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21.
The charge-transfer (CT) transition of complexes involving alkylated aromatic electron donors shifts hypsochromically upon benzylic deuteration. This is attributed to hyperconjugative effects. 相似文献
22.
Tiggelaar RM Berenschot JW de Boer JH Sanders RG Gardeniers JG Oosterbroek RE van den Berg A Elwenspoek MC 《Lab on a chip》2005,5(3):326-336
In this paper the fabrication and electrical characterization of a silicon microreactor for high-temperature catalytic gas phase reactions, like Rh-catalyzed catalytic partial oxidation of methane into synthesis gas, is presented. The microreactor, realized with micromachining technologies, contains silicon nitride tubes that are suspended in a flow channel. These tubes contain metal thin films that heat the gas mixture in the channel and sense its temperature. The metal patterns are defined by using the channel geometry as a shadow mask. Furthermore, a new method to obtain Pt thin films with good adhesive properties, also at elevated temperatures, without adhesion metal is implemented in the fabrication process. Based on different experiments, it is concluded that the electrical behaviour at high temperatures of Pt thin films without adhesion layer is better than that of Pt/Ta films. Furthermore, it is found that the temperature coefficient of resistance (TCR) and the resistivity of the thin films are stable for up to tens of hours when the temperature-range during operation of the microreactor is below the so-called "burn-in" temperature. Experiments showed that the presented suspended-tube microreactors with heaters and temperature sensors of Pt thin films can be operated safely and in a stable way at temperatures up to 700 degrees C for over 20 h. This type of microreactor solves the electrical breakdown problem that was previously reported by us in flat-membrane microreactors that were operated at temperatures above 600 degrees C. 相似文献
23.
Characterisation of fatty acids in biological oil samples using comprehensive multidimensional gas chromatography 总被引:1,自引:0,他引:1
Comprehensive multidimensional gas chromatography can adequately resolve very complex mixtures of analytes such as the fatty acid mixtures which are contained in, e.g., fish and vegetable oils. Well-ordered patterns are obtained in the two-dimensional separation plane which can be used to tentatively identify peaks when no standard is available. The technique which can also be used for quantification, i.e., quantitative ratio analysis, should be especially useful for fingerprinting purposes. Unravelling the composition of complex mixtures such as fish oils appears to be highly rewarding. 相似文献
24.
Mass spectra of 1-phenylethanol-1 and its analogues, specifically deuterated in the aliphatic chain, suggest that the [M? CH3]+ ion is represented partly by an α-hydroxybenzyl fragment. Moreover, the molecular ion loses successively—after scrambling of all hydrogen atoms, except those of CH3? a hydrogen atom and C6H6, generation the CH3CO+ ion. Diffuse peaks, found in the spectra of of 2-phenylethanol-1 and its analogues, specifically deuterated in the aliphatic chain and in the phenyl ring, show that the molecular ion loses C2H4O, possibly via a four-center mechanism, after an exchange of aromatic and hydroxylic hydrogens. Mass spectra of 1-phenylpropanol-2 and its analogues, specifically, deuterated in the aliphatic chain, demonstrate that in the molecular ion exclusively the hydroxyl hydrogen atom is transferred to one of the ortho-positions of the phenyl ring via a McLafferty rearrangement, generating the [M ? C2H4O]+ ion. Furtherore, an eight-membered ring structure is proposed for the [M ? CH3]+ ion to explain the loss of H2O and C2H2O from this ion after an extensive scrambling of hydrogen atoms. 相似文献
25.
De Boer JL Ritsema R Piso S Van Staden H Van Den Beld W 《Analytical and bioanalytical chemistry》2004,379(5-6):872-880
Two screening methods were developed for rapid analysis of a great number of urine and blood samples within the framework of an exposure check of the population after a firework explosion. A total of 56 elements was measured including major elements. Sample preparation consisted of simple dilution. Extensive quality controls were applied including element addition and the use of certified reference materials. Relevant results at levels similar to those found in the literature were obtained for Co, Ni, Cu, Zn, Sr, Cd, Sn, Sb, Ba, Tl, and Pb in urine and for the same elements except Ni, Sn, Sb, and Ba in blood. However, quadrupole ICP–MS has limitations, mainly related to spectral interferences, for the analysis of urine and blood, and these cause higher detection limits. The general aspects discussed in the paper give it wider applicability than just for analysis of blood and urine—it can for example be used in environmental analysis. 相似文献
26.
