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71.
Amanda C. Santos Valtencir Zucolotto Carlos J. L. Constantino Helder N. Cunha José R. dos SantosJr. Carla Eiras 《Journal of Solid State Electrochemistry》2007,11(11):1505-1510
Multilayered nanostructured films have been widely investigated for electrochemical applications as modified electrodes, including
the layer-by-layer (LbL) films where properties such as thickness and film architecture can be controlled at the molecular
level. In this study, we investigate the electrochemical features of LbL films of poly(o-methoxyaniline; POMA) and tetrasulfonated phthalocyanines containing nickel (NiTsPc) or copper (CuTsPc). The films displayed
well-defined electroactivity, with redox pairs at 156 and 347 mV vs SCE, characteristic of POMA, which allowed their use as
modified electrodes for detecting dopamine and ascorbic acid at concentrations as low as 10−5 M.
This paper is dedicated to Prof. Francisco Nart, in memoriam. 相似文献
72.
Tormena CF Santos FP Neto AC Rittner R Yoshinaga F Temistocles JC 《The journal of physical chemistry. A》2007,111(2):295-298
Conformational preferences and electronic interactions of trans-2-fluorocyclopentanol (1), trans-2-chlorocyclopentanol (2), and trans-2-bromocyclopentanol (3) were analyzed using experimental and theoretical (3)J(HH) coupling constants, theoretical calculations, and natural bond orbital (NBO) analysis. The conformational equilibria of compounds 1-3 can be represented by their diaxial and diequatorial conformers as supported by theoretical calculations. From (3)J(HH) coupling constant values, it can be found that the diequatorial conformer is present in the equilibrium as 55% for compound 1 and as 60% for compounds 2 and 3. This behavior is in agreement with orbital interaction analyses obtained from NBO. 相似文献
73.
Santos LS Cunha RL Comasseto JV Eberlin MN 《Rapid communications in mass spectrometry : RCM》2007,21(9):1479-1484
Tellurium tetrachloride adds to alkynes via two pathways: a concerted syn-addition that yields Z-tri- and -tetrasubstituted alkenes or an anti-addition that yields E-alkenes. The mechanistic aspects of these divergent pathways for TeCl4 addition to alkynes have been investigated by on-line electrospray ionization (tandem) mass spectrometry (ESI-MS(/MS)). Via ESI-MS(/MS), we have been able to intercept and characterize the active electrophile TeCl3+ in tetrahydrofuran (THF) solutions of TeCl4, as well as its THF complex and several TeClx(OH)y+ derivatives. For the first time, also, key Te(IV) cationic intermediates of the electrophilic addition of TeCl4 to alkynes were captured for gas-phase MS investigation. The detailed structural data of cyclic tellurane intermediates intercepted herein seems to provide insights into the coordinative behavior of the Te(IV) atom and its mode of action towards biological targets. 相似文献
74.
We present variants of the block-GMRES() algorithms due to Vital and the block-LGMRES(,) by Baker, Dennis and Jessup, obtained with replacing the standard QR factorization by a rank-revealing QR factorization
in the Arnoldi process. The resulting algorithm allows for dynamic block deflation whenever there is a linear dependency between
the Krylov vectors or the convergence of a right-hand-side occurs. implementations of the algorithms were tested on a number of test matrices and the results show that in some cases a substantial
reduction of the execution time is obtained. Also a parallel implementation of our variant of the block-GMRES() algorithm, using and was tested on parallel computer, showing good parallel efficiency.
This work was carried out while the author was at IM/UFRGS. 相似文献
75.
M.A. Continentino J.C. Fernandes R.B. Guimar aes H.A. Borges A. Sulpice J.-L. Tholence J.L. Siqueira J.B.M. da Cunha C.A. dos Santos 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,9(4):613-618
The system Cu2FeO2BO3 is an oxyborate belonging to the family of the ludwigites. In this paper we present AC susceptibility, magnetization measurements
and M?ssbauer spectroscopy on this material which allows for a complete characterization of its complex magnetic behavior.
We find an hierarchy of interactions which clearly defines three regimes with decreasing temperature. These are associated
with, the freezing of the Fe moments, the antiferromagnetic ordering of the Cu sub-lattice and finally the coupling between
both systems.
Received 25 September 1998 相似文献
76.
H. N. da Cunha L. H. C. Mattoso R. M. Faria 《Journal of Polymer Science.Polymer Physics》1997,35(8):1201-1205
Structural changes in poly(vinylidene fluoride)-trifluoroethylene [P(VDF-TrFE)] copolymers caused by X-ray irradiation were investigated by molecular weight determination, EPR analysis, FTIR spectroscopy, gel content, DSC thermal analysis, X-ray diffraction, and piezoelectricity measurements. Samples exhibit radiation-induced conductivity (RIC) due to the formation of radical ions. These radicals are generated by bond cleavage, which could react, leading to structural changes such as oxidation, double bond formation, chain scission, and crosslinking. The increasing gel content with radiation dose indicated that crosslinkings of the polymer chains predominate. Irradiation on P(VDF-TrFE) caused the melting temperature, heat of fusion, and Curie temperature to decrease. These results are consistent with the partial destruction of crystalline domains. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1201–1205, 1997 相似文献
77.
