Enantioselective determination of thyroxine enantiomers by ligand-exchange CE with UV absorbance and ICP-MS detection.

A simple CE method has been developed for the separation and determination of thyroxine (T4) enantiomers in pharmaceutical formulations. The method was based on ligand-exchange mechanism using a Cu(II)/L-proline complex as chiral selector. The effects of different parameters affecting separation such as chiral selector concentration, organic additive, buffer pH and temperature were investigated. A baseline separation of the two enantiomers was obtained at a Cu(II)/L-proline ratio of 1:8 in a borate buffer (15 mmol/L, pH 9.6) containing 10% v/v acetonitrile. Under the optimized conditions, precision linearity range and detection limits of the developed enantioselective CE method were evaluated and compared using two different detection systems: conventional UV detection at 226 nm and iodine (127I)specific detection ("chiral speciation") with ICP-MS. Both methodologies show adequate analytical performance characteristics with detection limits around 0.30 microg/mL for each enantiomer of T4. Finally, a levothroid pharmaceutical formulation sample was successfully analyzed using both developed methods CE-UV and CE-ICP-MS.

[Ru(bpy)3]2+-doped silica nanoparticles within layer-by-layer biomolecular coatings and their application as a biocompatible electrochemiluminescent tag material.

[Ru(bpy)3]2+-doped silica (RuSi) nanoparticles were synthesized by using a water/oil microemulsion method. Stable electrochemiluminescence (ECL) was obtained when the RuSi nanoparticles were immobilized on a glassy carbon electrode by using tripropylamine (TPA) as a coreactant. Furthermore, the ECL of the RuSi nanoparticles with layer-by-layer biomolecular coatings was investigated. Squential self-assembly of the polyelectrolytes and biomolecules on the RuSi nanoparticles gave nanocomposite suspensions, the ECL of which decreased on increasing the number of bilayers. Moreover, factors that affected the assembly and ECL signals were investigated. The decrease in ECL could be assigned to steric hindrance and limited diffusion of the coreactant molecules in the silica matrix after they were attached to the biomolecules. Since surface modification of the RuSi nanoparticles can improve their biocompatibility and prevent leaking of the [Ru(bpy)3]2+ ions, the RuSi nanoparticles can be readily used as efficient and stable ECL tag materials in immunoassay and DNA detection.

CE coupling with end-column electrochemiluminescence detection for chiral separation of disopyramide.

CE with electrochemiluminescence (ECL) detection technique was successfully applied for the chiral separation of a kind of class IA antiarrhythmic racemic drug. To the best of our knowledge, this is the first report of ECL detection used in chiral CE. To get better detection sensitivity and good enantioresolution at the same time, the conditions of capillary inlet and outlet buffer were systematically optimized. Unlike the traditional chiral separation method, the buffers we used in the capillary inlet and outlet differed from each other in terms of buffer pH, ionic strength, type of BGE as well as buffer composition. Under the optimum conditions, baseline enantioseparation and highly sensitive detection of the enantiomers were achieved. Wide linear relationship of each enantiomer was achieved in the range of 5 x 10(-7) to 2 x 10(-5) mol/L with relative coefficients of 0.996 and 0.997, respectively. The detection limits were estimated to be 8 x 10(-8) and 1.0 x 10(-7) mol/L (S/N = 3) for the enantiomers, respectively. In addition, a successful application of this new method to the chiral separation of the racemic drug in spiked plasma samples confirmed the validity and applicability of the chiral CE-ECL method.

Microchip capillary electrophoresis with solid-state electrochemiluminescence detector.

We report microchip capillary electrophoresis (CE) coupling to a solid-state electrochemiluminescence (ECL) detector. The solid-state ECL detector was fabricated by immobilizing tris(2,2'-bipyridyl)ruthenium(II) (TBR) into an Eastman AQ55D-silica-carbon nanotube composite thin film on an indium tin oxide (ITO) electrode. After being made by a photolithographic method, the surface of the ITO electrode was coated with a thin composite film through a micromolding in capillary (MIMIC) technique using a poly(dimethylsiloxane) (PDMS) microchannel with the same pattern as an ITO electrode. Then the TBR was immobilized via ion exchange by immersing the ITO electrode containing the thin film in TBR aqueous solution. The whole system was built by reversibly sealing the TBR-modified ITO electrode plate with a PDMS layer containing electrophoresis microchannels. The results indicated that the present solid-state ECL detector displayed good durability and stability in the microchip CE-ECL system. Proline was selected to perform the microchip device with a limit of detection of 2 microM (S/N=3) and a linear range from 25 to 1000 microM. Compared with the CE-ECL of TBR in aqueous solution, while the CE microchip with solid-state ECL detector system gave the same sensitivity of analysis, a much lower TBR consumption and a high integration of the whole system were obtained. The present system was also used for medicine analysis.

