivity of the method. Optimum separation of the analytes was achieved using uncoated bare fused silica capillary employing 500 mM formic acid (pH 1.96) + 5 % (v/v) acetonitrile as BGE. tITP was utilized as an optimum preconcentration technique, achieving a 19- to 127-fold increase in the signal intensity when using 200 mM ammonium formate (adjusted to pH 4.00) as the leading electrolyte and BGE as the terminating electrolyte. Off-line microscale solid-phase extraction with various eluate treatment procedures was evaluated to ensure the compatibility of the sample pretreatment method with the selected in-capillary preconcentration, separation, and detection process. Achieved extraction recoveries of spiked proteins were in the range of 76–100 % for urine, 12–54 % for serum, 21–106 % for plasma, and 25–98 % for saliva when the eluate was evaporated and reconstituted in the solution of the leading electrolyte to achieve the tITP process. The optimum method was validated across different biological matrices, offering good linearity, accuracy, and precision, and making it suitable for proteomic studies (e.g., therapeutic drug monitoring, biomarker research) in different biological samples.

Ultrasensitive determination of serotonin in human urine by a two dimensional capillary isotachophoresis-capillary zone electrophoresis hyphenated with tandem mass spectrometry

A two-dimensional capillary isotachophoresis-capillary zone electrophoresis method hyphenated with tandem mass spectrometry was developed and validated for ultrasensitive quantification of serotonin in real human urine samples. Under optimal conditions, the separation was achieved within 12 min (including on-line sample preparation) with the limit of detection of 34 pg mL−1 (due to a large volume sample injection, here 10 µL, and isotachophoretic preconcentration). This concentration limit represents the lowest value for serotonin in comparison to other previously published separation methods employing mass spectrometry detection and applied to urine matrices. Thanks to high orthogonality, on-line concentration and clean-up effects of this approach, other excellent validation parameters such as linearity (coefficient of determination > 0.99), inter-day and intra-day precision (relative standard deviations 3.5–12.2%), accuracy (relative errors within 99–109.4%), and recovery (96–102%) could be easily obtained too. To demonstrate applicability of the method, we monitored serotonin levels in various real samples (from a healthy volunteer and clinical ones). The determined levels, normalized on the creatinine concentrations, were in the range of 6.81–12.86 ng mmol−1 creatinine This advanced method is suggested for an effective, reliable, high sample throughput, and low cost routine clinical screening or targeted metabolomic studies of serotonin in urine samples.

DNA fragment separations by on-line combination of capillary isotachophoresis-capillary zone electrophoresis with UV detection.

A high-speed DNA fragment separation system based on an on-line combination of capillary ITP with CZE (CITP-CZE) and using UV detection at 260 nm was developed. A novel CITP-CZE buffer system of pH 6.1 was designed for the separation of ten DNA fragments with sizes ranging from 100 to 1000 bp. An effect of underivatized α-, β- and γ-cyclodextrins on the resolution of DNA fragments in the CZE step of the CITP-CZE combination was systematically investigated. Methylhydroxyethylcellulose present in the BGE was used to eliminate the EOF. DNA ladder fragments were separated within 10 min with LODs in the range of 1-5 ng/μL (S/N = 3). The RSDs of the migration time and peak area of individual DNA fragments were in the range of 1-3 and 3-9%, respectively. The developed CITP-CZE system was further applied to the analysis of digest plasmid DNA samples.

Long-term analyses in automated electrophoretic analyzer in hydrodynamically closed separation system

Some potential problems that can occur during the analyses of complex samples by on-line combination of capillary isotachophoresis–capillary zone electrophoresis (cITP–CZE) in automated electrophoretic analyzer with the column-coupling configuration of the separation unit were studied in this work. The main focus was devoted on the reproducibility of important analytes’ parameters (migration time, peak height and peak area) and also on the stability studies of selected low and high molecular mass analytes of inorganic/organic origins (bromate, vitamins, proteins) present at low concentration levels in different kinds of matrices (mineral water, human urine).Such study was carried out for the first time for the electrophoretic analyzer operating in the hydrodynamically closed separation system provided with contact-less conductivity detectors and UV detector in CZE step. Hydrodynamic and electroosmotic flows of the buffer solutions were suppressed and therefore, only the electrophoretic transport of ions was significant. Obtained results showed the different stabilities of the analytes and samples depending on their origin. The focus in the long-term analyses should be paid on the storage of the samples and on the regular changing the contents of electrolyte vessels to keep the electrolyte composition and separation conditions as constant as possible.

