Open tubular capillary ion chromatography with online dilution for small ions determination in drinks.

This work aims to develop a more robust, easy-to-use, low-pressure, and cost-effective nonsuppressed open tubular capillary ion chromatography (NS-OTIC) approach with online dialysis for small ions determination in drinks. The fabricated device was applied for two selected columns, including poly(butadiene-maleic acid) on a 50-µm bore and AS18 Latex on 25-µm bore fused silica capillaries, for the separation of mixed cations (Na+, K+, Ca2+, Mg2+) and mixed anions (Cl-, Br-, NO2-, NO3-), respectively. High concentrations of ions (up to 100 mM) level can be directly introduced into the NS-OTIC system without an off-line (manual) dilution step. The linear relationship of the peak area and concentration of model ions can be obtained with a resolution > 1.1. The repeatability of the peak area for both OTIC columns was < 6% RSD. Juice and tea samples were successfully analyzed with % recoveries of 77-112 and 90-119 for cation and anion determinations, respectively.

A Cost-effective Liquid Core Waveguide Based on a Concentrated Acid Medium for Colorimetric Determination of Sulfide.

A cost-effective long-path absorption liquid core waveguide (LCW) device was fabricated from a typical Teflon tube, and using a high refractive index (RI) medium of acid. It was incorporated in a flow injection-gas diffusion system for the sensitive determination of sulfide via methylene blue (MB) chemistry. The gas diffusion unit could prevent some interferences in samples. The limit of detection of 0.13 µmol L-1 was achieved without using a preconcentration procedure. The proposed device was successfully applied for sulfide determination in canal water samples with 88.7 - 103% recovery.

Liquid handling employing a moving drop for electrokinetic sample introduction system for capillary zone electrophoresis.

A simple cost-effective moving drop device, with solenoid valves control for programmable liquid handling, was developed for electrokinetic injection in capillary zone electrophoresis (CZE). With a CZE of 50-µm bore fused silica capillary tube and contactless conductivity detector (C4D), mixed anions (Cl-, NO3-, and SO42- as the model) solution was injected at the ground side. Simultaneous quantitative chemical analysis can be achieved. A linear relationship of concentration and the peak height was achieved in the range of 0.5-10 mg L-1 for each anion, with LOD and LOQ being 0.02 mg L-1 and 0.5 mg L-1, respectively. The MVD-CZE system allows continuous operation with a sample throughput of 40 samples/hour. A real sample application was demonstrated for air samples, with one drop (25 µL) collected from a midget bubbler based air sampling unit. The recoveries were found to be 74.4-115.0 %. The developed device was also preliminarily applied for the injection of mixed cations (NH4+, Na+, K+, Ca2+, and Mg2+) at the high voltage side end with optimistic results.

Colorimetric Determination of Sulfide in Turbid Water with a Cost-effective Flow-batch Porous Membrane-based Diffusion Scrubber System.

A cost-effective flow-batch analysis approach with colorimetric measurement has been developed for sulfide ion determination in turbid water samples without using a conventional pump and valve. Under an acidic condition, sulfide ion was converted to hydrogen sulfide gas and liberated out from other complicated matrices. The porous membrane-based diffusion scrubber was utilized as a gas trapping unit for hydrogen sulfide gas separation/preconcentration. From the correlation of sulfide ion concentration and disappearance of sodium nitroprusside reagent detection by using a homemade LED-photodiode based colorimetry, a linear relationship of sulfide ion concentration and absorbance can be obtained with relative standard deviation (%RSD) less than 5%. The limit of detection was 5.6 µmol L-1. The proposed system was applied for sulfide ion determination in wastewater samples with the recoveries of 91.0 - 105.2%. The proposed system is a robust setup and able to handle turbid water samples without a sample filtering step.

Indirect photo-electrochemical detection of carbohydrates with Pt@g-C3N4 immobilised into a polymer of intrinsic microporosity (PIM-1) and attached to a palladium hydrogen capture membrane.

An "indirect" photo-electrochemical sensor is presented for the measurement of a mixture of analytes including reducing sugars (e.g. glucose, fructose) and non-reducing sugars (e.g. sucrose, trehalose). Its innovation relies on the use of a palladium film creating a two-compartment cell to separate the electrochemical and the photocatalytic processes. In this original way, the electrochemical detection is separated from the potential complex matrix of the analyte (i.e. colloids, salts, additives, etc.). Hydrogen is generated in the photocatalytic compartment by a Pt@g-C3N4 photocatalyst embedded into a hydrogen capture material composed of a polymer of intrinsic microporosity (PIM-1). The immobilised photocatalyst is deposited onto a thin palladium membrane, which allows rapid pure hydrogen diffusion, which is then monitored by chronopotentiometry (zero current) response in the electrochemical compartment. The concept is demonstrated herein for the analysis of sugar content in commercial soft drinks. There is no requirement for the analyte to be conducting with electrolyte or buffered. In this way, samples (biological or not) can be simply monitored by their exposition to blue LED light, opening the door to additional energy conversion and waste-to-energy applications.

