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991.
Odn Arjona Roberto Fernndez de la Pradilla Angel Martin-Domenech Joaquin Plumet 《Tetrahedron》1990,46(24):8187-8198
The nucleophilic Sn2' bridge opening of 7-oxabicyclo[2.2.1] hept-5-en-2-ols with organolithium reagents occurs in a regio- and stereospecific fashion to produce 6-substituted-cyclohex-4-en-1,3-diols, regardless of the stereochemistry at C-2. A free alcohol functionality is necessary to attain complete regiocontrol of the process. The methodology is utilized to prepare an optically pure cyclohexene derivative, (+)-(1S,3S,6R)-6-n-butyl-3-methyl-cyclohex-4-en-1,3-diol (5b), as a model system. 相似文献
992.
L. Turi Nagy P. Pelikn M. Lika M. Haring M. eppan M. Breza 《International journal of quantum chemistry》1979,16(3):485-500
The model systems of molecular nitrogen fixation [N2 + H]?, [N2 + H]+, [N2 + H]?, [N2 + H2], [N2 + H2]+, and [N2 + H2]? were studied by the semiempirical INDO method. The study was based on the formal analogy between the catalytic reactions and the photochemical, radical, and ionic reactions on the other side. Symmetrical and donor-acceptor properties of necessary catalytic systems were proposed using the dependence of energy characteristics and electron structure on reaction coordinate. On the basis of this MO study we have proposed the appropriate symmetry types of catalysts for each of acceptable models of nitrogen fixation. For one of the proposed systems there was realised a model MO computation with explicit inclusion of atoms of transition metals (Fe, V). 相似文献
993.
Katarína Györyová Ján Skoršepa Jozef Chomič 《Monatshefte für Chemie / Chemical Monthly》1983,114(10):1137-1139
Two cyano complexes of the type [R 3S]2 [Pd(CN)4] (R 3S+=Me 3S+,Ph 3S+ cations) were prepared. The identity of the obtained samples was verified by chemical analysis and investigated by IR-spectroscopy. Thev CN stretching frequencies of the complexes were compared with similar frequencies of the corresponding alkaline cyano complex. The thermal decomposition of the compounds was examined. 相似文献
994.
E. Robens D. Möhlmann Th. Gast R. Staudt M. Eger 《Journal of Thermal Analysis and Calorimetry》2006,86(1):27-29
The balance is the most widely used complex measuring instrument in
science and techniques. To install a balance on Mars is a challenge for numerous
aspects of in situ measurements in the next decade. By means of a balance
useful parameters could be determined and a variety of investigations could
be carried out there. Possible applications of a balance on Mars are reviewed.
Choice of type and demands on the balance with regard to the conditions on
Mars are discussed. The first step is to test a load cell with strain gauge
deflection sensor. 相似文献
995.
The degradation behaviour of methylmercury (MeHg) under microwave irradiation is investigated, as is the (different) degradation
behaviour of ethylmercury (EtHg) under similar irradiation. A simple and highly sensitive SPME-GC-pyrolysis-AFS system was
used to analyse the aqueous MeHg and EtHg standard solutions after derivatization with sodium tetraphenylborate (NaBPh4). Samples were irradiated in a microwave digester at microwave powers ranging from 20 to 160 W for durations of 2 to 10 min.
The different tolerances towards microwave treatment of the two organomercury species were evident. Practically no degradation
was experienced for MeHg for up to 8 minutes of irradiation at 120 W or for up to 4 minutes at 160 W. Significant analyte
loss was observed for EtHg after 2 minutes at 40 W of microwave power.
Awarded a Poster Prize on the occasion of the European Winter Conference on Plasma Spectrochemistry, February 2005, Budapest,
Hungary 相似文献
996.
Wulff WD Korthals KA Martínez-Alvarez R Gómez-Gallego M Fernández I Sierra MA 《The Journal of organic chemistry》2005,70(13):5269-5277
By means of deuterium-labeling experiments, we have carried out a systematic ESI-MS study to determine the mechanism of ESI ionization of alkenyl and alkynyl group 6 Fischer carbene complexes. These compounds can be ionized under ESI conditions only in the presence of additives such as hydroquinone (HQ) or tetrathiafulvalene (TTF). Our results demonstrate that in the ESI source an anion-radical is formed after the initial HQ- or TTF-mediated electron transfer to the metallic carbene complex. For alkenyl carbene complexes, this species evolves by extrusion of a hydrogen radical to form an allenylchromium anion that is detected as the [M - H](-) ion in the mass spectrum. The preference for this mechanistic pathway could be rationalized by DFT calculations. In the case of alkynyl carbene complexes, experiments combining deuterated substrate, additive, and solvent demonstrate that the previously proposed allene-anion carbene complex is not formed. Instead, the H transfer from the ethoxy group in the anion radical, followed by extrusion of a hydrogen radical, leads to an allenyl anion that is detected in the ESI-MS as [M - H - CO](-). 相似文献
997.