Sensitivity enhancement in direct coupling of supported liquid membrane extractions to capillary electrophoresis by means of transient isotachophoresis and large electrokinetic injections

Enhanced sensitivity for determination of basic drugs in body fluids was achieved by in-line coupling of extraction across supported liquid membrane (SLM) to large electrokinetic injection and transient isotachophoresis-capillary zone electrophoresis (tITP-CZE) in commercial CZE instrument. Twelve cm long tITP plug of 300mM ammonium acetate was formed in the separation capillary just before the electrokinetic injection of acceptor solution containing nortriptyline, haloperidol and loperamide extracted across the SLM. The tITP plug ensured efficient stacking and preconcentration of the injected basic drugs due to the tITP action of ammonium and the drugs were then separated by CZE using 5.2M acetic acid as background electrolyte. No interferences were observed from highly-abundant body fluid species (NaCl and human serum albumin) due to the excellent clean-up properties of SLMs and analytical sensitivity increased up to 340 times compared to SLM extractions coupled in-line to CZE with standard hydrodynamic injections. The SLM-tITP-CZE method was characterized by good repeatability (RSDs of peak areas below 7.8%), linearity over two orders of magnitude (r2 better than 0.994) and limits of detection (defined as 3×S/N) between 3 and 45μg/L. Interfacing of SLM extractions to CZE instrumentation was achieved by low-cost, disposable micro-extraction devices, which can be routinely prepared in every analytical laboratory. These devices eliminated sample carry-over, minimized the need for manual sample handling and ensured fully automated determination (including extraction, injection, preconcentration and separation) of the three basic drugs in 20μL of untreated body fluids.

Transient isotachophoresis-capillary zone electrophoresis with contactless conductivity and ultraviolet detection for the analysis of paralytic shellfish toxins in mussel samples

The accumulation of paralytic shellfish toxins (PSTs) in contaminated shellfish is a serious health risk making early detection important to improve shellfish safety and biotoxin management. Capillary electrophoresis (CE) has been proven as a high resolution separation technique compatible with miniaturization, making it an attractive choice in the development of portable instrumentation for early, on-site detection of PSTs. In this work, capillary zone electrophoresis (CZE) with capacitively coupled contactless conductivity detector (C4D) and UV detection were examined with counter-flow transient isotachophoresis (tITP) to improve the sensitivity and deal with the high conductivity sample matrix. The high sodium concentration in the sample was used as the leading ion while l-alanine was used as the terminating electrolyte (TE) and background electrolyte (BGE) in which the toxins were separated. Careful optimization of the injected sample volume and duration of the counter-flow resulted in limit of detections (LODs) ranging from 74.2 to 1020ng/mL for tITP-CZE-C4D and 141 to 461ng/mL for tITP-CZE-UV, an 8–97 fold reduction compared to conventional CZE. The LODs were adequate for the analysis of PSTs in shellfish samples close to the regulatory limit. Intra-day and inter-day repeatability values (percentage relative standard deviation, n=3) of tITP-CZE-C4D and tITP-CZE-UV methods for both migration time and peak height were in the range of 0.82–11% and 0.76–10%, respectively. The developed method was applied to the analysis of a contaminated mussel sample and validated against an Association of Official Analytical Chemists (AOAC)-approved method for PSTs analysis by high performance liquid chromatography (HPLC) with fluorescence detection (FLD) after pre-column oxidation of the sample. The method presented has potential for incorporation in to field-deployable devices for the early detection of PSTs on-site.

Comparison of hydrodynamically closed isotachophoresis–capillary zone electrophoresis with hydrodynamically open capillary zone electrophoresis hyphenated with tandem mass spectrometry in drug analysis: Pheniramine, its metabolite and phenylephrine in human urine

