Contactless Conductivity Detection in Capillary Electrophoresis: A Review

The popularity of contactless conductivity detection in capillary electrophoresis has been growing steadily over the last few years. Improvements have been made in the design of the detector in order to facilitate its handling, to allow easy incorporation into available instruments or to achieve higher sensitivity. The understanding of its fundamental working principles has been advanced and the detection approach has also been transferred to lab‐on‐chip devices. The range of applications has been extended greatly from the initial work on small inorganic ions to include organic species and biomolecules. Concurrent determination of cations and anions by dual injection from opposite ends has been demonstrated as well as sample introduction by using flow‐injection systems for easy automation of the process.     

Single-molecule fluorescence detection in microfluidic channels—the Holy Grail in μTAS?

Both single-molecule detection (SMD) methods and miniaturization technologies have developed very rapidly over the last ten years. By merging these two techniques, it may be possible to achieve the optimal requirements for the analysis and manipulation of samples on a single molecule scale. While miniaturized structures and channels provide the interface required to handle small particles and molecules, SMD permits the discovery, localization, counting and identification of compounds. Widespread applications, across various bioscience/analytical science fields, such as DNA-analysis, cytometry and drug screening, are envisaged. In this review, the unique benefits of single fluorescent molecule detection in microfluidic channels are presented. Recent and possible future applications are discussed.Dedicated to the memory of Wilhelm Fresenius     

Quantitative analysis of perchlorate in extracts of whole fish homogenates by ion chromatography: comparison of suppressed conductivity detection and electrospray ionization mass spectrometry

The perchlorate anion (ClO ₄ ^– ) is an anthropogenic contaminant of increasing concern in water supplies, and has been shown to disrupt thyroid activity. Most perchlorate analyses are currently carried out by ion chromatography (IC) with suppressed conductivity detection (SCD). While this procedure has been demonstrated to provide acceptable performance for analysis of water samples, the determination of perchlorate in high-conductivity aqueous extracts of plant or animal material is not readily accomplished by IC-SCD unless lengthy cleanup protocols are applied. With the addition of electrospray ionization mass spectrometry (ESI-MS) to IC, it was hypothesized that the interference imposed by various ionic species could be significantly reduced without the need for purification; however, the analysis of perchlorate in relatively unpurified extracts of biologically derived homogenates by IC-ESI-MS has not previously been described in the literature. The research presented here represents a comparison of the capabilities of IC-SCD and IC-ESI-MS to detect perchlorate in reagent water and in crude extracts of perchlorate-exposed fish (threespine stickleback, Gasterosteus aculeatus). ESI-MS was found to compare favorably to SCD for the detection of perchlorate in deionized water, and to exceed SCD performance in perchlorate analysis of fish-derived extracts.     

An In Situ Copper Plated Boron‐Doped Diamond Microelectrode Array for the Sensitive Electrochemical Detection of Nitrate

The first example of using a copper microelectrode array for use in electroanalysis is explored and exemplified with the electroanalytical quantification of nitrate. The analytical approach is based upon the in situ deposition of copper at a boron‐doped diamond (BDD) microelectrode array. The immobilized copper layer is electrocatalytic for nitrate reduction and exhibits an analytically useful range from 1.2 to 124 μM with a marked selectivity for nitrate ion over nitrate, with a limit of detection of 0.76 μM. The analytical applicability was examined through standard addition determinations of nitrate in drinking and river water samples.     

Application of Nafion／Cobalt Hexacyanoferrate Chemically Modified Electrodes for the Determination of Electroinactive Cations by Ion Chromatography

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On-line LC-GC-AED and LC-GC-MS – multidimensional methods for the analysis of PAC in fuels,combustion emissions and atmospheric samples

The composition and concentration of polycyclic aromatic compounds (PAC) in fuels. Theier combustion products and in the atmosphere remains a topic of considerable interest. Despite the wealth of literature on the identification of PAC, speciation at low concentrations remains difficult due to instrument limitation and the complexity of fuel and environmental samples. Consequently on line sample preparation procedures (SPE, SFE, LC, etc.) are becomeing an increasingly important step in the analysis procedure particularly where sample clean-up and fractionation are essential for improving analytical resolution. In this study a normal phase high pressure analytical resolution. In this study a normal phase high pressure liquid chromatography-gas chromatography (LC-GC) system has been developed to provide quantitative analysis of samples, as diverse as coal liquids, petroleum fuels, diesel exhaust particulates, and urban air particulates. Separation and identification of parent and alkylated PAH, hetercycline nitro-and oxy-PAC can be achieved by direct coupling to an atomic emission detector and a bech top mass spectrometer. For both systems the primary LC separation combined with the large sample volume transferred to GC vastly improves detection limits. Furthermore the complimentary nature of the two detectors used enables the positive indentification of many unknowns.     

