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81.
Lizarraga L Andrade EM Florit MI Molina FV 《The journal of physical chemistry. B》2005,109(40):18815-18821
The quasi-equilibrium electrochemomechanical behavior of relatively thick polyaniline films in sulfuric acid is investigated through experimental measurements and theoretical modeling. The leucoemeraldine (LE)-emeraldine (EM) conversion, or redox switching, is studied. The dependence of film volume and electrochemical charge is determined as a function of applied potential. It is observed that the film volume follows the charge, showing an expansion during the second half of the LE-EM oxidation. The model postulates the existence of a stable intermediate, protoemeraldine (PE), with a formal potential distribution for the PE-EM reaction. The volume change is modeled statistically considering contributions from mixing, polymer deformation, and electrostatic charge. The model shows very good agreement with the experiments, indicating that, in the conditions studied, the deformation contribution dominates the volume changes as a result of the conformational modifications undergone by the polymer in the PE-EM oxidation. 相似文献
82.
The seeds of Clitoria fairchildiana provided a new rotenoid, 6-hydroxy-2,3,9-trimethoxy-[1]benzopyrano[3,4-b][1]benzopyran-12(6H)-one. The structural elucidation was performed using detailed analyses of H- and 13C-NMR spectra including 2DNMR spectroscopic techniques (1H-13CHETCOR) and by comparison with spectrometric data from the literature. The anti-inflammatory activity was investigated using a capillary permeability assay. 相似文献
83.
We have measured the real space trajectory of the ultrafast magnetization dynamics in ferromagnetic metals induced by femtosecond optical pulses. Our approach allows the observation of the initial change of the modulus and orientation of the magnetization, occurring within a few hundreds of femtoseconds, as well as its subsequent precession and damping around the effective field. The role of the magnetocrystalline anisotropy shows up in the magnetization reorientation occurring during the electron-lattice relaxation. In addition, we propose a model which takes into account the initial demagnetization in the Bloch formalism describing the magnetization dynamics. 相似文献
84.
Velasco-Negueruela A Pérez-Alonso MJ Pérez de Paz PL Paúl-Palá J Sanz J 《Journal of chromatography. A》2003,1011(1-2):241-244
The essential oil from the aerial parts of Pimpinella junoniae Ceb. & Ort., growing in La Gomera, Canary Islands, Spain, was studied by gas chromatography and gas chromatography-mass spectrometry, and 43 constituents were identified. The major components were found to be alpha-zingiberene (20.6%), alpha-pinene (17.9%), (E)-beta-farnesene (9.3%), ar-curcumene (7.4%), beta-phellandrene (7.0%), beta-bisabolene (6.1%) and epoxypseudoisoeugenyl 2-methylbutyrate (6.0%). The decomposition product of epoxypseudoisoeugenol derivatives, 5-methoxy-2-methylbenzofuran (5.7%), moderate amounts of other arylpropanoids with the pseudoisoeugenol skeleton (total percentage, 5.2%) and other compounds such as beta-sesquiphellandrene (3.0%), cis-beta-guaiene (1.5%), alpha-phellandrene (1.5%) and alpha-bisabolol (1.3%), were also found. 相似文献
85.
[reaction: see text]. Mitomycin C is unchanged upon exposure to thiols under physiological conditions. Its more toxic variant, mitomycin A (MA), undergoes elimination of methanol to give a variety of mitosene derivatives, diagnostic of its activation to a reactive electrophile. Evidence is presented for a novel reductive mechanism, characterized by the transient addition of a thiol to the quinone of MA, followed by intramolecular electron transfer, leading to reduced quinone and oxidized thiol. 相似文献
86.
In the context of a gauge theory for the translation group, a conserved energy-momentum gauge current for the gravitational field is obtained. It is a true spacetime and gauge tensor, and transforms covariantly under global Lorentz transformations. By rewriting the gauge gravitational field equation in a purely spacetime form, it becomes the teleparallel equivalent of Einstein's equation, and the gauge current reduces to the Moller's canonical energy-momentum density of the gravitational field. 相似文献
87.