The advanced two dimensional isotachophoresis (ITP)–capillary zone electrophoresis (CZE) hyphenated with tandem mass spectrometry (MS/MS, here triple quadrupole, QqQ) was developed in this work to demonstrate analytical potentialities of this approach in the analysis of drugs in multicomponent ionic matrices. Pheniramine (PHM), phenylephrine (PHE), paracetamol (PCM) and their potential metabolic products were taken for the analysis by the ITP–CZE–ESI–QqQ technique working in hydrodynamically closed CE separation system and then a comparison with the conventional (hydrodynamically open) CZE–ESI–QqQ technique was made. The ITP–CZE–ESI–QqQ method was favorable in terms of obtainable selectivity (due to highly effective heart-cut analysis), concentration limits of detection (LOD at pgmL−1 levels due to enhanced sample load capacity and ITP preconcentration), sample handling (on-line sample pretreatment, i.e. clean-up, preconcentration, preseparation), and, by that, possibilities for future automation and miniaturization. On the other hand, this experimental arrangement, in contrast to the CZE–ESI–QqQ arrangement supported by an electroosmotic flow, is principally limited to the analysis of uniformly (i.e. positively or negatively) charged analytes in one run without any possibilities to analyze neutral compounds (here, PCM and neutral or acidic metabolites of the drugs had to be excluded from the analysis). Hence, these general characteristics should be considered when choosing a proper analytical CE–MS approach for a given biomedical application. Here, the analytical potential of the ITP–CZE–ESI–QqQ method was demonstrated showing the real time profiles of excreted targeted drugs and metabolite (PHM, PHE, M-PHM) in human urine after the administration of one dose of Theraflu® to the volunteers.

On-line column coupled isotachophoresis-capillary zone electrophoresis hyphenated with tandem mass spectrometry in drug analysis: Varenicline and its metabolite in human urine

A new highly advanced analytical approach, based on two-dimensional column coupled CE (ITP-CZE) hyphenated with tandem mass spectrometry (MS/MS, here triple quadrupole, QqQ) was developed, evaluated and applied in biomedical field in the present work. Capillary isotachophoresis (ITP) coupled on-line with capillary zone electrophoresis (CZE) used in hydrodynamically closed separation system was favorable for increasing the sample load capacity, increasing the analyte concentration, and removing the deteriorative highly conductive major matrix constituents. These factors considerably reduced the concentration limits of detection (cLOD) and external sample preparation (comparing to single column CZE), and, by that, provided favorable conditions for the mass spectrometry (enhanced signal to noise ratio, reproducibility of measurements, working life of MS). Here, the CZE–ESI combination provided more effective interfacing than ITP–ESI resulting in both a higher obtainable intensity of MS detection signal of the analyte as well as reproducibility of measurements of the analyte’s peak area. The optimized ITP-CZE–ESI-QqQ method was successfully evaluated as for its performance parameters (LOD, LOQ, linearity, precision, recovery/accuracy) and applied for the direct identification and ultratrace (pgmL−1) determination of varenicline and, in addition, identification of its targeted metabolite, 2-hydroxy-varenicline, in unpretreated/diluted human urine. This application example demonstrated the real analytical potential of this new analytical approach and, at the same time, served as currently the most effective routine clinical method for varenicline.

On-line capillary isotachophoresis–capillary zone electrophoresis analysis of bromate in drinking waters in an automated analyzer with coupled columns and photometric detection

A new, sensitive, and robust analytical method based on capillary zone electrophoresis with on-line capillary isotachophoresis sample pretreatment (ITP–CZE) using a column-coupling (CC) arrangement of automated capillary electrophoretic analyzer was developed for determination of bromate in different type of drinking water samples. Both columns were provided with contact-less conductivity detectors and in CZE step UV detection at 200nm wavelength was used. Electroosmotic flow of the buffer solutions was suppressed with the addition of 0.1% or 0.05% (m/v) methylhydroxyethylcellulose into the leading and terminating electrolyte, respectively. Hydrodynamic and electroosmotic flows of the buffer solutions were successfully suppressed and therefore, only the electrophoretic transport of ions was significant.Limit of detection for bromate approaching 0.6μg/L was achieved. Good repeatabilities of migration time (RSD less than 0.3%) and peak area (RSD less than 4.0%) at concentration level 1μg/L were obtained. Robustness of proposed ITP–CZE method and validation parameters were evaluated. Developed automated ITP–CZE method was applied to the determination of bromate in drinking water samples with different content of inorganic macroconstituents without the need of further sample preparation.

