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51.
Martin Kirchner Walter Schnelle Frank R. Wagner Rüdiger Kniep Rainer Niewa 《无机化学与普通化学杂志》2005,631(8):1477-1486
Single phase powders of (A19N7)[In4]2 (A = Ca, Sr) and (Ca4N)[In2] were prepared by reaction of melt beads of the metallic components with nitrogen. The crystal structure of (Ca19N7)[In4]2 was refined based on neutron and X‐ray powder diffraction data. The crystal structure of (Sr19N7)[In4]2 was solved from the X‐ray powder pattern. The structure refinements in combination with results from chemical analyses ascertain the compositions. The compounds (A19N7)[In4]2 (A = Ca, Sr) are isotypes of (Ca19N7)[Ag4]2; (Ca19N7)[In4]2 is probably identical to the earlier reported (Ca18.5N7)[In4]2. The crystal structure of the isotypes (A19N7)[In4]2 (A = Ca, Sr; cubic, , Ca: a = 1471.65(3) pm; Sr: a = 1561.0(1) pm) contains isolated [In4] tetrahedra embedded in a framework of edge‐ and vertex‐sharing (A6N) octahedra. Six of these octahedra are condensed by edge‐sharing around one central A2+ ion to form “superoctahedra” (A19N6) which are connected three‐dimensionally via further octahedra by corner‐sharing. The crystal structure of (Ca4N)[In2] (tetragonal, I41/amd, a = 491.14(4) pm, c = 2907.7(3) pm) consists of alternating layers of perovskite type slabs of vertex‐sharing octahedra (Ca2Ca4/2N) and parallel arranged infinite zigzag chains equation/tex2gif-stack-1.gif[In2]. In the sense of Zintl‐type counting the compounds (A2+)19(N3?)7[(In2.125?)4]2 present an electron excess, (Ca2+)4(N3?)[(In2.5?)2] is electron deficient. Metallic properties are supported by electrical resistivity and magnetic susceptibility measurements. The analysis of the electronic structures gives evidence for the existence of homoatomic interactions In–In and significant heteroatomic metal–metal interactions Ca–In which favor the deviations of the title compounds from the (8 – N) rule. 相似文献
52.
Pamela M. St. John Rainer D. Beck Robert L. Whetten 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1993,26(1):226-228
We review the processes which have been observed from collisions between alkali-halide clusters and solid surfaces. Soft impact of nanocrystalline NanF n?1 + clusters against solid surfaces causes them to cleave along the lowest energy (100) plane. At higher collision energies (Ei>1 eV/atom), an evaporative cascade occurs which is characteristic of a transformation of the nanocrystal to a molten state. Efficient F? transfer from the cluster to the surface can occur for the larger clusters (>60 atoms) scattering from Si(111), in direct competition with the cleaving channel at low energies. In this regime, strong bonds can form between the F? and silicon surface. The reaction probability increases with cluster size indicating that an impact-initiated shock wave is needed to enhance the reactive process. 相似文献
53.
Vilmos Fülöp Alajos Kalman Rainer Beckert Jürgen Fabian 《Monatshefte für Chemie / Chemical Monthly》1989,120(6-7):561-569
Summary The action of bisimidochlorides of oxalic acid on dithiocarbamates produces 2-thioxo-3-aryl(alkyl)-4,5-diiminothiazolidines by cycloacylation. The molecular structure of 2-thioxo-3-(4-methoxyphenyl)-4,5-bis(phenylimino)-thiazolidine is confirmed by X-ray crystal structure analysis.
Zur Reaktion von Dithiocarbaminaten mit stickstoffhaltigen Derivaten der Oxalsäure
Zusammenfassung Bei der Einwirkung von Bisimidchloriden der Oxalsäure auf Dithiocarbaminate entstehen durch Cycloacylierung 2-Thioxo-3-aryl(alkyl)-4,5-diiminothiazolidine. Die Molekülstruktur von 2-Thioxo-3-(4-methoxyphenyl)-4,5-bis(phenylimino)thiazolidin wird durch Röntgenkristallstrukturanalyse bestätigt.相似文献
54.
Rainer Domanig 《Monatshefte für Chemie / Chemical Monthly》1981,112(10):1195-1202
Starting with the chloromethyl compounds7 the new 2-azidomethyl-3-aryl-4-quinazolinones8 a-h were prepared, some of which have been reduced so far to the corresponding amines9 a, b, e, g by H2S in good yield. As a first example for the capability of the azides8 to undergo 1,3-dipolar cycloaddition the 2-quinazolinmethyl-1,2,3-triazol-4,5-dicarboxylicacid dimethylesters11 b, e, g were prepared by reacting8 with dimethylacetylenedicarboxylate (10).
