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81.
82.
《Tetrahedron letters》2019,60(24):1582-1586
Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred. 相似文献
83.
Studies on metabolism of total glucosides of paeony from Paeoniae Radix Alba in rats by UPLC‐Q‐TOF‐MS/MS
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Wenli Cao Xinguo Wang Haojie Li Xuliang Shi Wencheng Fan Shaohua Zhao Minyan Liu Liying Niu 《Biomedical chromatography : BMC》2015,29(11):1769-1779
Total glucosides of paeony are the active constituents of Paeoniae Radix Alba. In this study, a novel strategy was proposed to find more metabolites and the differences between paeoniflorin, albiflorin and total glucosides of paeony (TGP). This strategy was characterized as follows: firstly, the animals were divided into three groups (paeoniflorin, albiflorin and TGP) to identify the source of TGP metabolites from paeoniflorin or albiflorin; secondly, a generic information‐dependent acquisition scan for the low‐level metabolites was triggered by the multiple mass defect filter and dynamic background subtraction; thirdly, the metabolites were identified with a combination of data‐processing methods including mass defect filtering, neutral loss filtering and product ion filtering; finally, a comparative study was used in the metabolism of paeoniflorin, albiflorin and TGP. Based on the strategy, 18 metabolites of TGP, 10 metabolites of paeoniflorin and 13 metabolites of albiflorin were identified respectively. The results indicated that the hydrolysis, conjugation reaction and oxidization were the major metabolic pathways, and the metabolic sites were the glycosidic linkage, the ester bond and the benzene ring. This study is first to explore the metabolism of TGP, and these findings enhance our understanding of the metabolism and the interactions of paeoniflrin and albiflorin in TGP. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
84.
Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films
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Zhe Qiang Maurice L. Wadley Bryan D. Vogt Kevin A. Cavicchi 《Journal of Polymer Science.Polymer Physics》2015,53(15):1058-1064
Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064 相似文献
85.
86.
87.
Summary Carbon deposits on the surface ofRu/Fe2O3 catalysts used in the water-gas shift reaction have been investigated by Auger Electron Spectrometry. A correlation has been
found between the thickness of the carbon deposit and the catalytic activity in WGSR. The carbon deposit covers the metallic
active centers and blocks their contact with reagents. The dotting of the iron oxide support with sodium has been found to
reduce the amount of carbon deposit. . 相似文献
88.
Padavattan Govindaswamy Patrick J. Carroll Yurij A. Mozharivskyj Mohan Rao Kollipara 《Journal of Chemical Sciences》2006,118(4):319-326
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl2(κ1-P-PPh2Py)]3 and [(η5-C5Me5) IrCl2(ϰ1-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+
5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+
8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3 and [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+
7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3, [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+
6 are established by single-crystal X-ray diffraction methods 相似文献
89.
90.
G. Montero L. Gonzlez E. Flrez M. D. García A. Surez 《Numerical Linear Algebra with Applications》2002,9(3):239-247
Parallel preconditioners are presented for the solution of general linear systems of equations. The computation of these preconditioners is achieved by orthogonal projections related to the Frobenius inner product. So, minM∈??∥AM?I∥ F and matrix M0∈?? corresponding to this minimum (?? being any vectorial subspace of ??n(?)) are explicitly computed using accumulative formulae in order to reduce computational cost when subspace ?? is extended to another one containing it. Every step, the computation is carried out taking advantage of the previous one, what considerably reduces the amount of work. These general results are illustrated with the subspace of matrices M such that AM is symmetric. The main application is developed for the subspace of matrices with a given sparsity pattern which may be constructed iteratively by augmenting the set of non‐zero entries in each column. Finally, the effectiveness of the sparse preconditioners is illustrated with some numerical experiments. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献