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61.
A.?I.?DanilovEmail author R.?R.?Nazmutdinov T.?T.?Zinkicheva E.?B.?Molodkina A.?V.?Rudnev Yu.?M.?Polukarov J.?M.?Feliu 《Russian Journal of Electrochemistry》2008,44(6):697-708
Mechanism of copper underpotential deposition at stepped faces of platinum single crystals Pt(hkl) is studied using cyclic voltammetry, scanning probe microscopy, and quantum-chemical modelling. It is shown that the first stage of UPD is one-dimensional decoration of the (100)- or (110)-orientated steps, then copper monolayer forms at (111)-terraces. The final stage is the secondary step decoration. Quantum-chemical modelling, with the using of long-distance potentials of the Cu-Pt and Cu-Cu pair interactions, allows estimating the energy of copper adsorption at different structure elements of the substrate (steps, kinks, terraces) and revealing the succession of the adatom monolayer formation; it also provides additional information for the identifying of the nature of voltametric peaks for different stages of the copper adsorption-desorption. 相似文献
62.
P.J. Iunes G. Bigazzi J.C. Hadler Neto M.A. Laurenzi M.L. Balestrieri P. Norelli A.M. Osorio Araya S. Guedes C.A. Tello S. S.R. Paulo P.A.F.P. Moreira R. Palissari E.A.C. Curvo 《Radiation measurements》2005,39(6):665-668
Neutron dosimetry based on U and Th thin films was used for fission-track dating of the age standard Moldavite, the central European tektite, from the Middle Miocene deposit of Jankov (southern Bohemia, Czech Republic). Our fission-track age () agrees with a recent 40Ar/39Ar age, , based on several determinations on Moldavites from different sediments, including the Jankov deposit. This result indicates that the U and Th thin film neutron dosimetry represents a reliable alternative for an absolute approach in fission-track dating. 相似文献
63.
64.
Santiago PS Neto Dde S Barbosa LR Itri R Tabak M 《Journal of colloid and interface science》2007,316(2):730-740
Small angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been used to investigate the interaction of the water-soluble meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS(4)) with cationic cethyltrimethylammonium chloride (CTAC) micelles. To evaluate if the porphyrin protonation state affects its interaction with the micelle, both SAXS and EPR measurements were performed at pH 4.0 and 9.0. The best-fit SAXS curves were obtained assuming for CTAC micelle a prolate ellipsoidal shape in the absence and upon incorporation of 2-10 mM TPPS(4). SAXS results show that the presence of porphyrin impacts on micellar hydrophobic core, leading to a micellar reassembling into smaller micelles. Lineshapes of EPR spectra of 5- and 16-doxyl stearic acids (5- and 16-DSA, respectively) bound to 100 mM CTAC micelles exhibited slight changes as a function of porphyrin concentration. Spectral simulations revealed an increase of mobility restriction for both spin probes, especially at higher porphyrin concentration, where a small reduction of environment polarity was also observed for 16-DSA. The spin labels monitored only slight differences between pH 4.0 and 9.0, in agreement with the SAXS results. 相似文献
65.
Ana Luiza M. S. de Azevedo Benício B. Neto Ieda S. Scarminio Anselmo E. de Oliveira Roy E. Bruns 《Journal of computational chemistry》1996,17(2):167-177
Factorial design and principal component analyses are applied to CH3F infrared frequencies and intensities calculated from ab initio wave functions. In the factorial analysis, the quantitative effects of changing from a 6–31G to a 6–311G basis, of including polarization and diffuse orbitals, and of correcting for electron correlation using the second-order Møller-Plesset procedure are determined for all frequencies and intensities. The most significant main effect observed for the frequencies corresponds to the shift from Hartree-Fock to MP2 calculations, which tends to lower all frequency values by approximately 100 cm−1. For the intensities, the main effects are larger for the CF stretching and the CH3 asymmetric stretching modes. Interaction effects between two or more of the four factors are found to be of minor importance, except for the interaction between correlation and polarization. The principal component analysis indicates that wave functions with polarization and diffuse orbitals at the second-order Møller-Plesset level provide the best estimates for the harmonic frequencies, but not for the intensities. For the frequencies, the first principal component distinguishes between MP2 and Hartree-Fock calculations, while the second component separates the wave functions with polarization orbitals from those without these orbitals. For the intensities, the separation is similar but less well defined. This analysis also shows that wave function optimization to calculate accurate intensities is more difficult than an optimization for frequencies. © 1996 by John Wiley & Sons, Inc. 相似文献
66.
