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141.
Fourier-transform ion-cyclotron-resonance (FTICR) mass spectrometry has been used to uncover the mechanisms by which FeO+ dehydrates heptan-4-one ( 5a ) and nonan-5-one ( 6a ) in the gas phase. The study of isotopomeric ketones provides evidence that H2O loss is not due to a 1,1-elimination, thus ruling out the intermediacy of high-valent iron-carbene species. Rather, H2O is generated in a formal 1,2-elimination involving the ω/ω ? 1 positions of the alkyl chain (‘remote C? H bond activation’). In the consecutive alkene/H2O elimination, the olefins (ethylene from 5a and propene from 6a ) originate from the terminal part of one alkyl chain, and the H-atom is transferred to the FeO+ moiety in the course of this process, builds up together with an H-atom from the ω/ω-1 position of the other alkyl chain the H2O molecule. In either case, the O-atom of H2O is provided by the FeO+ species. 相似文献
142.
Mona Wells Michael Gösch Hauke Harms Jan Roelof van der Meer 《Mikrochimica acta》2005,151(3-4):209-216
This paper describes the development of an analytical technique for arsenic analyses that is based on genetically-modified
bioreporter bacteria bearing a gene encoding for the production of a green fluorescent protein (gfp). Upon exposure to arsenic
(in the aqueous form of arsenite), the bioreporter production of the fluorescent reporter molecule is monitored spectroscopically.
We compared the response measured as a function of time and concentration by steady-state fluorimetry (SSF) to that measured
by epi-fluorescent microscopy (EFM). SSF is a bulk technique; as such it inherently yields less information, whereas EFM monitors
the response of many individual cells simultaneously and data can be processed in terms of population averages or subpopulations.
For the bioreporter strain used here, as well as for the literature we cite, the two techniques exhibit similar performance
characteristics. The results presented here show that the EFM technique can compete with SSF and shows substantially more
promise for future improvement; it is a matter of research interest to develop optimized methods of EFM image analysis and
statistical data treatment. EFM is a conduit for understanding the dynamics of individual cell response vs. population response, which is not only a matter of research interest, but is also promising in the practical terms of developing
micro-scale analysis. 相似文献
143.
Detlef Schrder Jessica Loos Helmut Schwarz Roland Thissen Jana Roithova Zdenek Herman 《International journal of mass spectrometry》2003,230(2-3):113
Singly and doubly charged C4H3+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C4H32+ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IEv(C4H3+)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IEa(C4H3+)=16.33 eV and IEv(C4H3+)=16.49 eV for the most stable isomer H2C=C---CCH+. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C4H2+ has indeed a positive proton affinity of PA(C4H2+)=1.50±0.42 eV. 相似文献
144.
J. A. De Schutter F. De Croo G. Van der Weken W. Van den Bossche P. De Moerloose 《Chromatographia》1985,20(3):185-192
Summary A rapid and specific reversed-phase high-performance liquid chromatographic method (RPHPLC) is described for the determination of mebeverine hydrochloride in tablets. Elution was performed on an octyl silane column with a methanol-water mixture (75-25), containing 0.05% hexylamine as silanol-blocking agent, adjusted to pH 5.0 with phosphoric acid. The method gave accurate, precise and reproducible results. The mean recovery of the drug from six synthetic tablet mixtures was 100.0% with a relative standard deviation (RSD) of 0.94%. In order to test the specificity of the method, the interference of the degradation compounds of mebeverine hydrochloride and of the intermediates from the synthesis was investigated. None of them did interfere. By means of mass spectrometry and UV-spectrophotometry, the degradation compounds of mebeverine were identified as veratric acid and as 4-|ethyl-[2-(4-methoxyphenyl)-1-methylethyl]amino| 1-butanol. The stability study proved that mebeverine hydrochloride is very stable in tablets; the tablets still contain more than 95% of the declared drug potency after storage for more than one year at 50°C.Colofac; Duspatal; Duspatalin 相似文献
145.
Mikkelsen Ø Skogvold SM Schrøder KH Gjerde MI Aarhaug TA 《Analytical and bioanalytical chemistry》2003,377(2):322-326
Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L–1 (r2=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r2=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H2SO4 to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed. 相似文献
146.
The non-linear dielectric effect (NLDE), that is the increase in the dielectric constant divided by the square of the applied field, is measured for a number of non-polar molecular liquids and for liquid xenon. The values of the NLDE are compared with results in the literature and with values predicted by theory. The agreement with other experiments is quite good, but with theory is very poor, the only exception being Liquid xenon, where agreement is good. A possible explanation is given. The prediction that the NLDE should increase strongly near the critical point due to the divergence of the isothermal compressibility could not be established by experiment. The conclusion is drawn that this failure is due to the reduction by the theory of second-order effects to first-order thermodynamic and molecular properties. 相似文献
147.
Abstract— The photobehavior of the ciliates Climacostomuum virens, Euplotes daidaleos and Paramecium bursaria associated with endosymbiotic green algae ( Chlorella sp.) was compared with that of aposymbiotic ciliates (ciliates free of algae) and with the always aposymbiotic Paramecium arcticum . The aposymbiotic ciliates showed step-up photophobic responses. The responses were more frequent and occurred at lower light intensities when the organisms contained endosymbiotic algae. In contrast, step-down photophobic responses and photoaccumulations, as well as photokinesis, were never observed in aposymbiotic cells. These responses could be found only in ciliates when endosymbionts were present with the exception of C. virens , which showed none of these photoresponses. 相似文献
148.
W. Lautsch W. Broser W. Bandel W. Biedermann W. Gehrmann E. Schröder H. Gnichtel I. Zehmisch G. Kurth R. Krüger H. J. Kraege 《Colloid and polymer science》1954,138(3):129-142
Ohne Zusammenfassung
Die Arbeit wurde aus Mitteln des Marshall-Planes (ERP-Mittel) und mit Spenden aus dem „Fonds Chemie“ ausgeführt. Wir sprechen
den zust?ndigen Stellen für die Gew?hrung der Beihilfe unseren verbindlichsten Dank aus. Der Deutschen Forschungsgemeinschaft
danken wir für die überlassung einer Ultrazentrifuge, den Behring-Werken für die uns zur Verfügung gestellten Serumalbumin-
und -globulin-Pr?parate. 相似文献
149.
150.
Phosphine or phosphonium iodide react with boron triiodide in CS2 or benzene to form the adduct H3P–BI3. The water-sensitive white solid is thermally stable up to ~150°C. Its IR and NMR spectrum are recorded. 相似文献