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1.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
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.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
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A. Ádám 《Acta Mathematica Hungarica》1989,54(3-4):291-296
5.
A mean-field model of nonlinearly coupled oscillators with randomly distributed frequencies and subject to independent external white noises is analyzed in the thermodynamic limit. When the frequency distribution isbimodal, new results include subcritical spontaneous stationary synchronization of the oscillators, supercritical time-periodic synchronization, bistability, and hysteretic phenomena. Bifurcating synchronized states are asymptotically constructed near bifurcation values of the coupling strength, and theirnonlinear stability properties ascertained. 相似文献
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In this article we study the well-posedness of the initial value problem for quasi-linear weakly hyperbolic equations of second order. We obtain a sufficient condition for the Cauchy problem to be locally solvable in the class of smooth function. 相似文献
8.
Renato Mario Benazic Tome 《Bulletin of the Brazilian Mathematical Society》1997,28(2):211-231
In this paper, the desingularization problem for an absolutely isolated singularity of an-dimensional holomorphic vector field is solved. Also, we exhibit final forms under blowing-up for this type of singularities. 相似文献
9.
We introduce a family of matrices that define logics in which paraconsistency and/or paracompleteness occurs only at the level of literals, that is, formulas that are propositional letters or their iterated negations. We give a sound and complete axiomatization for the logic defined by the class of all these matrices, we give conditions for the maximality of these logics and we study in detail several relevant examples. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
10.
Renato Bruni 《Annals of Operations Research》2007,150(1):79-92
The paper is concerned with the problem of binary classification of data records, given an already classified training set
of records. Among the various approaches to the problem, the methodology of the logical analysis of data (LAD) is considered.
Such approach is based on discrete mathematics, with special emphasis on Boolean functions. With respect to the standard LAD
procedure, enhancements based on probability considerations are presented. In particular, the problem of the selection of
the optimal support set is formulated as a weighted set covering problem. Testable statistical hypothesis are used. Accuracy
of the modified LAD procedure is compared to that of the standard LAD procedure on datasets of the UCI repository. Encouraging
results are obtained and discussed. 相似文献