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991.
A fluorescence detection system for capillary liquid separation methods is described. The system is based on a silica capillary coated with a low refractive index fluoropolymer Teflon AF that serves both as a separation channel and as a liquid core waveguide (LCW). A fibre-coupled laser excites separated analytes in a detection point and arising fluorescence is collected at one end of the LCW capillary into the other optical fibre which brings it to a compact charge-coupled device (CCD) array spectrometer installed in a desktop computer. No additional components such as focusing optics or filters are necessary. This system was used for detecting isoelectrically focused fluorescent low-molecular-mass pI (isoelectric point) markers and fluorescein isothiocyanate (FITC) labelled proteins. The ability of the system to acquire fluorescent spectra is also demonstrated. 相似文献
992.
Karel Prikry 《Monatshefte für Mathematik》1976,81(1):41-57
We prove that if Kurepa's Hypothesis holds, then on a set of cardinality ?1, there does not exist a family of ?1 non-trivial measures such that each subset is measurable with respect to at least one of them. We also strengthen a theorem ofErdös andAlaoglu on the non-existence of enumerable families of measures. 相似文献
993.
Bednár P Lemr K Barták P Sevcík J Hlavác J Stýskala J Wiedermannová I Stránský Z 《Journal of mass spectrometry : JMS》2002,37(12):1213-1218
A method based on the coupling of capillary electrophoresis with mass spectrometry (CE/MS) was developed for the monitoring of 3-quinuclidinol and its four N-alkyl derivatives (methyl, ethyl, propyl and isopropyl derivatives). A fragmentation study (collision-induced dissociation of ions in an ion trap) and optimization of the ion optics set-up for CE/MS experiments using direct infusion of a methanolic solution of the standards into the mass spectrometer were carried out in advance. Molecular ions of all quaternary compounds and the quasi-molecular ion [M + H]+ of free 3-quinuclidinol prevail in the mass spectra. In the MS/MS of propyl and isopropyl derivatives, the elimination of the alkyl chain dominates, leading to the ion at m/z 128. The fragmentation of the other compounds is more complex. Previous CE separation of the mixture of isobaric propyl and isopropyl derivatives is necessary for their unambiguous identification. A 10 mM ammonium acetate buffer (pH 4.0) is the optimum running electrolyte, allowing the CE separation of methyl, ethyl, propyl and isopropyl derivatives. A 0.5% (v/v) solution of acetic acid in methanol provides sufficient detection sensitivity when used as the sheath liquid. Limits of detection of 0.1 ppm for 3-quinuclidinol and 0.05 ppm for quaternary derivatives were achieved under the optimum conditions. The optimized method was applied to the determination of 3-quinuclidinol and related quaternary derivatives spiked into a sample of pond water. The experimental set-up for CE/MS/MS was investigated, which strongly increases the identification capability of the technique. 相似文献
994.
The importance of capillary electrophoresis (CE), capillary electrochromatography (CEC), and ion chromatography (IC) in inorganic ion analyses is outlined. Methods for improving the reliability of the CE measurements are briefly described. Selectivity optimization in CE analyses of inorganic cations and anions is discussed. Using the Peakmaster program, CE system peaks (system zones, eigenmobilites) and some important CE parameters, such as effective mobilities, electromigration dispersion, indirect UV, and direct conductivity signals, are predicted and compared with experimental analyses. 相似文献
995.
Summers JS Base K Boukhalfa H Payne JE Shaw BR Crumbliss AL 《Inorganic chemistry》2005,44(10):3405-3411
Manganese/ligand association dynamics were studied using a series of structurally related anionic phosphorus ester ligand probes [CH(3)OP(O)(X)(Y)(-), where X = CH(3)O, CH(3)CH(2), or H and Y = O, S, or BH(3)]. Reactions of the probe ions with Mn(H(2)O)(6)(2+) and a manganese(III) porphyrin (Mn(III)TMPyP(5+)) were studied in aqueous solution by paramagnetic (31)P NMR line-broadening techniques. A satisfactory linear free energy relationship for reactions of the probe ions with Mn(H(2)O)(6)(2+) and Mn(III)TMPyP(5+) required consideration of both the basicity and solvent affinity of the probe ligands: log(k(app)) = log(k(0)) + alpha pK(a) + beta log(K(ext)), where k(0), alpha, and beta are metal complex dependent parameters and pK(a) and K(ext) represent the measured Bronsted acidity and water/n-butanol extraction constant for the probe anions, respectively. Reactions of Mn(H(2)O)(6)(2+) were relatively insensitive to changes in ligand basicity (alpha = -0.04) and favored the more hydrophilic anions (beta = -0.54). These observations are consistent with a dissociative ligand exchange mechanism wherein the outer-sphere complex is stabilized by hydrogen bonding between Mn(H(2)O)(6)(2+) and the incoming ligand. In contrast, reactions with Mn(III)TMPyP(5+) are accelerated by decreases in both the basicity (alpha = -0.43) and the hydrophilicity (beta = +0.97) of the probe. We conclude that reactions of Mn(III)TMPyP(5+) are also dissociative but that the aromatic groups of the porphyrin provide a hydrophobic environment surrounding the ligand binding site in Mn(III)TMPyP(5+). Thus, the probe/water solvent interactions must be significantly weakened in order to form the outer-sphere complex that leads to ligand substitution. This work demonstrates the utility of phosphorus relaxation enhancement (PhoRE) techniques for characterizing the second coordination sphere environment of metal complexes leading to ligation and will allow comparison of the second coordination spheres of Mn(H(2)O)(6)(2+) and Mn(III)TMPyP(5+) to those of other metal complexes. 相似文献
996.