The stability and characteristics of the ornithine (Orn), lysine (Lys), putrescine (Put), cadaverine (Cad), 1,7-diaminoheptane (Diah), spermidine (Spd) and spermine (Spm) derivatives obtained with the o-phthalaldehyde (OPA)-ethanethiol (ET)-fluorenylmethyl chloroformate (FMOC) reagent has been investigated. The stoichiometry of the introduced, two-step derivatization process has been followed by photodiode array (DAD) and fluorescence (FL) detections, simultaneously, while the composition of derivatives was confirmed by on-line HPLC-electrospray ionization (ESI) MS measurements. Depending on the composition of the OPA reagents, in addition to the secondary amino group-containing Spd and Spm, under common aqueous conditions also Orn and Lys do react with FMOC resulting in derivatives of various compositions. Applying the OPA-ET reagent of increasing methanol (Met) content (38-80%, v/v) the formation of the FMOC group containing Orn and Lys derivatives could be considerably decreased. Optimum elution condition (18 min, including equilibration) was developed for the simultaneous quantitation of Orn, Lys, Put, Cad, Diah, Spd and Spm, in the presence of the rest of protein amino acids. The practical utility of the method was demonstrated by the analysis of mouse tissues. Average reproducibility of quantitations, characterized with the relative standard deviation percentages of fluorescence intensities and UV responses, in order of listing, proved to be 2.1% and 2.1%, respectively. 相似文献
998.
Jakubowicz K Wong YS Chiaroni A Bénéchie M Marazano C 《The Journal of organic chemistry》2005,70(19):7780-7783
[reaction: see text] 3-Alkyl-1,4-dihydropyridines dimerize in acidic medium, at low temperature, to give polycyclic imminium salts derivatives that were reduced to afford new polycyclic diamine scaffolds. The reaction can be extended to enantiopure series starting from R-(+)- or S-(-)-1-phenylethylamine. Long exposure of the polycyclic imminium salt intermediates to air moisture at 20 degrees C resulted in formation of new amide derivatives. This is probably due to the addition of water followed by an intramolecular oxido-reduction process. 相似文献
999.
García Fernández R Montes Bayón M García Alonso JI Sanz-Medel A 《Journal of mass spectrometry : JMS》2000,35(5):639-646
A novel interface design for coupling gas chromatography and inductively coupled plasma mass spectrometry (GC/ICP-MS) was used to perform mercury speciation in biological tissues. Three derivatization approaches were optimized and compared for this purpose: anhydrous butylation using a Grignard reagent, aqueous ethylation by means of NaEt(4)B and aqueous propylation with NaPr(4)B. The last reagent was synthesized in the laboratory as it is not commercially available. Detection limits obtained by GC/ICP-MS ranged between 100 and 200 fg (as absolute mass) for methylmercury and between 500 and 600 fg for inorganic mercury using a 1 microl injection. Quantification of methyl- and inorganic mercury was carried out by resorting to aqueous calibration, using ethylmercury as internal standard for both propylation and butylation derivatization techniques. For ethylation procedures, a methylpropylmercury solution was used as internal standard. The absence of transmethylation during sample preparation was checked using a 97% enriched (202)Hg inorganic standard. The accuracy of the three derivatization approaches was evaluated by the analysis of the certified reference material DOLT-2 (dogfish liver) from the National Research Council of Canada and certified for methylmercury, with satisfactory results. 相似文献
1000.
Ramón Puyané Isabelle Guy Renaud Metz 《Journal of Sol-Gel Science and Technology》1998,13(1-3):575-578
The ceramic microstructure, the chemical homogeneity of specific dopants and the mechanical integrity of a varistor disc are critical parameters in determining the transient voltage suppression features of these devices. The material properties and overall quality of the starting ceramic powders used to produce such components are essential in achieving the desired properties. The present work describes a novel chemical method developed to produce doped zinc oxide powders and an industrial scale manufacturing process for the production of final varistor blocks for surge arrester applications. The results are compared with those obtained when using standard varistor powder made by the mixed oxide route is used. All the fundamental electrical properties of the discs have been determined and correlated with the relevant manufacturing steps. 相似文献