Determination of alcohol polyether average molar oligomer value/distribution via supercritical fluid chromatography coupled with UV and MS detection

Supercritical fluid chromatography (SFC) was used for the analysis of ethoxylated and propoxylated surfactants. Samples were derivatized to phenylated silyl ethers with a disilazane-chlorosilane mixture. Addition of a phenyl group to the surfactant allowed UV-absorbance detection of each oligomer. Acetonitrile and methanol were evaluated as mobile phase modifiers. Better peak shape was realized with methanol-modified CO2 on an octadecyl silica bonded phase than with acetonitrile-modified CO2. Peak assignments were made via SFC coupled with electrospray ionization-mass spectrometry (ESI-MS) in the positive ion mode. A sulfonamide-embedded alkyl stationary phase was also evaluated for separation of the derivatized samples. SFC-UV and SFC-ESI-MS data were jointly used for calculation of average molar oligomer values which were then compared to values calculated from 1H NMR data of non-derivatized samples. The derivatization or separation method using the sulfonamide embedded phase required no preliminary cleanup and yielded reproducible oligomer values that were consistent with those of the manufacturer's nominal values.     

Validation of a screening method for the simultaneous identification of fat-soluble and water-soluble vitamins (A,E, B<Subscript>1</Subscript>, B<Subscript>2</Subscript> and B<Subscript>6</Subscript>) in an aqueous micellar medium of hexadecyltrimethylammonium chloride

Simultaneous determination of the fat-soluble vitamins A and E and the water-soluble vitamins B₁, B₂ and B₆ has been carried using a screening method from fluorescence contour graphs. These graphs show different colour zones in relation to the fluorescence intensity measured for the pair of excitation/emission wavelengths. The identification of the corresponding excitation/emission wavelength zones allows the detection of different vitamins in an aqueous medium regardless of the fat or water solubility of each vitamin, owing to the presence of a surfactant which forms micelles in water at the used concentration (over the critical micelle concentration). The micelles dissolve very water insoluble compounds, such as fat-soluble vitamins, inside the aggregates. This approach avoids the use of organic solvents in determining these vitamins and offers the possibility of analysing fat- and water-soluble vitamins simultaneously. The method has been validated in terms of detection limit, cut-off limit, sensitivity, number of false positives, number of false negatives and uncertainty range. The detection limit is about g L^–1. The screening method was applied to different samples such as pharmaceuticals, juices and isotonic drinks.     

Cd(II) determination in the presence of aqueous micellar solutions

The equilibrium constants and molar absorptivities for the fast formation of a 1:3 complex between cadmium(II) (Cd(II)) and dithizonate anion, in the presence of cationic and non-ionic surfactants, allowed a simple and fast spectrophotometric determination of total cadmium. Indeed, the molar absorptivities of the Cd(II)-dithizone (Dz) complex formed in the presence of the neutral Triton X-100 and cationic cetyltrimethylammonium bromide (CTAB) surfactants are almost twice the value observed in the standard method and the maxima of absorption are shifted by about 40 nm when compared with the standard method. Clearly, the use of neutral and cationic surfactants promotes a higher value of the molar absorptivities of the complex, resulting in an increase in the sensitivity of the method. Application of the method to the desorption of Cd(II) ions from clays is illustrated.     

Micelles as pseudo-stationary phases in micellar electrokinetic chromatography

This review article describes some general comments on micellar electrokinetic chromatography (MEKC) from the viewpoint of pseudo-stationary phases and presents a compiled list of surfactants used for MEKC, prepared from published papers. We tried to give comments on some typical surfactants from the practical point of view.     

Optimization of solid-phase extraction and solid-phase microextraction for the determination of alpha- and beta-endosulfan in water by gas chromatography-electron-capture detection

The electrophoretic behaviour of ionizable and neutral alkylxanthines commonly used in pharmaceutical preparations was studied. The performance of various separation modes including capillary zone electrophoresis (CZE), cyclodextrin electrokinetic chromatography, and micellar electrokinetic chromatography (MEKC) with either sodium dodecyl sulfate (SDS) or bile salts as surfactants, was assessed. CZE in an alkaline medium successfully separates ionizable xanthines and dyphylline. The addition of carboxymethyl-β-cyclodextrin to the background electrolyte allows only partial resolution of neutral xanthines. Based on MEKC results, bile salts exhibit more discrimination ability than SDS to separate similar xanthines. The best results are provided by taurodeoxycholic acid, which ensures baseline separation of xanthines.     