Determination of selected biogenic amines in red wines by automated on-line combination of capillary isotachophoresis–capillary zone electrophoresis

A screening analytical method based on an automated on-line combination of capillary isotachophoresis–capillary zone electrophoresis (cITP–CZE) in hydrodynamically closed separation system, equipped with photometric detection at 280nm, was developed for a routine determination of the selected biogenic amines, namely histamine, 2-phenylethylamine and tyramine, in red wines. The evaluated limits of detection (LODs) were 0.35mgL−1 for histamine, 0.33mgL−1 for 2-phenylethylamine and 0.37mgL−1 for tyramine. The repeatability of the migration time and peak area for histamine were 1.1% and 2.6%, respectively, for 2-phenylethylamine 0.7% and 2.0%, respectively, and for tyramine 0.8% and 2.1%, respectively. The method recoveries were 92.1% for histamine, 96.4% for 2-phenylethylamine and 95.5% for tyramine. The developed automated cITP–CZE–UV method was applied for the determination of histamine, 2-phenylethylamine and tyramine in seven red wine samples originating from Czech Republic.

Direct quantitative determination of amlodipine enantiomers in urine samples for pharmacokinetic study using on-line coupled isotachophoresis-capillary zone electrophoresis separation method with diode array detection

The present work illustrates possibilities of column-coupling capillary electrophoresis (CE-CE) combined with chiral selector (2-hydroxypropyl-β-cyclodextrin, HP-β-CD) and fiber-based diode array detection (DAD) for the direct quantitative enantioselective determination of trace drug (amlodipine, AML) in biological multicomponent ionic matrices (human urine). Capillary isotachophoresis (ITP) served as an ideal injection technique in CE-CE. Moreover, the ITP provided an effective on-line sample pretreatment prior to the capillary zone electrophoresis (CZE) separation. Enhanced separation selectivity due to the combination of different separation mechanisms (ITP vs. CZE–HP-β-CD) enabled to obtain pure zones of the analytes, suitable for their detection and quantitation. The DAD, unlike single wavelength UV detection, enabled to characterize the purity (i.e. spectral homogeneity) of the analytes zones. A processing of the raw DAD spectra (the background correction and smoothing procedure) was essential when a trace analyte signal was evaluated. Obtained results indicated pure (i.e. spectrally homogeneous) zones of interest confirming effective ITP–CZE separation process. The proposed ITP–CZE–DAD method was characterized by favorable performance parameters (sensitivity, linearity, precision, recovery, accuracy, robustness, selectivity) and successfully applied to an enantioselective pharmacokinetic study of AML.

Determination of iodate in table salt by transient isotachophoresis–capillary zone electrophoresis

A transient isotachophoresis–capillary zone electrophoresis (tITP–CZE) method was first time developed for determining iodate in table salt. Sensitivity enhancement was accomplished by coupling on-capillary tITP with CZE. The interference of sample matrix was overcome by using electrophoretic buffer containing high concentration of sodium chloride. The optimal terminating electrolyte for tITP was 1500 mmol/L phosphate and the separation buffer of capillary zone electrophoresis was 10 g/L sodium chloride (pH 8.0) containing 20 mmol/L cetyltrimethylammonium chloride (CTAC). Calibration graphs based on peak height and peak area showed good linearity. Use of chromate as the internal standard significantly improved the precision of the quantitative results. The wavelength of UV detection for iodate was set at 218 nm with the detection limits of 3.5 μg/L for iodate. The quantitative results of iodate in table salt measured by the tITP–CZE method were compared with those measured by the redox titration and there was no significant difference between the two means. The method developed was sensitive, fast and simple.

Possibilities of column coupling electrophoresis provided with a fiber-based diode array detection in enantioselective analysis of drugs in pharmaceutical and clinical samples

The present work illustrated possibilities of column coupling electrophoresis combined with ionizable chiral selector and diode array detection (DAD) for the enantioselective analysis of trace drugs (pheniramine and its analogs) in pharmaceutical and clinical samples. Isotachophoresis (ITP), on-line coupled with capillary zone electrophoresis (CZE), served as an ideal injection technique (high sample load capacity, narrow and sharp drugs zones) of on-line pretreated samples (preseparation, purification and preconcentration of drugs) for the CZE stage. Enhanced (enantio)separation selectivity of CZE with ionizable chiral selector (carboxyethyl-β-cyclodextrin recognized between drugs enantiomers on one hand as well as between drugs and sample matrix constituents on the other hand) enabled to obtain pure zones of the drugs enantiomers, suitable for their detection and quantitation. DAD in comparison with single wavelength UV detection enhanced value of analytical information verifying purity of drugs enantiomers zones (indicating interferents with different spectra to those of drugs). Obtained results indicated pure zones of interest confirming effective ITP–CZE (enantio)separation process. Distinguishing the trace analytes signals superposed on the baseline noise was provided with sufficient reliability (for this purpose the background correction and smoothing procedure had to be applied to the raw DAD spectra). The proposed ITP–CZE–DAD methods were characterized by favorable performance parameters (sensitivity, linearity, precision, recovery, accuracy, robustness, selectivity) and successfully applied for (i) enantiomeric purity testing of dexbrompheniramine in commercial pharmaceutical tablets and (ii) enantioselective metabolic study of pheniramine in human urine.