On-line sorption preconcentration of metals based on mixed micelle cloud point extraction prior to their determination with micellar chemiluminescence: Application to the determination of chromium at ng l levels

The on-line incorporation of cloud point extraction (CPE) to flow injection analysis (FIA) is modified to extract and preconcentrate metal species rapidly, avoiding the formation of hydrophobic complexes, using a mixed micellar medium. Coupling the procedure with chemiluminescence (CL) detection based on the catalytic activity of metal species on the luminol-hydrogen peroxide reaction and enhancing the signal with the presence of a micellar carrier containing bromide ions produces a powerful tool for the preconcentration and determination of metal species at ng l⁻¹ levels. As an analytical demonstration ultratrace concentrations of chromium were conveniently detected and quantified in samples with a complex matrix such as seawater and wastewater. The figures of merit for the determination of chromium were: 0.9-1.6% R.S.D. (n=5) with detection and quantification limits 0.5 and 2.0 ng l⁻¹, respectively. The calibration graph was rectilinear from 2 to 200 ng l⁻¹ (r=0.9996, n=6). Several other metal ions were determined in ideal situations, with analogous results.     

Silicomolybdate‐Doped PEDOT Modified Electrode: Electrocatalytic Reduction of Bromate and Oxidation of Ascorbic Acid

Electrically conducting poly(3,4‐ethylenedioxythiophene) (PEDOT) film doped with silicomolybdate (SiMo₁₂O₄₀^4? or SiMo₁₂) was synthesized by electrochemical polymerization. The synthesized film is capable of fast charge propagation during redox reactions in strong acid medium 0.2 M H₂SO₄ solution. The modified electrode was used towards reduction of bromate and successfully employed as an amperometric sensor for bromate and also above modified electrode was investigated for ascorbic acid oxidation.     

Determination of thiol by high-performance liquid chromatography and fluorescence detection with 5-methyl-(2-(<Emphasis Type="Italic">m</Emphasis>-iodoacetylaminophenyl)benzoxazole

A new high-performance liquid chromatographic (HPLC) method for measuring low molecular weight (LMW) thiol-containing compounds, including cysteine (CysH), glutathione (GSH), N-acetylcysteine (Nac), penicillamine (PA), and 2-mercaptoethanol (2-ME), has been developed by using 5-methyl-(2-(m-iodoacetylaminophenyl)benzoxazole (MIPBO) as fluorescence-labeling reagent. The derivatization and separation conditions have been investigated in detail. Detection limits ranging from 3.5 to 15.0 fmol were achieved for the thiols investigated in a 16 min separation with detection wavelengths 310 and 375 nm for the excitation and emission, respectively. The utility of the proposed method has been validated by measuring CysH in human urine samples.     

Quantification of volatile PAHs present at trace levels in air flow by aqueous trapping—SPE and HPLC analysis with fluorimetric detection

In the context of a European project, a new approach of sampling of volatile polycyclic aromatic hydrocarbons (PAHs) from air was developed. In fact, the aim of this project was to test the efficiency of an air cleansing prototype reactor, which was operating by non-thermal plasmolysis. With an eye to model the atmosphere ejected by the prototype, we needed to vaporise the volatile PAHs in an air stream at concentrations as low as those recommended by European Directives (96/62/CE) for PAHs in ambient air (i.e. 1 ng m⁻³). Our strategy was based on the analysis of PAHs trapped in an aqueous medium, in order to avoid important losses of volatile compounds observed during the delicate desorption-concentration step when classical solid supports are used. Then a study was carried out to determine: the design of the collecting part, the flow-rate of the air sampling, the nature and concentration of chemical additives used to enhance PAH solubility in water. The very highly diluted aqueous media obtained after the bubbling step were concentrated by solid-phase extraction (SPE) on hydrophobic cartridges and analysed on-line by reversed-phase HPLC with UV and fluorimetric detections. Lastly, the sampling technique was directly applied to the outlet of the air cleansing prototype and the analysis after 3-6 h of non-thermal plasmolysis showed that the target volatile PAHs were not present in an air stream initially polluted by volatile organic compounds.