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1.
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.  相似文献   
2.
A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C−O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.  相似文献   
3.
We herein report that flash heating microwave irradiation is a helpful tool in the formation of arylpyrimidines from the corresponding halopyrimidines. The palladium-catalyzed cross-coupling reactions of 2,4-di- and 2,4,5-trihalopyrimidines with phenylboronic acid under the above conditions are described. By use of the appropriate catalyst and the adequate halopyrimidine, good regioselectivity can be achieved in the 2-, 4-, or 5-positions of the heterocycle. In addition, we show that this methodology is ameneable for the stepwise preparation of mono-, di-, and triphenylpyrimidines.  相似文献   
4.
When an organization solves a portfolio problem with public projects evaluated by multiple criteria, in which the economic dimension is not essential or not well characterized, the classical methods are not useful. We propose a non-linear preference model developed from normative Value Theory and using fuzzy sets to model some sources of imprecision. This model can be considered as a generalization of the classical approaches. However, the optimization problem is very complex in order to be solved with non-linear programming techniques. Therefore, the model is exploited by an evolutionary algorithm, able to achieve a strong improvement of the quality of solution.  相似文献   
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6.
The notion of Kuratowski convergence is applied to describe a kind of convergence in the context of holomorphic functions. We associate it to a convenient topology, explore its relation with the compact-open topology, thus providing a new set theoretic point of view of this classic topology, and present it in the framework of set-valued mappings.  相似文献   
7.
The isotopic production cross sections of heavy residues in relativistic heavy-ion collisions have been investigated in inverse kinematics. The primary reaction products were fully identified in mass and atomic number prior to beta decay using the fragment separator FRS. The huge collection of data obtained helps in the understanding of the two main reaction mechanisms involved: fragmentation and fission. These data provide basic information for future radioactive ion beam facilities and for technical applications like intense neutron sources by means of spallation targets.  相似文献   
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Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature.  相似文献   
10.
An experimental analysis of graded-index (GRIN) planar waveguides produced by ion exchange in soda-lime glass is presented. This study is based on a recent model describing nonlinear diffusion. Likewise the modal coupling between planar waveguides, produced in the same substrate, is analyzed in order to design efficient integrated optical components. Finally, waveguiding structures induced by Kerr effect in glass are proposed and analyzed.  相似文献   
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