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51.
Surmont R Verniest G De Schrijver M Thuring JW ten Holte P Deroose F De Kimpe N 《The Journal of organic chemistry》2011,76(10):4105-4111
Fluorinated pyrazoles bearing additional functional groups that allow further functionalization are of considerable interest as building blocks in medicinal chemistry. The developed synthetic strategy for new 3-amino-4-fluoropyrazoles consists of a monofluorination of β-methylthio-β-enaminoketones using 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) toward the corresponding monofluorinated enaminoketones, followed by condensation with different hydrazines. 相似文献
52.
DNA block copolymer doing it all: from selection to self-assembly of semiconducting carbon nanotubes
53.
M. J. van Bommel P. M. C. ten Wolde T. N. M. Bernards 《Journal of Sol-Gel Science and Technology》1994,2(1-3):167-170
The influence of MPS on the hydrolysis and condensation process of TEOS is studied by means of hydrolysis time (t
H) and gelation time (t
G) curves. The addition of MPS to a mixture of TEOS, ethanol and water results in a substantial increase in t
G. The increase is most pronounced when adding takes place in the acid step of the sol-gel process of TEOS.In acid environment hydrolysis of MPS will be dominant compared to hydrolysis of TEOS. This results in an effective decrease of the amount of water available for the hydrolysis of TEOS. However, this decrease in water concentration cannot explain the complete effect of the addition of MPS. The hydrolysed MPS will also be incorporated in the gel network and will strongly influence the cross-linking ability. The lesser functionality of MPS compared to TEOS and the steric hindrance of the acrylate group results in a large increase in t
G. 相似文献
54.
In liquid-crystal elastomers, the simultaneous presence of rubber elasticity due to the crosslinked backbone chains and of optical birefringence due to the mesogens in the side chains lead to exceptional physical properties. An elastic deformation of the network influences the order of the mesogens and, therefore, the optical properties. A theory based on a Landau-de Gennes expansion of the free energy is proposed. In the opaque polydomain phase, the local orientation is given by a compromise between the external mechanical field and a local anchoring interaction. As the field is increased, it becomes energetically favorable for the mesogens to align parallel to the mechanical field, and a transition to a transparent monodomain structure occurs. Results for the average orientation, the stress and the chain conformation are given. 相似文献
55.
Gaikwad AV Holuigue A Thathagar MB ten Elshof JE Rothenberg G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(24):6908-6913
Leaching of palladium species from Pd nanoparticles under C--C coupling conditions was observed for both Heck and Suzuki reactions by using a special membrane reactor. The membrane allows the passage of palladium atoms and ions, but not of species larger than 5 nm. Three possible mechanistic scenarios for palladium leaching were investigated with the aim of identifying the true catalytic species. Firstly, we examined whether or not palladium(0) atoms could leach from clusters under non-oxidising conditions. By using our membrane reactor, we proved that this indeed happens. We then investigated whether or not small palladium(0) clusters could in fact be the active catalytic species by analysing the reaction composition and the palladium species that diffused through the membrane. Neither TEM nor ICP analysis supported this scenario. Finally, we tested whether or not palladium(II) ions could be leached in the presence of PhI by oxidative addition and the formation of [Pd(II)ArI] complexes. Using mass spectrometry, UV-visible spectroscopy and 13C NMR spectroscopy, we observed and monitored the formation and diffusion of these complexes, which showed that the first and the third mechanistic scenarios were both possible, and were likely to occur simultaneously. Based on these findings, we maintain that palladium nanoparticles are not the true catalysts in C--C coupling reactions. Instead, catalysis is carried out by either palladium(0) atoms or palladium(II) ions that leach into solution. 相似文献
56.
57.
Witte PT Chowdhury SR ten Elshof JE Sloboda-Rozner D Neumann R Alsters PL 《Chemical communications (Cambridge, England)》2005,(9):1206-1208
A "sandwich" type polyoxometalate catalyst ([MeN(n-C8H17)3]12[WZn3(ZnW9O34)2]) was very efficiently recycled by nanofiltration with almost quantitative retention, using an alpha-alumina supported mesoporous gamma-alumina membrane. 相似文献
58.
We have developed a new numerical technique, called Green's-function reaction dynamics (GFRD), that makes it possible to simulate biochemical networks at the particle level and in both time and space. In this scheme, a maximum time step is chosen such that only single particles or pairs of particles have to be considered. For these particles, the Smoluchowski equation can be solved analytically using Green's functions. The main idea of GFRD is to exploit the exact solution of the Smoluchoswki equation to set up an event-driven algorithm, which combines in one step the propagation of the particles in space with the reactions between them. The event-driven nature allows GFRD to make large jumps in time and space when the particles are far apart from each other. Here, we apply the technique to a simple model of gene expression. The simulations reveal that spatial fluctuations can be a major source of noise in biochemical networks. The calculations also show that GFRD is highly efficient. Under biologically relevant conditions, GFRD is up to five orders of magnitude faster than conventional particle-based techniques for simulating biochemical networks in time and space. GFRD is not limited to biochemical networks. It can also be applied to a large number of other reaction-diffusion problems. 相似文献
59.
Evgeny?PolushkinEmail author Gert?Alberda van Ekenstein Olli?Ikkala Gerrit?ten?Brinke 《Rheologica Acta》2004,43(4):364-372
A tooth rheometer designed to investigate the influence of large amplitude oscillatory shear on the macroscopic orientation of complex fluids is described. The rheometer allows in-situ two-directional small-angle scattering measurements, making it possible to observe in particular the orientation process of hierarchically structured block copolymers in dynamics. Experiments performed with a linear poly(vinyl methyl ether) show that, despite a considerable gap/width ratio, the rheometer can be used for adequate rheological measurements. In addition we found an unexpected dependence of the dynamic parameters on the rheometer gap. The small amount of sample required favors the use of this rheometer for measuring the rheological characteristics of new compounds. 相似文献
60.
Asiya R. Mustafina Svetlana V. Fedorenko Nelya A. Makarova Ella KH. Kazakova Zul'fiya G. Bazhanova Vladimir E. Kataev Alexander I. Konovalov 《Journal of inclusion phenomena and macrocyclic chemistry》2001,40(1-2):73-76
The inclusion behaviour of a new water-soluble sulfonated calix[4]resorcinarene towards alkylammonium and N-methylpyridinium cations has been investigated on the basis of 1H NMR spectroscopy and pH-potentiometry data. The inclusion of the N-methylpyridinium cation has been found to be dependent on pH with the preferable inclusion of the methyl substituent in alkaline and the aromatic ring in neutral aqueous media. 相似文献