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101.
Cesare Oliva Marco Scavini Agusti Sin Yuri Dubitsky 《Journal of solid state chemistry》2004,177(11):4104-4111
EPR analysis is carried out with Ce1−xGdxO(4−x)/2 (x=0.1; 0.2) nanopowders aiming at obtaining information about their oxidation and reduction properties. The EPR spectrum of these systems is composed of a single feature. The first derivative peak-to-peak spectral intensity decreases at higher temperatures, but this trend deviates from that of Curie's law with the x=0.1 sample, at difference with the x=0.2 sample. This unexpected result is related to oxygen deficiency, due to gas-solid equilibrium, present in the former sample only. As a consequence, some Ce3+ ions would form providing it with conduction electrons propagating as small polarons in a percolative way. This would result in a thinner skin depth at higher temperatures, able to explain the deviation of the spectral intensity from its expected value. Indeed, this deviation from Curie's law is reduced or disappears at all after thermal treatment of the x=0.1 sample with O2. 相似文献
102.
Sabrina M. Nobre Mauro N. Muniz Marcus Seferin Wagner M. da Silva Adriano L. Monteiro 《应用有机金属化学》2011,25(4):289-293
We have developed a sequential and selective Pd‐catalyzed double‐Heck arylation of ethylene that results in non‐symmetrical nitro‐stilbene analogs of trans‐resveratrol at excellent yields. A catalytic system consisting of Pd(OAc)2 and P(o‐tolyl)3 permitted us to carry out the two consecutive Heck arylations without losing activity from the first to the second Heck reaction. After the first Heck arylation of ethylene, no isolation or additional catalyst loading is required for the second Heck arylation reaction. This protocol was applied to the synthesis of methylated trans‐resveratrol, which was obtained at a 65% overall yield. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
103.
Paolo Costa Iris Trosien Miguel Fernandez‐Oliva Elsa Sanchez‐Garcia Wolfram Sander 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(9):2694-2698
The fluorenyl cation is a textbook example for a 4π antiaromatic cation. However, contrasting results have been published on how the annelated benzene rings compensate the destabilizing effect of the 4π antiaromatic five‐membered ring in its core. Whereas previous attempts to synthesize this cation in superacidic media resulted in undefined polymeric material only, we herein report that it can be generated and isolated in amorphous water ice at temperatures below 30 K by photolysis of diazofluorene. Under these conditions, the fluorenylidene is protonated by water to give the fluorenyl cation, which could be characterized spectroscopically. Its absorption in the visible‐light range matches that previously obtained by ultrafast absorption spectroscopy, and furthermore, its IR spectrum could be recorded. The IR bands in amorphous ice very nicely match predictions from DFT and DFT/MM calculations, suggesting the absence of strong interactions between the cation and surrounding water molecules. 相似文献
104.
Alfonso Oliva Aurora Molinari Jean Angulo Ricardo Schrebler Humberto Gómez Ricardo Córdova 《合成通讯》2013,43(23):4353-4360
The electrooxidation of 1-phenyl-3-methyl-4-butyldithiocarboxylate-5-pyrazolone 1 has been studied in ethanol/water solution, using a glassy carbon electrode surface. The electrochemical and spectroscopic data are in agreement with a bis-ketenedithioacetal disulphide compound 2 as the only product of the reaction. 相似文献
105.
M.I. Oliva P.G. Bercoff H.R. Bertorello 《Journal of magnetism and magnetic materials》2008,320(14):e100-e103
Magnetic interactions in hexaferrite samples of Ba1-xLax+δFe12-xCoxO19 composition were studied. The precursor powders—barium carbonate (BaCO3), lanthanum oxide (La2O3), hematite (Fe2O3) and cobalt acetate—were milled for 100 h in air atmosphere and heat-treated for 1 h at . The structural characterization was performed by X-ray diffraction. The FORC distributions show a single peak at high switching fields, indicating that the substituted systems are formed by weakly interacting particles. La excess induces the decoupling of the particles. 相似文献
106.
Lucia Caporaso Leone Oliva 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):7008-7013
In this paper, the synthesis of isotactic polypropylenes (i‐PP) modified with ? OH groups in sides (iPP‐OH), by combination of polyinsertion ansa‐metallocene catalysis and ring opening of propene oxide (PO), is described. i‐PP sequences interrupted by isolated ethylene/p‐methylstyrene units forms the backbone. This enchainment is obtained by controlled copolymerization of propene with ethylene and p‐methylstyrene comonomers in the presence of rac‐ethylenebis(1‐indenyl)zirconiumdichloride/methylalumoxane system. The metallation reaction of the p‐methyl group with sec‐BuLi generates an anionic center that can be reacted with PO. The iPP‐OH is the result of the monoaddition reaction of PO followed by hydrolysis with acidified methanol. By changing experimental conditions in the backbone synthesis, a tuned number of the functionalizable sites as well as polypropylene sequence lengths can be obtained. As a consequence, iPP samples with a different number of ? OH groups for the backbone can be synthesized after the PO monoaddition reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7008–7013, 2006 相似文献
107.
We generalize the theory of Kobayashi and Oliva (On the Birkhoff Approach to Classical Mechanics. Resenhas do Instituto de Matemática e Estatística da Universidade de São Paulo, 2003) to infinite dimensional Banach manifolds with a view towards applications in partial differential equations. 相似文献
108.
4-Alkyldithiocarboxylate-3,5-dihydroxy-1-phenylpyrazoles 2, are prepared in good yield by the reaction of 3-hydroxy-1-phenyl-2-pyrazolin-5-one 1 with sodium acetate in dimethylformamide (DMF), carbon disulfide and alkyl halides. 相似文献
109.
M. Noguera R. Ríos-Font L. Rodríguez-Santiago X. Solans-Monfort A. Oliva J. Bertran M. Sodupe 《Theoretical chemistry accounts》2009,123(1-2):105-111
The influence of π-stacking interactions between guanine (G) and the side chain of tyrosine (Tyr) on the N7 and O6 proton affinities of guanine and on the capability of these sites to act as hydrogen bond acceptors is analyzed at the B3LYP-D, M05-2X and MP2 levels of theory. With all methods, results from full geometry optimizations indicate that stacking interactions increase the N7 and O6 proton affinities by about 5–6 kcal mol?1, the increase being slightly larger for N7. Consistently with these results, hydrogen bond distances between guanine and one water molecule decrease in the stacked system. Moreover, interaction energy between H2O and (G-Tyr) is found to be 2–3 kcal mol?1 larger than in G···H2O. This strengthening arises from the additional Tyr–H2O stabilizing interactions and from a cooperative interplay between stacking and hydrogen bond forces. 相似文献
110.
This work introduces a calibrated B3LYP/6-31G(d) study on the electronic structure of singlet and triplet neutral species of 1,2-substituted icosahedral 1,2-R(2)-1,2-C(2)B(10)H(10) and octahedral 1,2-R(2)-1,2-C(2)B(4)H(4) molecules with R = {H, OH, SH, NH(2), PH(2), CH(3), SiH(3)} and their respective dianions formed by proton removal on each R group. A variety of small adiabatic singlet-triplet gaps DeltaE(ST) are obtained from these systems ranging from 2.93 eV (R = NH(2)) 相似文献