Determination of glycyrrhizin in liqueurs by on-line coupled capillary isotachophoresis with capillary zone electrophoresis

An on-line coupled capillary isotachophoresis-capillary zone electrophoresis method for the determination of glycyrrhizin in liqueurs is described. The optimised electrolyte system was 5 mM HCl + 11 mM ɛ-aminocaproic acid + 0.05% hydroxyethylcellulose + 30% methanol (leading electrolyte), 5 mM caproic acid + 30% methanol (terminating electrolyte) and 20 mM caproic acid + 10 mM histidine + 0.1% hydroxyethylcellulose + 30% methanol (background electrolyte). Method characteristics, i.e., linearity (20–500 ng/ml), accuracy (recovery 99 ± 4%), intra-assay repeatability (2%), intermediate repeatability (3.8%) and detection limit (8 ng/ml) were determined. Speed of analysis, low laboriousness, high sensitivity and low-running cost are the typical attributes of the capillary isotachophoresis-capillary zone electrophoresis method. Developed method was successfully applied to analysis of liqueurs with liquorice extract and some foods (sweets and food supplements) containing liquorice. Found levels of glycyrrhizin in liqueurs, sweets and food supplements varied between 1–16 mg/l, 850–1050 mg/kg and 1.6–1.8 g/kg, respectively.

Potentialities of ITP-CZE method with diode array detection for enantiomeric purity control of dexbrompheniramine in pharmaceuticals

The present work illustrates potentialities of on-line combined isotachophoresis-capillary zone electrophoresis (ITP-CZE) separation techniques coupled with on-capillary diode array detector (DAD) for enantiomeric purity testing of drugs in pharmaceuticals. The general advantages of the proposed method are its (i) high selectivity, (ii) low concentration limit of detection (LOD) obtainable, (iii) enhanced sample loadability, and (iv) enhanced reliability. For separation of brompheniramine (BP) enantiomers, serving as model analytes, carboxyethyl-β-cyclodextrin (CE-β-CD) was appropriate chiral selector providing complete enantioresolution. Given by a high sample load capacity (30 μl sample injection volume) and preconcentration of the analytes in ITP stage, concentration LOD of levobrompheniramine (LBP), serving as model impurity, was 2.5 ng/ml (8 × 10 −9 mol/l). Such separation and detection conditions enabled to easily determine LBP in samples containing a 10 3 excess of dexbrompheniramine (DBP). DAD detection in comparison with single wavelength detection can enhance value of analytical information when analytes and interferents have different spectra (distinguishing impurities in analyte zone, confirmation of migration positions of migrants). In this context purity of BP zones was confirmed with higher reliability in pharmaceutical sample. Moreover, distinguishing the trace analyte signal superposed on the baseline noise was provided with sufficient reliability (for this purpose the background correction and smoothing procedure had to be applied to the raw DAD spectra). Successful validation and application of the proposed ITP-CZE-DAD method suggest its routine use for the enantiomeric purity testing of pharmaceuticals.

Determination of Phenolic Acids in Herba Epilobi by ITP–CE in the Column-Coupling Configuration

The combination of capillary isotachophoresis (ITP) and capillary zone electrophoresis (CZE) in the column-coupling configuration has been optimized in a mode in which the background electrolyte employed in the CZE step was different from the leading and terminating electrolytes of the ITP step. The optimum composition of the electrolyte system was 0.01 M HCl, 0.02 M IMI, 0.2% HEC, pH 7.2 (leading electrolyte), 0.01 M HEPES, pH 8.2 (terminating electrolyte), and 25 mM MES, 50 mM TRIS, 30 mM boric acid, 0.2% HEC, pH 8.3 (background electrolyte). All solutions contained 20% methanol. The timing of the transfer of isotachophoretically stacked analyte zones into the CZE column was also optimized. An ITP–CZE method with UV detection at 270 nm was developed for separation of nine phenolic acids (protocatechuic, syringic, vanillic, cinnamic, ferulic, caffeic, ρ-coumaric, chlorogenic, and gentisic acids) in a model mixture and used for assay of some of these acids in a methanolic extract of herba epilobi. Application of ITP–CZE resulted in 100-fold better sensitivity than conventional CZE; limits of detection ranged between 10 and 60 ng mL−1. When MES–TRIS–borate-based buffer, pH 8.3, was used in the CZE separation step the linearity of the ITP–CZE response was satisfactory (correlation coefficients were from 0.9937 to 0.9777). Repeatability was also satisfactory (RSD values ranged between 0.77% and 1.28% for migration times and between 1.65% and 13.69% for peak area).