Van den Bergh V Coeckelberghs H Vanhees I De Boer R Compernolle F Vinckier C 《Analytical and bioanalytical chemistry》2002,372(5-6):630-638
Biogenic non-methane hydrocarbons such as isoprene, alpha-pinene, and beta-pinene, are emitted by forests in very large quantities. To evaluate the role of alpha- and beta-pinene and their contribution to the global production of trace gases and especially aerosol precursors, a study of the oxidation mechanism of alpha- and beta-pinene with hydroxyl radicals must be conducted.The degradation products of both monoterpenes with hydroxyl radicals were identified and quantified in a fast-flow reactor. The products were collected on a liquid-nitrogen trap coated with a 2,4-DNPH solution to which two internal standards (benzaldehyde-2,4-DNPH and tolualdehyde-2,4-DNPH) had been added. The collection method was based on the in situ conversion of aldehyde and/or ketone compounds to their 2,4-dinitrophenylhydrazone derivatives. The derivatives were analyzed by HPLC-MS using APCI(-). TIC chromatograms and mass spectral data for the various oxidation products are presented.For alpha-pinene, pinonaldehyde is the most important degradation product, with smaller amounts of acetone, formaldehyde, campholenealdehyde, and acetaldehyde. For beta-pinene, nopinone and formaldehyde are the most abundant products, of almost equal importance, whereas acetone and acetaldehyde are minor compounds. 相似文献
27.
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29.
F. Azaiez W. H. Kelly W. Korten M. A. Deleplanque F. S. Stephens R. M. Diamond J. E. Draper A. O. Macchiavelli E. Rubel J. de Boer M. Rohn J. A. Becker E. A. Henry M. J. Brinkman S. W. Yates A. Kuhnert T. F. Wang 《Zeitschrift für Physik A Hadrons and Nuclei》1991,338(4):471-472
Two superdeformed (SD) bands have been found and assigned to195Tl on the basis of excitation function and cross bombardment results. The two bands are almost identical in transition energies to those observed in193Tl. They are signature partners with a splitting, presumably due to the proton i13/2 (=5/2) orbital, characteristic of all known SD bands in the thallium isotopes. Their alignments relative to the193Tl bands were found to be zero.On leave from Comision National de Energia Atomica 1429 Buenos Aires, Argentina. 相似文献
30.
Jacob de Boer Quy T. Dao Peter G. Wester Sren Bwadt Udo A. Th. Brinkman 《Analytica chimica acta》1995,300(1-3):155-165
The mono-ortho chlorobiphenyls (CBs) 60, 74, 114, 123, 157, 167 and 189 were determined in Aroclor mixtures and aquatic organisms by multidimensional gas chromatography with electron capture detection (MDGC/ECD), using a combination of an Ultra 2 and an FFAP column. MDGC/ECD is recommended as the most suitable technique for direct determination of these CBs, without a liquid chromatographic (LC) pre-separation of mono-ortho CBs from the other CBs. Dependent, to some extent, on the stationary phase used, single-column determinations of these CBs easily yield too high results due to the presence of interferences. The contribution of the mono-ortho CBs studied to the total 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) from CBs in fish is highly dependent on the toxic equivalency factors (TEFs) used and varies between 0.02 and 22%. This contribution is mainly due to CBs 74, 114, 157 and 167 which may easily be determined by taking three heart-cuts and combining them into one MDGC/ECD run. The analytical error is negligible compared with the huge uncertainty of the TEFs. A need for more precise TEFs is emphasized. 相似文献