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51.
Alessandro Bismuto Gary S. Nichol Fernanda Duarte Michael J. Cowley Stephen P. Thomas 《Angewandte Chemie (International ed. in English)》2020,59(31):12731-12735
The reaction of a Lewis acidic borane with an alkyne is a key step in a diverse range of main group transformations. Alkyne 1,1‐carboboration, the Wrackmeyer reaction, is an archetypal transformation of this kind. 1,1‐Carboboration has been proposed to proceed through a zwitterionic intermediate. We report the isolation and spectroscopic, structural and computational characterization of the zwitterionic intermediates generated by reaction of B(C6F5)3 with alkynes. The stepwise reactivity of the zwitterion provides new mechanistic insight for 1,1‐carboboration and wider B(C6F5)3 catalysis. Making use of intramolecular stabilization by a ferrocene substituent, we have characterized the zwitterionic intermediate in the solid state and diverted reactivity towards alkyne cyclotrimerization. 相似文献
52.
Fernanda R. Santana Liany Luna-Dulcey Víctor U. Antunes Claudio F. Tormena Marcia R. Cominetti Marcelo C. Duarte 《Natural product research》2020,34(1):102-109
AbstractHyptis pectinata is a herb popularly used in Brazil for the treatment of inflammations, pain, bacterial infections and cancer. In the present study, inflorescences (MPIn), leaves (MPL), branches (MPB), root (MPR) extracts and three compounds isolated from MPIn were assayed against breast tumor cell lines. The structures of the three compounds (pectinolide J, hyptolide and pectinolide E) were determined by means of spectroscopic analysis. Pectinolide J was isolated for the first time. The MPIn, MPL and MPR exhibited specific antiproliferative activity on tumor cell lines when compared to normal cell lines with IC50 of 52.01?±?0.64, 45.91?±?0.02?μg/mL and 82.84?±?0.03?μg/mL, respectively. Although the isolated substances did not present good antiproliferative activity, when the three were associated, a greater biological effect was observed, suggesting a synergistic effect. Hyptolide (5.6?±?0.4?μg/mL) showed IC50 sufficiently low to be considered as a drug prototype. 相似文献
53.
Bernardo Duarte Renato Mamede Irina A. Duarte Isabel Caador Susanne E. Tanner Marisa Silva David Jacinto Teresa Cruz Vanessa F. Fonseca 《Molecules (Basel, Switzerland)》2022,27(4)
The stalked barnacle Pollicipes pollicipes is an abundant species on the very exposed rocky shore habitats of the Spanish and Portuguese coasts, constituting also an important economical resource, as a seafood item with high commercial value. Twenty-four elements were measured by untargeted total reflection X-ray fluorescence spectroscopy (TXRF) in the edible peduncle of stalked barnacles sampled in six sites along the Portuguese western coast, comprising a total of 90 individuals. The elemental profile of 90 individuals originated from several geographical sites (N = 15 per site), were analysed using several chemometric multivariate approaches (variable in importance partial least square discriminant analysis (VIP-PLS-DA), stepwise linear discriminant analysis (S-LDA), linear discriminant analysis (LDA), random forests (RF) and canonical analysis of principal components (CAP)), to evaluate the ability of each approach to trace the geographical origin of the animals collected. As a suspension feeder, this species introduces a high degree of background noise, leading to a comparatively lower classification of the chemometric approaches based on the complete elemental profile of the peduncle (canonical analysis of principal components and linear discriminant analysis). The application of variable selection approaches such as the VIP-PLS-DA and S-LDA significantly increased the classification accuracy (77.8% and 84.4%, respectively) of the samples according to their harvesting area, while reducing the number of elements needed for this classification, and thus the background noise. Moreover, the selected elements are similar to those selected by other random and non-random approaches, reinforcing the reliability of this selection. This untargeted analytical procedure also allowed to depict the degree of risk, in terms of human consumption of these animals, highlighting the geographical areas where these delicacies presented lower values for critical elements compared to the standard thresholds for human consumption. 相似文献
54.
Vnia Andr M. Teresa Duarte Clara S. B. Gomes Mafalda C. Sarragua 《Molecules (Basel, Switzerland)》2022,27(1)
In Portugal, publications with mechanochemical methods date back to 2009, with the report on mechanochemical strategies for the synthesis of metallopharmaceuticals. Since then, mechanochemical applications have grown in Portugal, spanning several fields, mainly crystal engineering and supramolecular chemistry, catalysis, and organic and inorganic chemistry. The area with the most increased development is the synthesis of multicomponent crystal forms, with several groups synthesizing solvates, salts, and cocrystals in which the main objective was to improve physical properties of the active pharmaceutical ingredients. Recently, non-crystalline materials, such as ionic liquids and amorphous solid dispersions, have also been studied using mechanochemical methods. An area that is in expansion is the use of mechanochemical synthesis of bioinspired metal-organic frameworks with an emphasis in antibiotic coordination frameworks. The use of mechanochemistry for catalysis and organic and inorganic synthesis has also grown due to the synthetic advantages, ease of synthesis, scalability, sustainability, and, in the majority of cases, the superior properties of the synthesized materials. It can be easily concluded that mechanochemistry is expanding in Portugal in diverse research areas. 相似文献
55.
CM Silva MF Duarte ML Mira MH Florêncio K Versluis AJ Heck 《Rapid communications in mass spectrometry : RCM》1999,13(12):1098-1103
Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
56.
N. Euler W. -H. Steeb L. G. S. Duarte I. C. Moreira 《International Journal of Theoretical Physics》1991,30(9):1267-1271
The techniques of invertible point transformations and the Painlevé analysis can be used to construct integrable ordinary differential equations. We compare both techniques for the second Painlevé transcendent. 相似文献
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59.
The study of ecological systems has generated deep interest in exploring the complexity of chaotic food chains. The role of chaos in ecosystems is not entirely understood. One approach to have a better comprehension of ecological chaos is by analyzing it in mathematical models of basic food chains. In this article it is considered a classical chaotic food chain model from the literature. We use the theory of symbolic dynamics to study the topological entropy and the parameter space ordering of kneading sequences associated with one-dimensional maps that reproduce significant aspects of the model dynamics. The topological entropy allows us to distinguish different chaotic states in some realistic system parameter region. Another numerical invariant is introduced in order to characterize isentropic dynamics. Studying a set of maps with the same topological entropy, we exhibit numerical results about the relation between the second topological invariant and each of the control parameters in consideration. This work provides an illustration of how our understanding of ecological models can be enhanced by the theory of symbolic dynamics. 相似文献
60.
Maria J. Alves Vera C.M. Duarte Hélio Faustino António Gil Fortes 《Tetrahedron: Asymmetry》2010,21(15):1817-1820
Erythrose benzylidene-acetal 1,3-butadienes are studied as partners in Diels–Alder cycloadditions. A high diastereofacial improvement is found in cases where both the alcohol function is protected and a π–π interaction between the diene and dienophile is possible. Several competing factors have been studied independently in order to explain its influence on the selectivity of the cycloadditions. 相似文献