Separation of antidepressants by capillary electrophoresis with in-line solid-phase extraction using a novel monolithic adsorbent

The separation of three selective serotonin reuptake inhibitors (SSRIs) by capillary electrophoresis (CE) with fully integrated solid-phase extraction (SPE) is described. Polymeric monolithic SPE modules were prepared in situ within a fused silica capillary from either butyl methacrylate-co-ethylene dimethacrylate or 3-sulfopropyl methacrylate-co-butyl methacrylate-co-ethylene dimethacrylate. Using a 1 cm SPE module placed at the inlet of the capillary, a mixture of sertraline, fluoxetine and fluvoxamine was extracted from aqueous solution by applying a simple pressure rinse. Under pressure-driven conditions, efficient elution was possible from both SPE materials investigated using 50 mM phosphate buffer, pH 3.5 in acetonitrile (20/80, v/v). Two different strategies were investigated for the efficient elution and subsequent CE separation. Injection of an aqueous sample plug directly into the non-aqueous elution/separation buffer was found to be unsuitable with poor elution profiles observed in the electrodriven mode. Alternatively, a sample plug equivalent to several capillary volumes could be injected by pressure followed by filling the capillary with the non-aqueous elution/separation buffer from the outlet end using a combination of pressure and electrodriven flow. Using a neutral monolith, efficient elution/separation was not possible due to an unstable electroosmotic flow (EOF), however, by adding the ionisable monomer, 3-sulfopropyl methacrylate to the SPE module to increase and stabilise the EOF, it was possible to achieve efficient elution from the SPE module, followed by baseline separation by CE using a 200 mM acetate buffer, pH 3.5 in acetonitrile (10/90, v/v). With enrichment factors of over 500 achieved for each of the analytes this demonstrates the potential of in-line SPE-CE for the sensitive analysis of these drugs.     

Muon transfer from protium to helium isotopes at low temperature

The transfer reaction of negative muons from muonic protium to ³ and ⁴ in binary and triple gas mixtures was studied. In the binary mixtures the transfer rates to the two helium isotopes were determined from the time distribution of the 7-keV X-rays of the intermediate muonic molecule (pμHe)*. The experimental transfer rate to ⁴ is in good agreement with theoretical predictions, whereas the rate to ³ is a factor 2 to 3 smaller than the predicted ones. Radiative branching ratios of the (pμHe)8 molecular decay were obtained. Muon transfer from excited states of muonic protium gives the main contribution to the total intensity of the μHe Lyman series in the binary mixtures. Values of q _1s ^He are determined. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nitrite-selective microelectrodes

The development of nitrite-selective liquid membrane microelectrodes based on a synthetic charged ionophore is described. The addition of potassium tetrakis(4-chlorophenyl)borate and poly(vinyl chloride) to the membrane phase is essential to lower the ohmic resistance and to prolong the lifetime of the microelectrodes. The detection limits for sodium nitrite solutions without and with an ion background of 0.1M chloride are 10(-5.1) and 10(-4.2)M, respectively. The comparison with macroelectrodes shows that the miniaturization reduces, to some extent, the selectivity and the slopes of the EMF response functions.     

Determination of environmental caused chlorophenol levels in urine of the general population

Summary A sensitive, specific and analytically reliable method for the determination of mono-, di-, tri- and tetrachlorophenols in human urine has been elaborated. After acid hydrolysis and a simultaneous steam distillation of the urine samples, spiked with an internal standard, the chromatographically concentrated chlorophenols have been derivatized with pentafluorobenzoylchloride and analyzed by capillary gas chromatography/mass spectrometry. The detection limits for the chlorophenols ranged from 0.2 to 2.5 g/l. Using this method we were able to detect 4-MCP, 2,4-+2,5-DCP, 2,4,6-TCP, 2,4,5-TCP and 2,3,4,6-+2,3,5,6-TeCP in urine samples of a group of 258 men and women which had no known occupational contact to hazardous chemical substances. The 95 percentiles for the concentrations of these substances in the urine samples under investigation were 7.5 (4-MCP); 33.6(2,4-+2,5-DCP); 4,7 (2,4,6-TCP); 4,5 (2,4,5-TCP) and 22.2 (2,3,4,6-+2,3,5,6-TeCP) g per liter. That means, that these chlorophenols are constituents of urine of the normal population in concentrations which in part are greater than that of pentachlorophenol (PCP).     

