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51.
Yamada Kaoru Matsutani Shigeaki Uchiyama Akira Takahashi Toshio 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(1):49-54
Analyses of crown ether complexes of alkali metal ions and characterization of the complexes formed inm-nitrobenzyl alcohol have been carried out by fast atom bombardment (FAB) mass spectrometry. By using m-nitrobenzyl alcohol as a matrix for measurements, the stoichiometry of the complexes was assessed on the basis of the observed FAB peaks. In addition, the formation of crown ether-alkali metal complexes at a 2 : 1 molar ratio was enhanced by increasing the ionic radius of the metal ion in agreement with previous observations. On these grounds, FAB mass spectrometry may provide a rapid means for investigation of the complexation behavior of crown ethers and the stoichiometry of the complexes. 相似文献
52.
This paper presents detailed information on the experience gained during the attempts to model a set of transitional flows
due to boundary layer separation. These flows are developed on a flat plate with a semi-circular leading edge and they have
been coded by the ERCOFTAC Special Interest Group on Transition, as T3L flows. Different freestream velocities and turbulence
intensities configure these transitional flows and, by consequence, govern the transition mechanism, resulting in larger or
smaller transitional regions. The modeling of the T3L flows has been performed by adopting a low-Reynolds number second-moment
closure turbulence model. The results showed satisfactory agreement with the experimental measurements, although some difficulties
regarding successful convergence have been faced. The final conclusion is that turbulence modeling can present quite accurate
results for transitional flows without any additional use of ad-hoc modifications or additional equations based on various
transition models and intermittency transport modeling. 相似文献
53.
Dmitry Yu. Murzin 《Reaction Kinetics and Catalysis Letters》2007,90(2):225-232
Reaction route analysis is applied to visualize reaction networks in several heterogeneous catalytic reactions. Combination
of the theory of complex reactions with the notion of catalytic cycles results in a topological representation of complex
mechanisms with the nodes comprising all possible surface species including free sites and branches indicating interconnections
between reactions. 相似文献
54.
Summary Multiconfigurational second order perturbation theory (CASSCF/CASPT2) has been used to investigate the dependence of computed valence excitation energies and transition moments on the basis sets. Pyrazine has been selected as the test molecule. Atomic normal orbital (ANO) type basis sets are used throughout. Contractions of the structure (4s3p1d/2s) are found to be an optimal compromise between the quality and the size of the calculations and are capable of yielding results virtually identical to more extended basis sets. 相似文献
55.
Marko D. Mihovilovic Bernhard Müller Markus Spina Arjumand I. Durrani Peter Stanetty Georg Dazinger Karl Kirchner 《Monatshefte für Chemie / Chemical Monthly》2006,137(6):785-794
Summary. Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was
observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established
by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful
enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones
produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids. 相似文献
56.
In this paper, according to the molecular fragment principle, a series of eight ternary luminescent lanthanide complex systems were assembled, and whose compositions were determined with elemental analysis and infrared spectrum: Ln(MA)3(L)·H2O, where Ln = Sm, Eu, Tb, Dy; HMA = α‐methylacrylic acid; L = 1,10‐phenanthroline (phen), 2,2′‐bipyridine (bipy). The photophysical properties of these functional molecular systems were studied with ultraviolet‐visible absorption spectrum, and fluorescence excitation and emission spectrum. It was found that the heterocylic compounds (phen and bipy) act as the main energy donor and luminescence sensitizer for their suitable energy match and effective energy transfer to the emission energy level of Ln3+ ions. MMA ligand was only used as the terminal structural ligand to influence the luminescence. Especially terbium complex systems show the strongest luminescence for the optimum energy match and transfer between phen (bipy) and Tb3+ ion. 相似文献
57.
New Schiff bases of 2,4‐dihydroxybenzaldehyde with siloxane‐α,ω‐diamines having different numbers of siloxane units in the chain have been synthesized and characterized by spectroscopy, elemental and thermal analyses. These azomethines were found to form complexes readily with copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). From IR and UV–Vis studies, the phenolic oxygen and imine nitrogen of the ligand were found to be the coordination sites. Thermogravimetric analysis (TGA) data indicate the chelates to be more stable than the corresponding ligands. The melting points increase with shortening of the siloxane segment from azomethine, as well as the result of complexation. The chelates obtained were covalently inserted in polymeric linear structures by polycondensation through the OH‐difunctionalized ligand with 1,3‐bis(carboxypropyl)tetramethyldisiloxane. Direct polycondensation, assisted either by acetic anhydride or N,N′‐dicyclohexylcarbodiimide as dehydrating agent and the complex 4‐(dimethylamino)pyridinium 4‐toluenesulfonate as catalyst, was used for the synthesis of these compound types. The structures of the polymers obtained were confirmed by IR, UV and 1H NMR. Characterization was undertaken by TGA, solubility tests and viscosity measurements. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
58.
A. O. Manyashin A. I. Fomenko V. N. Storozhenko N. T. Berberova 《Russian Journal of Electrochemistry》2003,39(11):1240-1244
Stoichiometry and kinetics of reactions of 2,6-diphenyl-4-chloropyrylium, 4-chloroflavylium, 4-bromoflavylium, and 4-iodoflavylium perchlorates with nucleophiles N,N-dimethylaniline and n-phenylenediamine are studied using cyclic voltammetry and spectroscopy. Nucleophilic substitution in these compounds proceeds via the formation of a charge-transfer complex, which converts into a radical ion pair as a result of the electron transfer. Heterolytic clevage of the C–Hal bond occurs at the stage of pyranyl (flavanyl) radical. 相似文献
59.
Mooson Kwauk 《中国颗粒学报》2004,(1)
IntroductionInmaterialscience,differentmicrostructuresofthesamematerialsmayinducediversebehaviorsanddifferentcharacteristics.Westwood(1988)showed,asanexample,thatthetreatmentofaluminumsurfacewithcommercialphosphoricacidproducedmechanicallyinterlockedoxide搘hiskers?approximately10nmindiameterand400nminlength,whichmechanicallyinterlocked.Thismicro-structurecankeepsuchaconglomeratebondedoverconsiderablerangesofstressandtemperature.Inahumidatmosphere,especiallythatcontainingchlorine,however,suchox… 相似文献
60.
Using the full-potential linearized augmented plane wave (FP-LAPW) method, we have studied the effect of chemistry on the average intercalation voltage (AIV) caused by the Na ions intercalating into transition metal oxides. The effect of transition metal was systematically studied by varying M=Co, Ni and Mn in NaMO2 and fixing the α-NaFeO2 layered structure. The effect of the guest atoms into the host material is discussed in terms of the structural and electronic properties. Comparatively to Li intercalation, a significant electron transfer towards transition metal was found. This observation suggests that the transition metal contribute to the AIV determination and confirms the common assumption that intercalated electron reduces M4+ to M3+. 相似文献