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51.
Zvonimir B. Maksi Mirjana Eckert-Maksi Martin Klessinger 《Chemical physics letters》1996,260(5-6):572-576
It is shown, by the MP2(fc)/6-31G* */ /HF/6-31G* +ZPE(HF/6-31G*) theoretical model and concomitant use of homodesmic reactions, that the ipso proton affinities in polyfluorinated benzenes follow a simple additivity rule. Performance of the latter is good, as evidenced by a low average absolute deviation Δabs = 0.8 kcal/mol from the accurate ab initio results. Additional evidence supporting the additivity concept is provided by good accordance with the experimental proton affinity (PA) for perfluorobenzene. The present approach enables estimates of the ipso PAs of multiply substituted aromatics. It is particularly useful in those systems which involve or atomic groupings with lone pairs of electrons proximate to the aromatic π moiety. The additivity rule of thumb offers a simple rationalization of the ipso proton affinities. The origin of the PA additivity is briefly discussed. 相似文献
52.
J. Kuruc A. Petrů R. Čech P. Rajec 《Journal of Radioanalytical and Nuclear Chemistry》1996,208(1):351-368
It was found that the main ionogenic radiolytical degradation products of tributylphosphate were monobutylphosphate dibutylphosphate, phosphoric acid, formic, acetic, propionic and butyric acids as the result of gamma-irradiation of two-phase water-tributylphosphate system. In the case of irradiation of two-phase water-di(2-ethylhexyl)-phosphoric acid system, the main radiolytic degradation products are 2-ethylhexylphosphoric acid and phosphoric acid. All products were determined using isotachophoresis. According two-phase theory the total and partial radiation yields of products were calculated from the results.Dedicated to 65th birthday of prof. L. T. Bugaenko 相似文献
53.
Ondřej Linhart Alžběta Kolorosová-Mrázová Jan Kratzer Jakub Hraníček Václav Červený 《Analytical letters》2019,52(4):613-632
An ultraviolet-photochemical generator (UV-PVG) capable of post-column on-line transformation of both organic and inorganic mercury species to cold vapor (Hg0) with subsequent detection by quartz tube-atomic absorption spectrometry (QT-AAS) was developed. Mercury(II), methylmercury(I), ethylmercury(I), and phenylmercury(I) were successfully detected after separation by reversed-phase high-performance liquid chromatography (RP-HPLC). Two types of AAS detectors were compared. The first was a commonly used line-source instrument while the second was a high-resolution continuum source (HR-CS) AAS. The latter provided better limits of detection: 0.47?µg?L?1 for Hg(II), 0.84?µg?L?1 for methylmercury(I), 0.80?µg?L?1 for ethylmercury(I), and 2.0?µg?L?1 for phenylmercury(I). The repeatability at 30?μg?L?1 was 3.6%, 4.1%, 6.2%, and 4.5% for these species (n?=?10). These figures of merit were comparable with those reported for more sensitive atomic fluorescence spectrometry. Nine sample extraction procedures were investigated. Extraction by tetramethylammonium hydroxide and HCl at 75?°C was selected as the only method compatible with the proposed separation and detection steps providing high extraction efficiency and no changes in mercury speciation. The applicability of the proposed high-performance liquid chromatography–ultraviolet-photochemical vapor generation–quartz tube-atomic absorption spectrometry method was demonstrated using fish samples and certified reference materials (CRM) DOLT-4 (dogfish liver) and ERM-CE464 (tuna fish). The results were comparable to those obtained by a reference method based on L-cysteine extraction and high-performance liquid chromatography–inductively coupled plasma-mass spectrometry (HPLC–ICP-MS) determination. 相似文献
54.
Kourkine IV Ristic-Petrovic M Davis E Ruffolo CG Kapsalis A Barron AE 《Electrophoresis》2003,24(4):655-661
As the number of incidents of bacterial infections continues to rise around the globe, simpler, faster, and more sensitive diagnostic techniques are required to improve the safety of the food supply and to screen for potential bacterial infections in humans. We present here direct and indirect approaches for the detection of bacteria, which are based upon a combination of immunofluorescent staining and capillary electrophoresis. In the direct approach, Escherichia coli O157:H7 bacteria stained with fluorescein-tagged specific antibodies are detected by CE, while in the indirect approach fluorescein-tagged specific antibodies to E. coli are first captured by E. coli O157:H7 bacteria and then released and detected by CE. We have identified suitable bacteria staining and CE protocols, which involved a 10 mM Tris-borate-EDTA (TBE) buffer, 0.25 micro g antibody/1 million bacteria, and capillaries dynamically coated with poly-N-hydroxyethylacrylamide (polyDuramide). We have also successfully detected the presence of E. coli O157:H7 in contaminated meat. The total time required for analysis was 6-8 h, which is less than that realized in most commercial assays presently available. 相似文献
55.
A new approach to the evaluation of spin-orbit interaction (SOI) constants is presented. The SOI constants ξp and ξd of 4p and 3d electrons have been evaluated by employing the available atomic spectral data for the first transition row atoms and ions possessing the electron configuration K(2)L(8)3s23p63dα4sβ4pγ. 相似文献
56.
We propose a model for the production of extra (additional) lepton pairs in deep inelastic lepton-hadron scattering, e+e– annihilation and large pT processes. Extra lepton pairs are supposed to be originated by annihilations of quarks and antiquarks created during the space-time evolution of quark initiated jets. This mechanism yields predominantly dileptons with rather low masses. Predictions following from the model are compared with the recent data on trimuon production in neutrino-nucleon interactions. It is also suggested that internal hard processes can lead to dileptons with both small and large masses. The latter mechanism has rather small cross section but it is particularly interesting from the point of view of the simple quark-parton model.Dedicated to Academician Václav Votruba on the occasion of his seventieth birthday. 相似文献
57.
58.
In this paper, we demonstrate how to apply recently discovered ferromagnetic nematic liquid crystal for visualisation of magnetic fields. The material exhibits strong optical response to both external electric and magnetic fields, which gives us an opportunity to use it for the detection of an area of magnetic vector field in a way that both, the magnitude and the direction of a given field can be simultaneously measured. We discuss the physical model that describes the behaviour of ferromagnetic liquid crystal placed in a liquid crystal cell and demonstrate the method of extracting the information about an arbitrary magnetic field from the combination of magneto-optic and electro-optic response of the sample placed in that field. We have applied the principle to a special case, where magnetic field was visualised on a 2D area near a cylindrical permanent magnet. 相似文献
59.
Mesoporous molecular sieve SBA‐15 and conventional silica gel were grafted with 3‐[2‐(diethylamino)ethylamino]propyl groups and used as supports for the preparation of deposited palladium catalysts, which were subsequently evaluated in Stille cross‐coupling reaction of aryl bromides. The highest conversions were achieved with the metal‐saturated catalyst resulting from the modified SBA‐15. Influence of various reaction parameters (solvent, additive, temperature, etc.) on the overall yield and selectivity was studied. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
60.