An exploiting of cost-effective direct current conductivity detector in gas diffusion flow injection system.

In this work, a homemade direct current (DC) conductivity detector as an alternative cost-effective detection device has been fabricated and investigated to use in flow analysis system. Under the selected appropriate conditions of flow system, the electrolysis of a carrier stream at the conductivity detector was negligible and provides well-defined signal. The cost-effective DC conductivity detector was demonstrated to couple with gas diffusion flow injection system for determination of dissolved inorganic carbon (DIC) in water. The method is based on the conversion of DIC (dissolved CO2, HCO3- and CO32-) presented in the injected sample to carbon dioxide in an acidic donor stream and then CO2 gas diffuses through a hydrophobic porous membrane to an acceptor stream. As a result, the change of conductivity signal was observed corresponding to DIC concentration. A linear calibration range of DIC in 1.0-10mmolL-1, with limit of detection of 70µmolL-1, repeatability of <3% RSD and 15 injections h-1 sample throughput can be obtained. This method was applied for DIC determination in natural water.

Conductometric determination of ammonium ion with a mobile drop.

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) of<5%. The mobile drop gave a constant volume of the gas absorbing solution and provided a cost-effective and simple analytical platform.

An open tubular ion chromatograph.

We describe an open tubular ion chromatograph (OTIC) that uses anion exchange latex coated 5 µm radius silica and 9.8 µm radius poly(methyl methacrylate) tubes and automated time/pressure based hydrodynamic injection for pL-nL scale injections. It is routinely possible to generate 50,000 plates or more (up to 150,000 plates/m, columns between 0.3 and 0.8 m have been used), and as such, fast separations are possible, comparable to or in some cases better than the current practice of IC. With an optimized admittance detector, nonsuppressed detection permits LODs of submicromolar to double digit micromolar for a variety of analytes. However, large volume injections are possible and can significantly improve on this. A variety of eluents, the use of organic modifiers, and variations of eluent pH can be used to tailor a given separation. The approach is discussed in the context of extraterrestrial exploration, especially Mars, where the existence of large amounts of perchlorate in the soil needs to be confirmed. These columns can survive drying and freezing, and small footprint, low power consumption, and simplicity make OTIC a good candidate for such a mission.

Micro coulometric titration in a liquid drop.

Miniaturized coulometric titration in a liquid drop has been investigated. Assays of ascorbic acid and thiosulfate with iodine titration were chosen as models. Constant volumes of falling liquid drops containing sample or reagent are manipulated via gravimetrical force to move along a slope hydrophobic path and directed to stop or to move out from an electrode. Such manipulation is useful for delivery of sample and reagents, in a way of flow without tubing. Electrochemical generation of titrant, in this case, iodine, is started at the electrode and micro coulometric titration can be performed in a drop by applying constant current. Timing in the titration can be made via naked eye with a stopwatch or via recording with a webcam camera connecting to a computer to detect the change due to the blue color complex of the excess iodine and starch.

Doped soap membranes selectively permeate a chiral isomer.

Soap films can not only be made with sub-µm thickness, they can have intrinsic permeabilities comparable to many commercial membranes, permitting very high transmembrane flux. Soap films readily incorporate a wide range of modifiers to allow highly tailored selectivity: We show that incorporating α-cyclodextrin in an 890 nm thick Triton-X-100 film allows, in a single stage, a high degree of chirally selective transport (1.6:1) of α(+)-pinene over α(-)-pinene.

Soap bubbles in analytical chemistry. Conductometric determination of sub-parts per million levels of sulfur dioxide with a soap bubble.

Soap bubbles provide a fascinating tool that is little used analytically. With a very low liquid volume to surface area ratio, a soap bubble can potentially provide a very useful interface for preconcentration where mass transfer to an interfacial surface is important. Here we use an automated system to create bubbles of uniform size and film thickness. We utilize purified Triton-X 100, a nonionic surfactant, to make soap bubbles. We use such bubbles as a gas-sampling interface. Incorporating hydrogen peroxide into the bubble provides a system where electrical conductance increases as the bubble is exposed to low concentrations of sulfur dioxide gas. We theoretically derive the conductance of a hollow conducting spherical thin film with spherical cap electrodes. We measure the film thickness by incorporating a dye in the bubble making solution and laser transmission photometry and find that it agrees well with the geometrically computed thickness. With the conductance of the bubble-making soap solution being measured by conventional methods, we show that the measured values of the bubble conductance with known bubble and electrode dimensions closely correspond to the theoretically computed value. Finally, we demonstrate that sub-ppm levels of SO(2) can readily be detected by the conductivity change of a hydrogen peroxide-doped soap bubble, measured in situ, when the gas flows around the bubble.