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101.
An investigation to determine the compounds present in the Ln2O3Nb2O5 systems (Ln = La, Gd, and Y) and attempts to activate such compounds with Ti, In, Sb, Bi, Eu, and Tb revealed that only the orthoniobate (LnNbO4) compound was a suitable host lattice and LnNbO4:Bi under 2537 Å excitation produced the best phosphors. GdNbO4:Bi is a brighter phosphor than the La and Y analogs, emitting at slightly higher energies. The position of the GdNbO4:Bi peak emission at 4500 Å is independent of the activator concentration whereas peak emissions for LaNbO4:Bi and YNbO4:Bi move to lower energies with increasing Bi concentration. 相似文献
102.
Thermally-induced reaction between bicyclo[5.1.0]octa-2,5-diene (I) and sulphur dioxide under dry conditions is toluene-d8 as solvent leads to the unexpected formation of the hitherto unknown diene sulphone 7-thiabicyclo[4.2.1]nona-2,4-diene 7,7-dioxide (II). 相似文献
103.
Patrick DL Flanagan JF Kohl P Lynden-Bell RM 《Journal of the American Chemical Society》2003,125(22):6762-6773
Chemical force microscopy and related force measurement techniques have emerged as powerful tools for studying fundamental interactions central to understanding adhesion and tribology at the molecular scale. However, detailed interpretation of these interactions requires knowledge of chemical and physical processes occurring in the region of the tip-sample junction that experiments cannot provide, such as atomic-scale motions and distribution of forces. In an effort to address some of these open issues, atomistic molecular dynamics simulations were performed modeling a chemical force microscope stylus covered with a planar C12 alkylthiolate self-assembled monolayer (SAM) interacting with a solid wall. A complete loading-unloading sequence was simulated under conditions of near-constant equilibrium, approximating the case of infinitely slow tip motion. In the absence of the solid wall, the stylus film existed in a fluid state with structural and dynamic properties similar to those of the analogous planar SAM at an elevated temperature. When the wall was brought into contact with the stylus and pressed against it, a series of reversible changes occurred culminating with solidification of the SAM film at the largest compressive force. During loading, the chemical composition of the contact changed, as much of the film's interior was exposed to the wall. At all tip heights, the distribution of forces within the contact zone was uneven and subject to large local fluctuations. Analysis using the Johnson-Kendall-Roberts, Derjaguin-Muller-Toporov, and Hertz contacts mechanics models revealed significant deviations from the simulation results, with the JKR model providing best overall agreement. Some of the discrepancies found would be overlooked in an actual experiment, where, unlike the simulations, contact area is not separately known, possibly producing a misleading or incorrect interpretation of experimental results. These shortcomings may be improved upon by using a model that correctly accounts for the finite thickness of the compliant components and nonlinear elastic effects. 相似文献
104.
A heterocyclic peptide nanotube 总被引:3,自引:0,他引:3
An open-ended hollow tubular structure is designed based on hydrogen-bond-directed self-assembly of a chimeric cyclic peptide subunit comprised of alternating alpha- and epsilon-amino acids. The design features a novel 1,4-disubstituted-1,2,3-triazole epsilon-amino acid and its utility as a peptide backbone substitute. The N-Fmoc-protected epsilon-amino acid was synthesized in high yield and optical purity in three steps from readily available starting materials and was employed in solid-phase peptide synthesis to afford the desired cyclic peptide structure. The cyclic peptide self-assembly has been studied in solution by (1)H NMR and mass spectrometry and the resulting tubular ensemble characterized in the solid state by X-ray crystallography. 相似文献
105.
Submicrogram amounts of vanadium in rat liver tissue have been analyzed by rapid activation analysis. A 5-min radiochemical separation coupled with γ-ray spectrometry permitted utilization of the 3.8-min vanadium-52 radioisotope. With this procedure the lower limit of detection at a thermal neutron flux of 1012 n/cm2/sec was about 3·10-9 g of vanadium. 相似文献
106.
Ze'ev V. I. Zaretskii Albert Avraham Ben-Bassat David Lavie 《Journal of heterocyclic chemistry》1975,12(5):837-840
The mass spectra of α-, β- and γ-pyridine aldoximes and the respective O-methyl ethers were studied. The mass spectral behaviour of α-pyridine aldoxime is characterized by the elimination of NO, while the molecular ion of the γ-isomer expels H2 CN. In the case of the β-isomer the formation of the m/e 67 ion (C4H5N) in a concerted process is the main feature. In the α-pyridine aldoxime methyl ether, in sharp contrast to the hydroxy analog, the M-30 peak was found to be due to the elimination of CH2O, the expulsion of NO being absent. The mechanism of the fragmentation reactions is discussed, the conclusion drawn being based on the high resolution measurements as well as on the spectra of the respective deuterioanalogs and on the metastable transitions. 相似文献
107.
A computational strategy to model the amorphous phase of comblike polymers is presented. The strategy, denoted SuSi/CB (CB-configurational bias), combines the strength of an algorithm recently developed to generate reliable microstructures of dense amorphous polymers, which is based on a random search of energy minima, and configurational bias Monte Carlo method. The influence of different parameters used to define the characteristics of SuSi/CB on both the reliability of the generated structures and the computational effort has been examined in detail. Finally, we have modeled and characterized the supramolecular organization of poly(octadecyl acrylate) in the amorphous state. 相似文献
108.
Birney DM 《Organic letters》2004,6(5):851-854
Two possible pathways for the nitrosation of formamide and N-methyl formamide by nitrosonium ion (NO(+)) have been investigated at the B3LYP/6-31G(d,p) level. The key steps are pseudopericyclic 1,3-sigmatropic rearrangements to give the observed N-nitrosamides. The transition structures (8a and 8b) are close to planar on the amide moiety and have remarkably low barriers of only 6.6 and 4.8 kcal/mol from the lowest energy conformations of 6a and 6b, respectively. [reaction: see text] 相似文献
109.
Methods for the incorporation of non-natural amino acids into proteins have advanced significantly over recent years and in this tutorial review we aim to give a general overview of the area. These techniques offer the possibility of modulating the structures and functions of proteins and thus permit the generation of novel designed systems for both biocatalytic and mechanistic studies. Four complementary approaches are discussed in detail along with examples of their application. The advantages and disadvantages of each technique are also discussed. 相似文献
110.
(E)-beta-Trialkylstannyl-alpha,beta-unsaturated ketones are readily available from secondary propargylic alcohols via a two-step sequence involving highly regio- and stereoselective Pd(0)-catalyzed hydrostannation followed by mild oxidation (TPAP). The methodology has been applied to the synthesis of enantiomerically pure enone 12 which is a key intermediate for the total synthesis of zoanthamine, a structurally complex marine natural product. 相似文献