1. Mitt.:Domanig R., Arch. Pharm., im Druck. 相似文献
55.
The molybdenum oxo complexes 1a and 1b catalyze efficiently the sulfur transfer to a series of alkenes 4 and allenes 6, for which elemental sulfur, phenylthiirane, or methylthiirane have been employed as sulfur sources to afford the corresponding episulfides 5 and 7. The most effective catalytic episulfidation system to date is the combination of the dithiophosphate-ligated oxo complex 1b and phenylthiirane (Ibeta). This metathesis process is efficient enough to convert usually reluctant alkenes (cyclopentene, cycloheptene, Z-cyclooctene, Z-cyclononene, E-cyclodecene, norbornene, and even bicyclopropylidene) to their episulfides in good yields under mild conditions. The direct catalytic sulfuration of allenes (cyclonona-1,2-diene, cyclonona-1,2,5-triene, cyclodeca-1,2-diene, and 2,4-dimethylpenta-2,3-diene) to their labile methylenethiiranes is unprecedented. 相似文献
56.
Dalvit C Mongelli N Papeo G Giordano P Veronesi M Moskau D Kümmerle R 《Journal of the American Chemical Society》2005,127(38):13380-13385
NMR-based binding and functional screening performed with FAXS (fluorine chemical shift anisotropy and exchange for screening) and 3-FABS (three fluorine atoms for biochemical screening) represents a potential alternative approach to high-throughput screening for the identification of novel potential drug candidates. The major limitation of this method in its current status is its intrinsic low sensitivity that limits the number of tested compounds. One approach for overcoming this problem is the use of a cryogenically cooled (19)F probe that reduces the thermal noise in the receiver circuitry. Sensitivity improvement in the two screening techniques achieved with the novel cryogenic (19)F probe technology permits an increased throughput, detection of weaker binders and inhibitors (relevant in a fragment-based lead discovery program), detection of slow binders, and reduction in protein and substrate consumption. These aspects are analyzed with theoretical simulations and experimental quantitative performance evaluation. Application of 3-FABS combined with the cryogenic (19)F probe technology to rapid screening at very low enzyme concentrations and the current detection limits reached with this approach are also presented. 相似文献
57.
58.
Rainer P. H. Garten 《中国化学会会志》1994,41(3):259-274
Selected prominent problems in the analysis of advanced ceramic materials are surveyed. The importance of reliability of results is discussed in the field of elemental trace- and microanalysis in view of its interaction with economy, power of detection, local resolution and speciation selectivity. Particular problems in the analysis of major constituents, trace components and microlocal distributions are based on the striking propertics of ceramics; they are exemplified. Analytical assistance must start from the beginning of the production processing, in the preparation of the powdered base materials. Determination of the stoichiometry requires high accuracy and differentiation of chemical species in bulk and surface analysis of ceramic base powders. Element trace determination by direct instrumental methods requires standard reference materials for calibration; these are currently inavailable in a sufficient variety. For optimum reliability and power of detection, element traces must be prepared in isolated form in a small excitation volume for analysis. A review on the state-of-the-art of wet-chemical combined procedures is presented. Decomposition position procedures are emphasized, due to their risk of contributing severe systematic error. Combustion in elementary fluorine is presented for decomposition of refractory materials. The performance of some direct procedures is discussed. Very efficient methods are available for element trace determinations in ceramic materials, offering high detection power. Several approaches for high-resolution local microanalysis in non-conductive ceramic materials are identified as the most promising development in the analysis of sintered compact ceramic products and devices. 相似文献
59.
J rg Enderlein Peter M. Goodwin Alan Van Orden W. Patrick Ambrose Rainer Erdmann Richard A. Keller 《Chemical physics letters》1997,270(5-6):464-470
We have developed a maximum likelihood estimator to distinguish between similar molecules at the single molecule level based upon fluorescence decay measurements. Time resolved fluorescence measurements for single Rhodamine 6G and tetramethylrhodamine isothiocyanate molecules in fluid flow are derived from time-correlated single photon counting. A maximum likelihood estimator is developed and applied to data from a mixture of molecules. Single molecules are identified and distinguished by their fluorescence time decays. Comparison is made between identification error rates and theoretical predictions. To our knowledge, this is the first reported example of single molecule identification by fluorescence decay in a mixture. 相似文献
60.