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991.
A detailed experimental and theoretical investigation of the first-reported barrierless reaction between two closed-shell molecules [J. Chem. Phys. 127, 101101 (2007)] is presented. The translational energy and angular distributions of two product channels, HF+CH(2)SFCH(3) and F+CH(3)SFCH(3), determined at several collision energies, have been analyzed to reveal the dynamics of the studied reaction. Detailed analysis of the experimental and computational results supports the proposed reaction mechanism involving a short-lived F-F-S(CH(3))(2) intermediate, which can be formed without any activation energy. Other possible reaction mechanisms have been discriminated. The decay of the intermediate and competition between the two product channels have been discussed. 相似文献
992.
Alvarez Sánchez B Capote FP Jiménez JR Luque de Castro MD 《Journal of chromatography. A》2008,1207(1-2):46-54
A method for determination of free and glucuronide-conjugated female steroid hormones in urine at the pgmL(-1) level is here presented. For this purpose, a dual approach with or without beta-glucuronidase hydrolysis has been developed to succeed in this analysis. The target analytes were two progestogens - progesterone and pregnenolone - and three endogenous estrogens - estradiol, estriol and estrone. Separation and detection were carried out by liquid chromatography electrospray ionization and tandem mass spectrometry (LC-ESI-MS-MS) with a triple quadrupole (qQq) mass detector. The determination step was optimized by multiple reaction monitoring for highly selective identification and sensitive quantification of female hormones in a complex sample such as human urine. As these compounds are present in urine at very low concentration (ngmL(-1) level), a preconcentration and clean-up step by solid-phase extraction was automatically carried out prior to the chromatographic step in order to improve the sensitivity of the method. This sample pretreatment was performed using a lab-on-valve (LOV) manifold which provided preconcentration factors ranging from 59.1 to 72.3 for 10mL urine. The detection and quantification limits were in the ranges 1.8-18pg and 6-61pg on-column, respectively, with precision values from 1.93 to 10.99%, expressed as relative standard deviation. These results enable to conclude the suitability of the LOV-LC-qQq approach for determination of the lipidomic profiling of the main female steroid hormones in a difficult matrix as human urine. The method can be potentially applied to the clinical and other metabolomic areas. 相似文献
993.
Estévez RE Paradas M Millan A Jiménez T Robles R Cuerva JM Oltra JE 《The Journal of organic chemistry》2008,73(4):1616-1619
We describe the first Ti-catalyzed Reformatsky-type coupling between alpha-halo ketones and aldehydes. The reaction affords beta-hydroxy ketones under mild, neutral conditions compatible with ketones and other electrophiles. The catalytic cycle possibly proceeds via bis(cyclopentadienyl)titanium enolates. 相似文献
994.
Avalos M Babiano R Cintas P Jiménez JL Light ME Palacios JC Pérez EM 《The Journal of organic chemistry》2008,73(2):661-672
A series of chiral imines derived from 1-amino-1-deoxyalditols such as d-glucamine, a rather unexplored raw material from the chiral pool, have been serendipitiously transformed into a novel family of N-acetyl-1,3-oxazolidines by means of an unexpected acetylation. The structure of these substances is supported by spectroscopic and crystallographic data. The acetylates also trigger a complex dynamic transformation, in which an initially configured trans oxazolidine converts into a more stable cis-configured derivative. Both isomers can also exist as rotational conformers (E,Z) as a consequence of the restricted rotation around the N-acetyl bond. The barriers to rotation have been determined by variable-temperature experiments. Overall, this transformation most likely involves the intermediacy of a chiral iminium ion, which has been documented in the synthesis of nitrogen heterocycles, thus explaining the experimental facts. 相似文献
995.
Amelia Bilbao-Terol Mariano Jiménez Mar Arenas-Parra 《Annals of Operations Research》2016,245(1-2):137-162
In this paper a multi-criteria group decision making model is presented in which there is a heterogeneity among the decision makers due to their different expertise and/or their different level of political control. The relative importance of the decision makers in the group is handled in a soft manner using fuzzy relations. We suppose that each decision maker has his/her preferred solution, obtained by applying any of the techniques of distance-based multi-objective programming [compromise, goal programming (GP), goal programming with fuzzy hierarchy, etc.]. These solutions are used as aspiration levels in a group GP model in which the differences between the unwanted deviations are interpreted in terms of the degree of achievement of the relative importance amongst the group members. In this way, a group GP model with fuzzy hierarchy (Group-GPFH) is constructed. The solution for this model is proposed as a collective decision. To show the applicability of our proposal, a regional forest planning problem is addressed. The objective is to determine tree species composition in order to improve the values achieved by Pan-European indicators for sustainable forest management. This problem involves stakeholders with competing interests and different preference schemes for the aforementioned indicators. The application of our proposal to this problem allows us to be able to comfortably address all these issues. The results obtained are consistent with the preferences of each stakeholder and their hierarchy within the group. 相似文献
996.