Electrochemiluminescence quenching as an indirect method for detection of dopamine and epinephrine with capillary electrophoresis.

An electrochemiluminescence (ECL) inhibition method was developed as an indirect detection method for the determination of dopamine and epinephrine separated by capillary electrophoresis (CE). When the concentration of Ru(bpy)(3) (2+) was 50 muM diluted by 50 mM phosphate (pH 8.5) in the cell and 0.5 M tripropylamine (TPA) was added to the running buffer (10 mM phosphate, pH 9.0), an inhibition of ECL of the Ru(bpy)(3) (2+)/TPA system by the analytes was observed. Under the optimized conditions, the relative standard deviations of migration time and negative peak area were less than 1% and 3%, respectively, for 1 microM dopamine or 1 microM epinephrine (n = 10). Linear ranges of 0.1-10 microM for both analytes and the detection limits (signal-to-noise ratio S/N = 3) of 10 nM for dopamine and 30 nM for epinephrine were obtained.

Dynamic coating for resolving rhodamine B adsorption to poly(dimethylsiloxane)/glass hybrid chip with laser-induced fluorescence detection.

In this paper a method was described about dynamic coating for resolving rhodamine B (RB) adsorption on a hybrid poly(dimethylsiloxane) (PDMS)/glass chip. The results showed that when the non-ionic surfactant Triton X-100 was higher than 0.5% (v/v) into the phosphate buffer, the adsorption of RB appeared. Besides, some separation conditions for RB were investigated, including concentration of Triton X-100, concentration and pH value of running buffer, separation voltage and detection site. Through comparing electroosmotic flow, plate numbers and other parameters, an acceptable separation condition was obtained. Under optimized conditions, the precisions of RB detection (R.S.D., n=10) were 2.62% for migration time, 4.78% for peak height respectively. Additionally, RB concentration linearity response was excellent with 0.9996 of correlation coefficient between 1 and 100muM, and a limit of detection (S/N=3) was 0.2muM. Finally, we separated rhodamine B isothiocyanate and lysine deriving from the fluorescent probe, and the result displayed that the dynamic coating method was applicable by CE separations using PDMS/glass chip.

Short-capillary electrophoresis with electrochemiluminescence detection using porous etched joint for fast analysis of lidocaine and ofloxacin.

Fast analysis of ofloxacin and lidocaine, as bactericide and analgesic or anesthetics, is of clinic importance for understanding the patient's medical process. This paper presented a high throughput, simple analysis method of lidocaine and ofloxacin by capillary electrophoresis coupled with electrochemiluminescence (ECL) using porous etched joint. To shorten the analysis time and to improve the analytical performance, a capillary with 10 cm in length was used as the separation channel. The cyclic voltammograms of Ru(bpy)3(2+) with different capillary length at same field strength showed that the porous etched joint eliminated the effect of electrophoretic current on the ECL detection. Following micro total analysis systems (microTAS), some advantages of which this approach has, the fabrication of channel in chip was not needed. Compared with capillary electrophoresis with 40-cm-long capillary, the high sample throughput and low zone broadening may be the main advantage of the present system. Under optimal condition, the detection limits of lidocaine and ofloxacin based on peak height were 3.0 x 10(-8) and 5.0 x 10(-7) molL(-1) and a 60 h(-1) of sampling frequency was obtained. The precision (R.S.D.) of the migration time and the peak height for five replicate injections of a mixture of lidocaine (1.0 x 10(-6) molL(-1)) and ofloxacin (4.0 x 10(-6) molL(-1)) were 3.2-3.9% and 4.7-5.3%, respectively.

Cyanex 923 as the extractant in a rare earth element impurity analysis of high-purity cerium oxide.

In this work, the feasibility of employing Cyanex 923 as an extractant into the non-cerium REE (rare earth elements) impurity analysis of high-purity cerium oxide was investigated. Through investigations on the choice of the extraction medium, the optimium extraction acidity, matrix Ce4+ effect on the non-cerium REE ion extraction, the optimium extractant concentration and suitable extracting time, and oscillation strengh, it was found that when the phase ratio was at 1:1 and the acicidity was about 2% H2SO4, by gently shaking by hand for about 2 min, 10 mL of 30% Cyanex 923 could not extract even for a 20 ng amount of non-cerium REE3+ ions. However, the extraction efficiency for Ce4+ of 100 mg total amount under the same conditions was about 96%, indicating that a 25-fold preconcentration factor could be achieved. Thus, it was concluded that Cyanex 923 could be used in a REE impurity analysis of 99.9999% or so pure cerium oxide for primary sepapation to elimilate matrix-induced interferences encountered in an ICP-MS (inductively coupled plasma mass spectroscopy) determination.