Y. Rojas Martinez H. Bustos Rodriguez D. Oyola Lozano G. A. Pérez Alcázar J. C. Paz 《Hyperfine Interactions》2007,175(1-3):29-34
The alloys between a transition metal and a rare earth present magnetic and magneto optical properties of exceptional interest for the production of magnetic devices for information storage. In this work we report the magnetic and structural properties, obtained by Mössbauer spectrometry (MS) and X-ray diffraction (XRD), of Tb0.257?x Nd x Fe0.743 alloys with x?=?0 and 0.257 prepared by mechanical alloying during 12, 24 and 48 h, to study the influence of the milling time in their magnetic and structural properties. The X-rays results show for all the samples that the α-Fe and an amorphous phase are always present. The first decreases and the second increases with the increase of the milling time. Mössbauer results show that the amorphous phase in samples with Nd is ferromagnetic and appears as a hyperfine field distribution and a broad doublet, and that as the milling time increases the paramagnetic contribution increases. For samples with Tb the amorphous phase is paramagnetic and appears as a broad doublet which increases with the milling time and for 48 h milling it appears an additional broad singlet. 相似文献
88.
Selecting the correct dimensionality is critical for obtaining partial least squares (PLS) regression models with good predictive ability. Although calibration and validation sets are best established using experimental designs, industrial laboratories cannot afford such an approach. Typically, samples are collected in an (formally) undesigned way, spread over time and their measurements are included in routine measurement processes. This makes it hard to evaluate PLS model dimensionality. In this paper, classical criteria (leave-one-out cross-validation and adjusted Wold's criterion) are compared to recently proposed alternatives (smoothed PLS-PoLiSh and a randomization test) to seek out the optimum dimensionality of PLS models. Kerosene (jet fuel) samples were measured by attenuated total reflectance-mid-IR spectrometry and their spectra where used to predict eight important properties determined using reference methods that are time-consuming and prone to analytical errors. The alternative methods were shown to give reliable dimensionality predictions when compared to external validation. By contrast, the simpler methods seemed to be largely affected by the largest changes in the modeling capabilities of the first components. 相似文献
89.
Viviane B. de Oliveira Nizamara S. Pereira Carlos Kleber Z. Andrade Maria José A. Sales 《Macromolecular Symposia》2012,319(1):203-209
Summary: In recent years, an important class of new compounds, ionic liquids (ILs), has been investigated as additives for polymers. In this work, we carried out the synthesis of 4 different ILs: 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM.BF4), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM.PF6), and the chiral ILs acetyl-(−)menthol-1-buthylimidazole tetrafluoroborate ([amebim]BF4) and acetyl-(−)menthol-1-buthylimidazole hexafluorophosphate ([amebim]PF6). These ILs were added to poly(methyl methacrylate) (PMMA) in 10, 20 and 30% ratios by weight and the ILs, PMMA and the obtained materials (PMMA:ILs) were characterized by infrared, visible spectroscopy and atomic force microscope. The ILs added to PMMA did not provide significant changes in the infrared spectra, compared to pure PMMA. However, the absorption spectra in the visible region of the PMMA:ILs materials showed differences, compared to the spectrum of pure PMMA. 相似文献
90.
Olefin Cyclopropanation by Radical Carbene Transfer Reactions Promoted by Cobalt(II)/Porphyrinates: Active‐Metal‐Template Synthesis of [2]Rotaxanes 下载免费PDF全文
Arthur F. P. Alcântara Liniquer A. Fontana Vitor H. Rigolin Yuri F. S. Andrade Dr. Marcos A. Ribeiro Prof. Wdeson P. Barros Prof. Catia Ornelas Prof. Jackson D. Megiatto Jr. 《Angewandte Chemie (International ed. in English)》2018,57(29):8979-8983
A CoII/porphyrinate‐based macrocycle in the presence of a 3,5‐diphenylpyridine axial ligand functions as an endotopic ligand to direct the assembly of [2]rotaxanes from diazo and styrene half‐threads, by radical‐carbene‐transfer reactions, in excellent 95 % yield. The method reported herein applies the active‐metal‐template strategy to include radical‐type activation of ligands by the metal‐template ion during the organometallic process which ultimately yields the mechanical bond. A careful quantitative analysis of the product distribution afforded from the rotaxane self‐assembly reaction shows that the CoII/porphyrinate subunit is still active after formation of the mechanical bond and, upon coordination of an additional diazo half‐thread derivative, promotes a novel intercomponent C?H insertion reaction to yield a new rotaxane‐like species. This unexpected intercomponent C?H insertion illustrates the distinct reactivity brought to the CoII/porphyrinate catalyst by the mechanical bond. 相似文献