Humpolícková J Stepánek M Procházka K Hof M 《The journal of physical chemistry. A》2005,109(48):10803-10812
The hydration of the poly(oxyethylene) shell in polystyrene-block-poly(2-vinylpyridine)-block-poly(oxyethylene) micelles was investigated by monitoring the solvent relaxation response of a solvent-sensitive fluorophore (patman). It has been found that the relaxation occurs on the nanosecond time scale. Results for triblock copolymer micelles have been compared with those obtained for polystyrene-block-poly(2-vinylpyridine) micelles in order to evaluate the effect of the outer polyoxyethylene layer. Considerable pH-dependent changes in the hydration of poly(oxyethylene) units at the poly(2-vinylpyridine)/polyoxyethylene interface were observed. Additionally, the paper shows that the solvent relaxation technique is a suitable tool for studying polymeric nanoparticles and that the measurement of time-dependent half-width of the emission spectrum allows for estimation of the extent of relaxation process observed by a given experimental setup. 相似文献
997.
We present a fast detection of M467T, the major mutation causing cystinuria, by capillary electrophoresis version of single-strand conformation polymorphism (SSCP). The DNA fragment (317 bp) carrying the point mutation was amplified by polymerase chain reaction (PCR) on the exon 8 of the SLC3A1 gene, which encodes for the transmembrane glycoprotein rBAT, a part of the active cystine and dibasic amino acids transporter. The complementary strands of the fragment were labeled by fluorescein and TAMRA, respectively. Thus, the electromigration of both strands was recorded independently as a laser-induced fluorescence (LIF) signal, what enabled an effective optimization of separation conditions. The injected sample was denatured by immersing the inlet of the separation capillary into a vial with 0.1 M solution of NaOH prior to analysis. Under optimum conditions, the SSCP analysis in poly(vinyl alcohol) (PVA)-coated silica-fused capillary of an effective length of 15 cm, filled with 4% linear polyacrylamide (LPA) solution, was accomplished in approximately 6 min. The experimentally observed mobility shifts of single-stranded DNA (ssDNA) fragments were compared to the appearance of their calculated two-dimensional conformations using Version 3.0 of MFOLD software. The number of nucleotides involved in the duplex regions of theoretical structures correlates well with their real migration order in the sieving medium. 相似文献
998.
Karel Mach Helena Antropiusová Vladimiŕ Hanuš Alena Dosedlová 《Transition Metal Chemistry》1980,5(1):5-10
Summary The reduction of Cp2TiCl2 with LiAlH4 in olefinic solvents at temperatures above 100° leads to the formation of µ-(
5 :
5-fulvalene)-di-µ-chloro-bis(
5-cyclopentadienyl-titanium) (1) and finally to µ-(
5 :
15-fulvalene)-di-µ-hydrido-bis (
5-cyclopentadienyltitanium). The first step of the reduction includes mainly the formation of the dimer of bis(
5-cyclopentadienyl)titanium(III) chloride, (Cp2TiCl)2. The mechanism of its conversion into (1) involves the formation of an intermediate bis(
5-cyclopentadienyl)titanium(III) hydride species which reacts immediately with the olefinic solvent to give bis(
5-cyclopentadienyl)alkyltitanium(III) compounds. The formation of the fulvalene ligand in (1) is explained by the interaction of the alkyltitanium compound with the cyclopentadienyl ligands of (Cp2TiCl)2 resulting in hydrogen transfer to the olefinic solvent. 相似文献
999.