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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
3.
4.
Kleandrova Valeria V. Rojas-Vargas Julio A. Scotti Marcus T. Speck-Planche Alejandro 《Molecular diversity》2022,26(5):2523-2534
Molecular Diversity - Hypertension is a medical condition that affects millions of people worldwide. Despite the high efficacy of the current antihypertensive drugs, they are associated with... 相似文献
5.
András Gy. Németh Renáta Szabó Dr. Attila Domján Prof. György M. Keserű Dr. Péter Ábrányi-Balogh 《ChemistryOpen》2021,10(1):16-27
The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol. 相似文献
6.
Julio Castellanos 《Mathematische Zeitschrift》2002,239(4):777-802
We consider complete ideals supported on finite sequences of infinitely near points, in regular local rings with dimensions
greater than two. We study properties of factorizations in Lipman special *-simple complete ideals. We relate it to a type
of proximity, linear proximity, of the points, and give conditions in order to have unique factorization. Several examples
are presented.
Received: 2 February 2000 / in final form: 14 March 2001 / Published online: 18 January 2002 相似文献
7.
The MPEG-1 Layer 3 compression schema of audio signal, commonly known as mp3, has caused a great impact in recent years as it has reached high compression rates while conserving a high sound quality. Music and speech samples compressed at high bitrates are perceptually indistinguishable from the original samples, but very little was known about how compression acoustically affects the voice signal. A previous work with normal voices showed a high fidelity at high-bitrate compressions both in voice parameters and the amplitude-frequency spectrum. In the present work, dysphonic voices were tested through two studies. In the first study, spectrograms, long-term average spectra (LTAS), and fast Fourier transform (FFT) spectra of compressed and original samples of running speech were compared. In the second study, intensities, formant frequencies, formant bandwidths, and a multidimensional set of voice parameters were tested in a set of sustained phonations. Results showed that compression at high bitrates (96 and 128 kbps) preserved the relevant acoustic properties of the pathological voices. With compressions at lower bitrates, fidelity decreases, introducing some important alterations. Results from both works, Gonzalez and Cervera and this paper, open up the possibility of using MPEG-compression at high bitrates to store or transmit high-quality speech recordings, without altering their acoustic properties. 相似文献
8.
9.
JOSEF MÁLEK JINDŘICH NEČAS K. R. RAJAGOPAL 《Archive for Rational Mechanics and Analysis》2002,165(3):243-269
To describe the flows of fluids over a wide range of pressures, it is necessary to take into account the fact that the viscosity
of the fluid depends on the pressure. That the viscosity depends on the pressure has been verified by numerous careful experiments.
While the existence of solutions local-in-time to the equations governing the flows of such fluids are available for small,
special data and rather unrealistic dependence of the viscosity on the pressure, no global existence results are in place.
Our interest here is to establish the existence of weak solutions for spatially periodic three-dimensional flows that are
global in time, for a large class of physically meaningful viscosity-pressure relationships.
(Accepted May 1, 2002) Published online November 15, 2002
Communicated by S. S. ANTMAN 相似文献
10.
Pierre Degond Stéphane Génieys Ansgar Jüngel 《Journal de Mathématiques Pures et Appliquées》1997,76(10):991-1015
The time-dependent equations for a charged gas or fluid consisting of several components, exposed to an electric field, are considered. These equations form a system of strongly coupled, quasilinear parabolic equations which in some situations can be derived from the Boltzmann equation. The model uses the duality between the thermodynamic fluxes and the thermodynamic forces. Physically motivated mixed Dirichlet-Neumann boundary conditions and initial conditions are prescribed.The existence of weak solutions is proven. The key of the proof is (i) a transformation of the problem by using the entropic variables, or electro-chemical potentials, which symmetrizes the equations, and (ii) a priori estimates obtained by using the entropy function. Finally, the entropy inequality is employed to show the convergence of the solutions to the thermal equilibrium state as the time tends to infinity. 相似文献