Simone S. Rosatto Lauro T. Kubota Graciliano de Oliveira Neto 《Analytica chimica acta》1999,390(1-3):65-72
Horseradish peroxidase (HRP) was immobilised on silica gel modified with titanium oxide. This material was employed to prepare modified carbon paste electrode. The direct electron transfer of the hydrogen peroxide reduction by HRP was blocked when immobilised on silica–titanium. This biosensor presented a very sensitive response for phenol (1 μmol l−1) at an applied potential of 0 mV vs SCE. The best condition was achieved in phosphate buffer pH 6.8, ratio of hydrogen peroxide/phenol higher than 0.35. The biosensor showed a linear response range between 10 and 50 μmol l−1 of phenol, adjusted by the equation j=−32.8+16.3 [phenol], for n=5 with a correlation coefficient of 0.9995. The response time of the biosensor was about 3 s. 相似文献
67.
Hery Mitsutake Eloiza Guimares Helieder C. Freitas Lucas C. Gontijo Douglas Q. Santos Waldomiro Borges Neto 《Journal of Chemometrics》2015,29(7):411-419
In this work, mid‐infrared spectroscopy and multivariate control charts based on net analyte signal were applied for quality control of B5 blends of biodiesel/diesel (5% biodiesel/95% diesel). Control charts were constructed using instrumental signal decomposition, generating three charts: the net analyte signal chart for monitoring the analyte of interest (methyl soybean biodiesel); the interference chart, which corresponds to the contribution of all other compounds in the diesel sample (diesel); and the residual chart, which corresponds to non‐systematic variations. Statistical limits were established for each developed chart, using samples inside quality specifications (normal operation conditions). To validate multivariate control charts, new samples were analyzed. The new samples represented samples in‐control and samples out‐of‐control in relation to the content of biodiesel, adulterated biodiesel with severe vegetable oils and adulterated diesel with residual automotive lubricant oil, kerosene, and gasoline. The results obtained show an excellent distinction between the samples inside and out of the quality specifications, with 91% and 100% correctly classified, respectively, which demonstrates that the methodology developed is a viable alternative for quality monitoring of this type of fuel. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
68.
Andreia F. Sousa Alessandro Gandini Armando J. D. Silvestre Carlos Pascoal Neto José J. C. Cruz Pinto Christer Eckerman Bjarne Holmbom 《Journal of polymer science. Part A, Polymer chemistry》2011,49(10):2281-2291
This article reports the successful synthesis and characterization of two types of completely biobased polymers prepared by the polycondensation or polytransesterification of suberin fragments, isolated by different procedures and from two different vegetable sources. These polymerizations were conducted with different experimental conditions in terms of the type of catalyst, the reaction medium and temperature, as well as the molar ratio between the reactive moieties. The ensuing linear or partly crosslinked polyesters were characterized by conventional spectroscopic techniques, SEC, DSC, XRD, DMA, and TGA. These hydrophobic materials represent an original contribution to the growing field of polymers from renewable resources. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
69.
B.S. Santos P.M.A. Farias A. Fontes A.G. Brasil Jr. C.N. Jovino A.G.C. Neto F.D. de Menezes R. Ferreira 《Applied Surface Science》2008,255(3):796-798
Semiconductor nanoparticles in the quantum confinement regime used as biolabels present many advantages over the other chemical species used as fluorophores. They are composed of 2000-6000 atoms rendering a far greater photostability and allowing for long time bioimaging experiments. In this work we present a synthetic route for the obtention of large quantities of highly fluorescent CdSe and CdTe/CdS core-shell nanocrystals based on aqueous colloidal chemistry. The methodologies were optimized and the systems were characterized by optical spectroscopy, transmission electronic microscopy and X-Ray diffractometry. The fluorescent biolabels were tested in live macrophages. 相似文献
70.
Tércio de Freitas Paulo Solange de Oliveira Pinheiro Maria Aparecida S. Da Silva Luiz Gonzaga de França Lopes Lucidalva S. Pinheiro Gil F. A. Aquino Márcia Laudelina Arruda Temperini Pedro de Lima Neto Izaura Cirino Nogueira Diógenes 《Electroanalysis》2009,21(9):1081-1089
STM and impedance results of the self‐assembled monolayer (SAM) formed with thionicotinamide (TNA) on gold indicate the presence of defects that increase with the immersion time of the electrode in the TNA solution affecting the SAM electroactivity toward the electron transfer reaction of the cytochrome c metalloprotein and [Fe(CN)6]4? and [Ru(NH3)6]3+ complexes. It was observed that this electroactivity was also affected by the pH of the electrolyte solution. SERS and STM data indicate sulfur coordination to the surface with contribution of the NH2 group. From the dependence of the TNA surface coverage on the temperature and concentration in solution, thermodynamic parameters of adsorption were determined. 相似文献