Breaking the phonon bottleneck in semiconductor nanocrystals via multiphonon emission induced by intrinsic nonadiabatic interactions

We observe ultrafast 1P-to-1S intraband relaxation in PbSe and CdSe nanocrystals (NCs) that have distinct energy spectra. While ultrafast dynamics in CdSe NCs has typically been interpreted in terms of electron-hole energy transfer, this mechanism is not active in PbSe NCs because of sparse densities of states in the conduction and valence bands. Our observations of temperature activation and confinement-enhanced relaxation in PbSe NCs can be explained by efficient multiphonon emission triggered by nonadiabatic electron-phonon interactions and are indicative of large, size-dependent, intraband Huang-Rhys parameters.     

Studies on the synthesis of 2,3-o-hydroxyalkyl ethers of cellulose

Novel 2,3-O-hydroxyethyl- and 2,3-O-hydroxypropyl cellulose products were synthesized by heterogeneous etherification of 6-O-(4-monomethoxytrityl) cellulose (MMTC). Due to the very hydrophobic character of MMTC, the reaction was successful in the presence of anionic and non-ionic detergent in the reaction mixture yielding the 2,3-O-cellulose ethers with a molar degree of substitution (MS) varying between 0.25 and 2.00 after detritylation. The products were characterized by means of (1)H and (13)C NMR spectroscopy including two-dimensional methods. The 2,3-O-hydroxypropyl cellulose samples are soluble in water at a MS as low as 0.8. The spectroscopic studies showed that the unusual solubility results from a preferred substitution of hydroxy groups of the anhydroglucose unit while the newly formed hydroxy moieties are included in the reaction to a minor extent only. In contrast, conventionally synthesized hydroxypropyl cellulose is soluble in water starting at a MS of about 4.0 because of the formation of oxyethylene side chains. (13)C DEPT 135 NMR spectrum of 2,3-O-hydroxypropyl cellulose.     

Analytical validity of the determination of mercury in whole blood and urine--results of the German external assurance programme for toxicological analysis in biological materials

The determination of mercury concentrations in blood and urine is currently the best way of monitoring individual uptake of organic and inorganic mercury. In Germany these determinations must be carried out under the conditions of an external quality assurance programme. The German performance evaluation, based on reference values established by reference laboratories yields success rates in percent for the participants in the intercomparison programme of about 60%. A Canadian evaluation system based on two evaluations scores, yields success rates of 25-50% for "good performance" and of 65-80% for "acceptable performance". The determination of mercury in blood and urine is at present not carried out with the necessary reliability.     

Über gemischtvalente Ruthenium-Perowskite Ba3B3+Ru24,5+O9 – zur katalytischen Aktivität von Sauerstoffperowskiten mit vier- und fünfwertigen Edelmetallen

On Mixed Valent Perovskites Ba₃B³⁺Ru₂^4,5+O₉ – Catalytic Activity of Perovskite Oxides with Noble Metals The black compounds Ba₃B³⁺Ru₂O₉ crystallize with B³⁺ = La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y in a hexagonal BaTiO₃ structure (6 L, sequence (hcc)₂) with an ordered distribution (1:2 order) of B³⁺ and ruthenium (BO₆ single octahedra; Ru₂O₉ double groups). The mean oxidation state of ruthenium is about +4.5. The properties are compared with that of other isotypic stacking polytypes Ba₃B³⁺M₂^4,5O₉ (M₂ = IrRu, Ir₂, PtRu) and Ba₃B²⁺M₂⁵⁺O₉ (M = Ru, Ir). The results of activity tests concerning the efficiency of perovskite oxides with noble metals in respect of the oxidation of CO or CH_x and the reduction of NO_x are reported.