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161.
162.
Raul Aguayo Felipe Arias Alvaro Cañete Carolina Zuñiga Enrique A. Castro Paulina Pavez José G. Santos 《国际化学动力学杂志》2013,45(3):202-211
The reactions of the title compounds with phenoxides, secondary alicyclic (SA) amines, and pyridines, in 44 wt% ethanol–water, at 25°C and an ionic strength of 0.2 M, were subjected to kinetic and product studies. From analytical techniques (HPLC and NMR), two pathways were detected (nucleophilic attack at the phosphoryl center and at the C‐1 aromatic carbon) for the reactions of all the nucleophiles with the phosphate ( 2 ) and for the pyridinolysis of the thionophosphate ( 1 ). Only aromatic nucleophilic substitution was found for the reactions of 1 with phenoxides and SA amines. For the dual reactions, the nucleophilic rate constants (kN) were separated in two terms: $k_{\rm N}^{\rm P}$ and $k_{\rm N}^{{\rm Ar}}$, which are the rate constants for the corresponding electrophilic centers. The absence of a break in the Brønsted‐type plots for the attack at P is consistent with concerted mechanisms. The Brønsted slopes, βAr 0.32–0.71, for the attack at the aromatic C‐1, are in agreement with stepwise mechanisms where formation of a Meisenheimer complex is the rate‐determining step. © 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 202–211, 2013 相似文献
163.
Ariana Borges Souza Monique Rodrigues Moreira Carly Henrique Gambeta Borges Marília Rodrigues Simão Jairo Kenupp Bastos João Paulo Barreto de Sousa Sérgio Ricardo Ambrosio Rodrigo Cassio Sola Veneziani 《Biomedical chromatography : BMC》2013,27(3):280-283
The Copaifera species (Leguminoseae) are popularly known as ‘copaíba’ or ‘copaíva’ and are grown in the states of Amazonas, Pará and Ceará in northern Brazil. The oleoresins obtained from these species have been extensively used owing to their pharmacological potential and their application in cosmetic and pharmaceutical preparations. In the present study, the development and validation of a novel, rapid and efficient RP‐HPLC methodology for the analysis of the diterpene (?)‐copalic acid (CA), pointed out as the only chemical marker of the Copaifera genus, are described. The regression equation (Y = 26,707x ? 29,498) was obtained with good linearity (r2 = 0.9993) and the limits of quantification and detection were 9.182 and 3.032 µg/mL, respectively. The precision and the accuracy of the method were adequate (lower than 4%). Finally, the validation parameters evaluated were satisfactorily met, so the developed method represents a suitable tool for application in the quality control of such natural products. Further studies aiming to develop analytical methodologies for each Copaifera species using a more representative number of chemical markers should be performed. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
164.
In this paper we report a simple methodology for obtaining (+) trans - 1,2 - epoxylimonene (1b) in high purity (>99% HRGC) and reasonable quantity. The mixture of 1a and 1b in CH2Cl2 is stirred with 1M NaHSO3 in water. Under these conditions 1a is completely destroyed, while 1b is only partially destroyed. 相似文献
165.
dos Santos Poli Anne Karoline Hilário Rodrigo Barbosa Gama Adriana Medeiros Baldan Mauricio Ribeiro Gonçalves Emerson Sarmento 《Journal of Solid State Electrochemistry》2019,23(1):33-52
Journal of Solid State Electrochemistry - Polyaniline was electrosynthesized using three voltammetric cycles on carbon fiber felts annealed at 1400, 1600, 2000, and 2300 K. Felts and... 相似文献
166.
167.
Benvenuti Jaqueline Capeletti Larissa Brentano Gutterres Mariliz dos Santos João Henrique Zimnoch 《Journal of Sol-Gel Science and Technology》2018,85(2):446-457
Journal of Sol-Gel Science and Technology - This study reports the development of a functional adsorbent synthesized by the molecular imprinting method in a sol–gel matrix. The adsorption... 相似文献
168.
Sunny K. S. Freitas Felipe L. Oliveira Thiago C. dos Santos Danilo Hisse Claudia Merlini Célia M. Ronconi Prof. Dr. Pierre M. Esteves 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2342-2347
A thermally stable carbocationic covalent organic network (CON), named RIO-70 was prepared from pararosaniline hydrochloride, an inexpensive dye, and triformylphloroglucinol in solvothermal conditions. This nanoporous organic material has shown a specific surface area of 990 m2 g−1 and pore size of 10.3 Å. The material has CO2 uptake of 2.14 mmol g−1 (0.5 bar), 2.7 mmol g−1 (1 bar), and 6.8 mmol g−1 (20 bar), the latter corresponding to 3 CO2 molecules adsorbed per pore per sheet. It is shown to be a semiconductor, with electrical conductivity (σ) of 3.17×10−7 S cm−1, which increases to 5.26×10−4 S cm−1 upon exposure to I2 vapor. DFT calculations using periodic conditions support the findings. 相似文献
169.
Eugene Santos Qi Gu Eunice E. Santos 《International Journal of Approximate Reasoning》2013,54(8):1000-1012
For a knowledge-based system that fails to provide the correct answer, it is important to be able to tune the system while minimizing overall change in the knowledge-base. There are a variety of reasons why the answer is incorrect ranging from incorrect knowledge to information vagueness to incompleteness. Still, in all these situations, it is typically the case that most of the knowledge in the system is likely to be correct as specified by the expert (s) and/or knowledge engineer (s). In this paper, we propose a method to identify the possible changes by understanding the contribution of parameters on the outputs of concern. Our approach is based on Bayesian Knowledge Bases for modeling uncertainties. We start with single parameter changes and then extend to multiple parameters. In order to identify the optimal solution that can minimize the change to the model as specified by the domain experts, we define and evaluate the sensitivity values of the results with respect to the parameters. We discuss the computational complexities of determining the solution and show that the problem of multiple parameters changes can be transformed into Linear Programming problems, and thus, efficiently solvable. Our work can also be applied towards validating the knowledge base such that the updated model can satisfy all test-cases collected from the domain experts. 相似文献