Highly selective and efficient separations of a wide range of acidic species in capillary electrophoresis employing non-aqueous media

Summary The novel application of CE using non-aqueous media has been studied for the separation of a range of acidic compound types. This enabled the first quantitative assay by CE employing non-aqueous media to be performed. Separation selectivity manipulation for closely related species was achieved through variation of organic solvent types and composition, ionic strength changes, alteration of pH^* values and the addition of cyclodextrin additives soluble in organic solvents. This offers a greater range of possibilities during method development than use of aqueous buffer. The generation of low operating currents permitted rapid, highly efficient and selective separations to be achieved by applying high field strengths across short capillaries. Optimised rinsing and capillary regenerating procedures were devised which allowed highly repeatable separations to be achieved with migration time repeatability below 1% RSD. Use of internal standards also allowed 1% RSD values to be obtained for injection precision. Routine operating effects were assessed and it was observed that stacking effects remain important in non-aqueous CE. Also, optimal separations are obtained when the samples are diluted in the pure solvent used to prepare the electrolyte. The application range of non-aqueous CE was appreciably extended to include acidic drugs, dyes, surfactants and preservatives.     

A new dodecylsulfate-selective supported liquid membrane electrode based on its N-cetylpyridinium ion-pair

A supported liquid and a poly(vinyl chloride) (PVC)-based membrane selective for dodecylsulfate (DS⁻) ion are described. The active element is a membrane containing a dissolved ion association complex of DS⁻ with cetylpyridinium (CP⁺) cation. The supported liquid membrane electrode (acetophenone as solvent) showed a Nernstian response towards the DS⁻ anion over the concentration range of sodium dodecylsulfate (SDS) from 8.3×10⁻³ to 1.0×10⁻⁶ mol dm⁻³ at 25 °C. The proposed electrode also showed a super-Nernstian potential response (108±2 mV decade⁻¹) at low concentrations (1.0×10⁻⁹ to 1.0×10⁻⁶ mol dm⁻³). Moreover, this electrode showed good selectivity and precision (R.S.D.?2.0%), and was usable within the pH range 4.0-6.8. The proposed electrode revealed a lower limit of detection of 6.3×10⁻⁷ mol dm⁻³ and improved selectivity in comparison with the some previously reported DS⁻ ion selective electrodes. The isothermal temperature coefficient of this electrode amounted to −0.001 V °C⁻¹. The liquid membrane electrode may find application in the direct determination of SDS by the standard addition method at pH 5.0, and in the physicochemical studies of surfactant solutions.     

Microcolumns with self-assembled particle frits for proteomics

LC-MS-MS experiments in proteomics are usually performed with packed microcolumns employing frits or outlets smaller than the particle diameter to retain the packing material. We have developed packed microcolumns using self-assembled particles (SAPs) as frits that are smaller than the size of the outlet. A five to one ratio of outlet size to particle diameter appears to be the upper maximum. In these situations the particles assembled into an arch over the outlet like the stones in a stone bridge. When 3 microm particles were packed into a tapered column with an 8 microm outlet, two particles bridged the outlet with 0.3 pl dead volume and perfect success rate. In peptide analysis by LC-MS, the peak width at half height was normally less than 6 s, compared to 12 s without SAPs. The LC-MS-MS system provided 37% sequence coverage (21 matched peptides) for a tryptically-digested sample of 10 fmol bovine serum albumin. We also describe application of the SAP principle to make disposable pipette tip columns with short pieces of fused-silica capillary as the outlet.     

Morphological evolution and visible light-induced degradation of Rhodamine 6G by nanocrystalline bismuth tungstate prepared using a template-based approach

The cleaning of water contaminated with organic dyes is a crucial problem nowadays. The search for good catalysts is intense, and bismuth tungstates have attracted a lot of attention because of their catalytic properties which are related to their crystal structure and morphology. In this study, we show that Bi₂WO₆ (BWO) crystals synthesized by the surfactant-assisted hydrothermal method create a different morphology than non-assisted crystals. With the assistance of the PVP surfactant, even the BWO crystalline structure could change, crystallizing into a high-symmetry metastable phase. These changes in morphology imply a decrease in BWO catalytic activity, which shows that insightful control of BWO synthesis is necessary to improve the BWO properties.