Aline G. Cunha Gloria Fernández-Lorente Melissa L. E. Gutarra Juliana V. Bevilaqua Rodrigo V. Almeida Lúcia M. C. Paiva Roberto Fernández-Lafuente Jose M. Guisán Denise M. G. Freire 《Applied biochemistry and biotechnology》2009,156(1-3):133-145
Lipases are an enzyme class of a great importance as biocatalysts applied to organic chemistry. However, it is still necessary to search for new enzymes with special characteristics such as good stability towards high temperatures, organic solvents, and high stereoselectivity presence. The present work’s aim was to immobilize the lipases pool produced by Penicillium simplissicimum, a filamentous fungi strain isolated from Brazilian babassu cake residue. P. simplissicimum lipases were separated into three different fractions using selective adsorption method on different hydrophobic supports (butyl-, phenyl-, and octyl-agarose) at low ionic strength. After immobilization, it was observed that these fractions’ hyperactivation is in the range of 131% to 1133%. This phenomenon probably occurs due to enzyme open form stabilization when immobilized onto hydrophobic supports. Those fractions showed different thermal stability, specificity, and enantioselectivity towards some substrates. Enantiomeric ratio for the hydrolysis of (R,S) 2-O-butyryl-2-phenylacetic acid ranged from 1 to 7.9 for different immobilized P. simplissicimum lipase fractions. Asymmetry factor for diethyl 2-phenylmalonate hydrolysis ranged from 11.8 to 16.4 according to the immobilized P. simplissicimum lipase fractions. Those results showed that sequential adsorption methodology was an efficient strategy to obtain new biocatalysts with different enantioselectivity degrees, thermostability, and specificity prepared with a crude extract produced by a simple and low-cost technology. 相似文献
78.
A method for the rapid trace analysis of 24 residual pesticides in apple juice by multidimensional gas chromatography–mass spectrometry (MD-GC/MS) using dispersive liquid–liquid microextraction (DLLME) was developed and optimized. Several parameters of the extraction procedure such as type and volume of extraction solvent, type and volume of dispersive solvent and salt addition were evaluated to achieve the highest yield and to attain the lowest detection limits. The DLLME procedure optimized consists in the formation of a cloudy solution promoted by the fast addition to the sample (5 ml) of a mixture of carbon tetrachloride (extraction solvent, 100 μl) and acetone (dispersive solvent, 400 μl). The tiny droplets formed and dispersed among the aqueous sample solution are further joined and sedimented (85 μl) in the bottom of the conical test tube by centrifugation. Once extracted, all the 24 pesticides were directly injected and separated by a dual GC column system, comprising a short wide-bore DB-5 capillary column with low film thickness connected by a Deans switch system to a second chromatographic narrower column, with identical stationary phase. The instrumental setting used, in combination with carefully optimized operational fast GC and MS parameters, markedly decreased the retention times of the targeted analytes. The total chromatographic run was 8 min. Mean recoveries for apple juice spiked at three concentrations ranged from 60% to 105% and the intra-repeatability ranged from 1% to 21%. The limits of detection of the 24 pesticides ranged from 0.06 to 2.20 μg/L. In 2 of a total of 28 analysed samples were found residues of captan, although at levels below the maximum limit legal established. 相似文献
79.
Valdecir Biondo Suzana Nóbrega de Medeiros Andrea Paesano Luis Ghivelder Bachir Hallouche João Batista Marimon da Cunha 《Solid State Sciences》2009,11(8):1444-1450
The Fex(Cr2O3)1?x system, with 0.10 ≤ X ≤ 0.80, was mechanically processed for 24 h in a high-energy ball-mill. In order to examine the possible formation of iron–chromium oxides and alloys, the milled samples were, later, thermally annealed in inert (argon) and reducing (hydrogen) atmospheres. The as-milled and annealed products were characterized by X-ray diffraction, Mössbauer spectroscopy, transmission electron microscopy and magnetization. The as-milled samples showed the formation of an Fe1+YCr2?YO4?δ nanostructured and disordered spinel phase, the α1-Fe(Cr) and α2-Cr(Fe) solid solutions and the presence of non-exhausted precursors. For the samples annealed in inert atmosphere, the chromite (FeCr2O4) formation and the recrystallization of the precursors were verified. The hydrogen treated samples revealed the reduction of the spinel phase, with the phase separation of the chromia phase and retention of the Fe–Cr solid solutions. All the samples, either as-milled or annealed, presented the magnetization versus applied field curves typical for superparamagnetic systems. 相似文献
80.
Alexandre Salles da Cunha Nelson Maculan Mauricio G.C. Resende 《Discrete Applied Mathematics》2009,157(6):1198-1217
Given an undirected graph G with penalties associated with its vertices and costs associated with its edges, a Prize Collecting Steiner (PCS) tree is either an isolated vertex of G or else any tree of G, be it spanning or not. The weight of a PCS tree equals the sum of the costs for its edges plus the sum of the penalties for the vertices of G not spanned by the PCS tree. Accordingly, the Prize Collecting Steiner Problem in Graphs (PCSPG) is to find a PCS tree with the lowest weight. In this paper, after reformulating and re-interpreting a given PCSPG formulation, we use a Lagrangian Non Delayed Relax and Cut (NDRC) algorithm to generate primal and dual bounds to the problem. The algorithm is capable of adequately dealing with the exponentially many candidate inequalities to dualize. It incorporates ingredients such as a new PCSPG reduction test, an effective Lagrangian heuristic and a modification in the NDRC framework that allows duality gaps to be further reduced. The Lagrangian heuristic suggested here dominates their PCSPG counterparts in the literature. The NDRC PCSPG lower bounds, most of the time, nearly matched the corresponding Linear Programming relaxation bounds. 相似文献