997.
Voltammetric Determination of Metronidazole Using a Sensor Based on Electropolymerization of α‐Cyclodextrin over a Carbon Paste Electrode
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Arturo Hernández‐Jiménez Gabriela Roa‐Morales Horacio Reyes‐Pérez Patricia Balderas‐Hernández Carlos E. Barrera‐Díaz Margarita Bernabé‐Pineda 《Electroanalysis》2016,28(4):704-710
An electrochemical sensor for metronidazole (MTZ) was built via the surface modification of a carbon paste electrode (CPE) by a film obtained through electropolymerization of α‐cyclodextrin (CPEα‐CD). The CPEα‐CD was characterized by cyclic voltammetry (CV) and atomic force microscopy (AFM), by both techniques was demonstrated that the polymer film is coating the electrode surface. The electroreduction behaviour of MTZ in HClO4 media as a supporting electrolyte was studied by differential‐pulse voltammetric (DPV) technique. The DPV electrochemical process was observed to be diffusion controlled and irreversible. Under optimal conditions, the peak current was proportional to MTZ concentration in the range of 0.5 to 103.0 μM with a detection limit of 0.28±0.02 μM. The method was successfully applied to quantify of MTZ in pharmaceutical formulations. In addition, this proposed MTZ sensor exhibited good reproducibility, long‐term stability and fast current response. 相似文献
998.
We place the hyperbolic quantum Ruijsenaars–Schneider system with an exponential Morse term on a lattice and diagonalize the resulting n-particle model by means of multivariate continuous dual q-Hahn polynomials that arise as a parameter reduction of the Macdonald–Koornwinder polynomials. This allows to compute the n-particle scattering operator, to identify the bispectral dual system, and to confirm the quantum integrability in a Hilbert space setup. 相似文献
999.
Carlos García-Delgado Felipe Yunta 《International journal of environmental analytical chemistry》2016,96(1):87-100
The aim of this work was to assess the impact of soil characteristics and constituents in the total extraction of hydrophobic organic pollutants, such as polycyclic aromatic hydrocarbons (PAH), in real polluted soil samples from different sources. Soil samples were obtained from a wood creosote treatment plant, in the vicinity of a metallurgy industry and coal thermal power stations. Soils showed a wide diversity of textures, organic matter (OM) and CaCO3 content, pH and electrical conductivity to assure representativeness of multiple situations. Two extraction procedures with soft (solid–liquid extraction, SLE) and intense (pressurised liquid extraction, PLE) extraction power were used to determine the total concentration of PAH in soils. Results obtained showed that soil properties affect the effectiveness of the extraction procedures tested. The validation of PAH extraction procedure with a reference soil did not confirm that the procedure was adequate for all kinds of soil. Results showed that OM content and clay were the main soil characteristics that should be taken into account to select the most adequate PAH extraction procedure for any given polluted soil. 相似文献
1000.
Ultra‐trace analysis of furanic compounds in transformer/rectifier oils with water extraction and high‐performance liquid chromatography
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Monica Lin Kham Lin Amanda Lin Ronda Gras Jim Luong 《Journal of separation science》2016,39(14):2777-2784
A novel approach for the determination of parts‐per‐billion level of 5‐hydroxymethyl‐2‐furaldehyde, furfuryl alcohol, furfural, 2‐furyl methyl ketone, and 5‐methylfurfural in transformer or rectifier oils has been successfully innovated and implemented. Various extraction methods including solid‐phase extraction, liquid–liquid extraction using methanol, acetonitrile, and water were studied. Water was by far the most efficient solvent for use as an extraction medium. Separation of the analytes was conducted using a 4.6 mm × 250 mm × 3.5 μm Agilent Zorbax column while detection and quantitation were conducted with a variable wavelength UV detector. Detection limits of all furans were at 1 ppb v/v with linear ranges range from 5 to 1000 ppb v/v with correlation coefficients of 0.997 or better. A relative standard deviation of at most 2.4% at 1000 ppb v/v and 7.3% at 5 ppb v/v and a recovery from 43% to 90% depending on the analyte monitored were obtained. The method was purposely designed to be environmental friendly with water as an extraction medium. Also, the method uses 80% water and 20% acetonitrile with a mere 0.2 mL/min of acetonitrile in an acetonitrile/water mixture as mobile phase. The analytical technique has been demonstrated to be highly reliable with low cost of ownership, suitable for deployment in quality control labs or in regions where available analytical resources and solvents are difficult to procure. 相似文献