Determination of domoic acid by on-line coupled capillary isotachophoresis with capillary zone electrophoresis

An on-line coupled capillary isotachophoresis—capillary zone electrophoresis (cITP-CZE) method for the determination of domoic acid in shellfish and algae is described. The optimised cITP-CZE electrolyte system was 10 mM HCl + 20 mM β-alanine (BALA) + 0.05% hydroxyethylcellulose (leading electrolyte), 5 mM caproic acid (terminating electrolyte) and 20 mM caproic acid + 20 mM BALA + 0.1% HPMC (background electrolyte). A clear separation of the domoic acid from the other components of methanolic sample extract was achieved within 25 min. Method characteristics, i.e., linearity (0–200 μg/l), accuracy (recovery 101 ± 3%), intra-assay repeatability (2.4%) and detection limit (1.5 μg/l) were determined. Speed of analysis, low laboriousness, high sensitivity and low running cost are the typical attributes of the cITP-CZE method. Developed method was successfully applied to analysis of shellfish samples and food supplements containing algae extract.

Electrophoretic analysis of gold nanoparticles: size-dependent electrophoretic mobility of nanoparticles

Efforts were made to realise a two-dimensional, on-line-coupled isotachophoresis-capillary zone electrophoresis system. The electrophoretic behaviour of gold nanoparticles was investigated with the idea that they could be used to improve the control of this electrophoretic set-up. The well-known citrate-ligated gold nanoparticles were not suitable for this application, because the ligand was desorbed, and the nanoparticle solutions were degraded. Therefore mercaptocarboxylic acids were used, because the chemisorption of thiols on the gold surface was improved. Isotachophoretic measurements were carried out with these nanoparticles. A size-dependent electrophoretic mobility was found according to theoretical predictions, and the surface and zeta-potential were discussed for the small particle range. A new method for concentration measurements of nanoparticles is presented by means of isotachophoresis.

Determination of inorganic oxyhalides in drinking water by on-line coupled capillary isotachophoresis— capillary zone electrophoresis

AbstractSome oxyhalides can be found in drinking waters as inorganic disinfection byproducts. An on-line coupled capillary isotachophoresis—capillary zone electrophoresis (CITP-CZE) method was developed for the analysis of chlorate, chlorite and bromate in water. The optimized CITP-CZE electrolyte system consisted of the following: 10 mM—HCl+20 mM—β-Alanine (leading electrolyte), 5 mM—succinic acid (terminating electrolyte), and 10 mM—succinic acid +5 mM—β-Alanine +0.1% HPMC (carrier electrolyte). A clear separation of oxyhalides from other components of drinking water was achieved within 25 min. Method characteristics, i.e., linearity (0–200 ng/mL), accuracy (88–110%), intra-assay (3–5%), quantification limit (5–15 ng/mL), and detection limit (2–5 ng/mL), were determined. Minimum labor requirements, sufficient sensitivity and low running cost are important attributes of this method. It was found that the developed method is useful for the routine analysis of oxyhalides in water.

Simultaneous determination of iodide and iodate in seawater by transient isotachophoresis–capillary zone electrophoresis with artificial seawater as the background electrolyte

We developed capillary zone electrophoresis with transient isotachophoresis (ITP) as an on-line concentration procedure for simultaneous determination of iodide and iodate in seawater. The effective mobility of iodide was decreased by addition of 20 mM cetyltrimethylammonium chloride to an artificial seawater background electrolyte so that transient ITP functioned for both iodide and iodate. Limits of detection for iodide and iodate were 4.0 and 5.0 μg/l (as iodine) at a signal-to-noise ratio of 3. Values of the relative standard deviation of peak area, peak height, and migration times for iodide and iodate were 2.9, 1.3, 1.0 and 2.3, 2.1, 1.0%, respectively. The proposed method was applied to simultaneous determination of iodide and iodate in seawater collected at a pond at our university.