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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.
Antonio R. Montoro Bustos Marta Garcia-Cortes Hector González-Iglesias Jorge Ruiz Encinar José M. Costa-Fernández Miguel Coca-Prados Alfredo Sanz-Medel 《Analytica chimica acta》2015
A generic strategy based on the use of CdSe/ZnS Quantum Dots (QDs) as elemental labels for protein quantification, using immunoassays with elemental mass spectrometry (ICP-MS), detection is presented. In this strategy, streptavidin modified QDs (QDs-SA) are bioconjugated to a biotinylated secondary antibody (b-Ab2). After a multi-technique characterization of the synthesized generic platform (QDs-SA-b-Ab2) it was applied to the sequential quantification of five proteins (transferrin, complement C3, apolipoprotein A1, transthyretin and apolipoprotein A4) at different concentration levels in human serum samples. It is shown how this generic strategy does only require the appropriate unlabeled primary antibody for each protein to be detected. Therefore, it introduces a way out to the need for the cumbersome and specific bioconjugation of the QDs to the corresponding specific recognition antibody for every target analyte (protein). Results obtained were validated with those obtained using UV–vis spectrophotometry and commercial ELISA Kits. 相似文献
3.
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
4.
5.
Mariusz Marć Marek Tobiszewski Bożena Zabiegała Miguel de la Guardia Jacek Namieśnik 《Analytica chimica acta》2015
This review summarizes the different tools and concepts that are commonly applied in air quality monitoring. The monitoring of atmosphere is extremely important as the air quality is an important problem for large communities. Main requirements for analytical devices used for monitoring include a long period of autonomic operation and portability. These instruments, however, are often characterized by poor analytical performance. Monitoring networks are the most common tools used for monitoring, so large-scale monitoring programmes are summarized here. Biomonitoring, as a cheap and convenient alternative to traditional sample collection, is becoming more and more popular, although its main drawback is the lack of standard procedures. Telemonitoring is another approach to air monitoring, which offers some interesting opportunities, such as ease of coverage of large or remote areas, constituting a complementary approach to traditional strategies; however, it requires huge costs. 相似文献
6.
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
7.
Ortiz Adolfo Yang Jianhua Coccolo Mattia Seoane Jesús M. Sanjuán Miguel A. F. 《Nonlinear dynamics》2020,102(4):2323-2337
Nonlinear Dynamics - The main purpose of this paper is to study both the underdamped and the overdamped dynamics of the nonlinear Helmholtz oscillator with a fractional-order damping. For that... 相似文献
8.
Brandão Pedro Francisco Ramos Rui Miguel Rodrigues José António 《Analytical and bioanalytical chemistry》2018,410(26):6873-6880
Analytical and Bioanalytical Chemistry - Formaldehyde is often applied in the industrial production of different products, such as textiles, insulation materials, or cosmetics, due to its... 相似文献
9.
We analyze new forms of aberrations affecting a time dependent magnetic field lens recently proposed. The lens consist of an axially symmetric ellipsoidal solenoid producing a spatially uniform but time pulsating homogeneous field. The dynamics of electrons emitted by some object and injected into this coil shows that this system is capable of focusing a parallel beam or produce images free of geometrical aberrations. The cardinal elements of this lens change periodically in positions and therefore to obtain a stationary image it is necessary to employ a chopped electron beam. Two forms of aberrations originate from the finite duration of the electron pulse and the energy dispersion of the incoming beam (chromatic aberration). Their image degradation effects are quite similar and result from recording different axially displaced images at some fixed stationary plane. We show how, by adjusting the parameters characterizing the magnetic pulse and introducing small apertures that increase the depth of focus, their effects can be reduced or in some cases eliminated. Other forms of instrumental aberrations characteristic of this time dependent magnetic field lens are briefly discussed. 相似文献
10.
Rossella Bartolo Anna Germinario Miguel Sánchez 《Annals of Global Analysis and Geometry》2002,21(1):63-84
In this paper the problem of the geodesic connectedness and convexity ofincomplete Riemannian manifolds is analyzed. To this aim, a detailedstudy of the notion of convexity for the associated Cauchy boundary iscarried out. In particular, under widely discussed hypotheses,we prove the convexity of open domains (whose boundaries may benondifferentiable) of a complete Riemannian manifold. Variationalmethods are mainly used. Examples and applications are provided,including a result for dynamical systems on the existence oftrajectories with fixed energy. 相似文献