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11.
Henk Buck 《International journal of quantum chemistry》2005,101(1):73-83
With semi‐empirical MO and ab initio calculations at different levels, we investigated the π conjugation of alternating X? Y bonds with X? Y for N/B and N/C combinations in an open and cyclic arrangement. Although the intrinsic symmetry is lost for the acyclic even‐membered compounds, the alternation is still reflected in its geometry and electron‐density transfer. For the cyclic π compounds, we focused our attention on borazine N3B3H6 (D3h symmetry), which is isoelectronic with benzene (D6h symmetry). Specific attention is given to the electrophilic behavior of borazine with respect to CH and SiMe. The dynamics based on the results of FT‐ICR mass spectrometry was studied in more detail. In addition, the results of the cyclic systems with 4n and 4n+2 π electrons concerning their geometries are compared with the corresponding carbon compounds. Attention is also given to the dication of borazine, because of the corresponding triplet ground state of the benzene dication. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
12.
Neil S. Arnold Cyorgy Hars Henk L. C. Meuzelaar 《Journal of the American Society for Mass Spectrometry》1994,5(7):676-688
Proceeding from the pseudopotential-well approximation for ion motion in a quadrupole ion trap, mathematical expressions are derived to describe the excitation amplitude of an ion packet at a given mass-to-charge ratio. Ion-neutral collisions are incorporated to describe the damping of ion trajectories and to describe the distribution of individual ion trajectories about a mean amplitude for the ion packet. The rate of increase of the amplitude during scanning is related to expressions that describe the amplitude dispersion of the ions at the time of ejection from the trap, which is operating in a resonance ejection scanning mode to describe the temporal line width of the ejected ion packet. The temporal line width is related to mass resolution under a number of different scanning conditions. Included in the discussion are considerations of the effect on resolution of the resonance excitation voltage, temperature, pressure, noise, and buffer-gas composition. An expression for the maximum possible resolution at high ion mass-to-charge ratios is developed, and these results are compared to an existing theoretical construction. The expressions derived under the pseudopotential-well approximation are further extended to high q z values and compared to experimental data previously published by two other researchers. 相似文献
13.
Summary The use of high voltages across a electrophoresis capillary will increase the temperature of the buffer due to Joule heating.
As a result temperature control in CE is rather important since variations in the buffer temperature will result in changes
in the pH of the buffer, peak shape, migration time, reproducibility, efficiency, 3-D structure of macromolecular analytes,
etc. Six different thermostating systems have been evaluated: (i) natural convection, (ii) fan, (iii) home-made and (iv and
v) two commercially available high-speed air and a (vi) liquid thermostated device. In all cases the temperature of the buffer
in the capillary is calculated according to the temperature-conductivity relationship. For this purpose two parameters are
introduced describing temperature control: the temperature onset (δT) and the temperature rise factor (α). From these results, it can be concluded that high speed air thermostating can be as
efficient as liquid thermostating. 相似文献
14.
Electrospray ionization mass spectrometry is applied for the selective detection of metal ligands after a post-column continuous-flow ligand-exchange reaction. The detection is based on the specific release of a reporter ligand from a metal-reporter ligand complex by a high affinity ligand. Constant infusion and direct-injection experiments are performed to optimize the method. The on-line coupling of a liquid chromatographic separation prior to the continuous flow ligand-exchange reaction enables the screening for high affinity ligands in complex samples. The feasibility of the method is demonstrated by using several ligands with a different affinity for either Cu(II) or Zn(II) ions. The selectivity of the ligand-exchange detection method can be tuned by the choice of the reporter ligand. This is demonstrated by using either 2,2'-bipyridyl or 5-methyl-1,10-phenanthroline as reporter ligands. 相似文献
15.
A simple high-performance liquid chromatographic method, using photodiode array detection was developed for the determination
of propylene glycol in human plasma and in the fluid retreived after continuous veno-venous hemofiltration. The method entailed
alkaline derivatization with benzoyl chloride and ethylene glycol as internal standard. The separation of the compounds, after
extraction with pentane, was carried out on a Pursuit C8 column with UV-detection at 230 nm. Validation samples were analyzed
with an accuracy between 95 and 105%, and intra- and inter-day coefficients of variation of less than 8%. The calibration
curve was linear over a concentration range of 5–100 mg L−1 with a detection limit of 1 mg L−1. Blood plasma samples of several patients were analysed by using the prescribed method with propylene glycol concentrations
varying from 5 to 98 mg L−1. Compared to previously described LC methods, this method is ten times more sensitive and thus suitable for use in pharmacokinetic
studies of propylene glycol. 相似文献
16.
Rozing G van de Goor T Yin H Killeen K Glatz B Kraiczek K Lauer HH 《Journal of separation science》2004,27(17-18):1391-1401
A systematic investigation of the influence of the perimeter shape of open and particle packed fused silica capillaries on chromatographic properties such as resistance to flow and dispersion of solutes propelled through these channels has been conducted. Verifications of these uncommon experiments with existing theoretical treatments are presented and the insights transferred to a novel polymer chip design with integrated facilities for complex separations. A comparison of the chromatographic performance of a real life proteomics sample on this chip with a capillary column of "similar" dimensions is presented. 相似文献
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19.
A system is described for the on-line extraction of a digested protein in a gel spot. The extract obtained was on-line transferred to a precolumn, used to desalinate and preconcentrate the sample. The precolumn was switched in-line with an LC-ESI-MS system to separate the digest products prior to detection. By using this approach sample losses were minimized and the sample was quantitatively transferred. The benefits of the system were shown for the in-gel tryptic digest of several model proteins. Using this system, the sensitivity was 13-fold increased compared to the off-line extraction of in-gel digest products leading to a higher sequence coverage and thus a better identification potential. Also, the within day repeatability was a factor 2.5 improvement using the on-line procedure compared to the off-line extraction procedure. 相似文献
20.
David D. Díaz Henk J. Bolink Luca Cappelli Eugenio Coronado 《Tetrahedron letters》2007,48(27):4657-4660
A series of new light emitting subphthalocyanines, lower homologues of phthalocyanines, were synthesized having color points covering the red-orange region of the visible spectrum. Additionally, they were found to be of potential use as narrow band emitters for red-light emitting diodes. 相似文献