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991.
Muñoz MG Encinar M Bonales LJ Ortega F Monroy F Rubio RG 《The journal of physical chemistry. B》2005,109(10):4694-4699
The dynamics of the liquid-air interface of aqueous solutions of a tensioactive triblock copolymer (Pluronic F-68) has been studied using surface quasielastic light scattering over a broad range of concentrations and temperatures. Ancillary surface tension and bulk rheometry data have been obtained for the same system. The results show that the classical theoretical spectrum for monolayers on a Newtonian fluid can be applied only for concentrations below 4.10(-2) mM. For concentrations above c = 14 mM a clear peak centered at zero frequency appears in the spectrum. This feature is incompatible with the classical theoretical spectrum. The SQELS spectra have been described in terms of the theory of Wang and Huang [Wang, C. H.; Huang, Q. R. J. Chem. Phys. 1997, 107, 5898] considering that the loss modulus of the concentrated solutions shows the existence of two relaxation modes even at low frequencies. The theory is able to explain the existence of a peak centered at zero frequency in the spectra, and the theoretical spectra point out the existence of an elastic peak together with the capillary one. There is a reasonable agreement between the relaxation times and the product Gtau obtained from the fits of the SQELS spectra to the theory of Wang and Huang and those obtained from bulk rheology. 相似文献
992.
Trivinho-Strixino F Pereira EC Mello SV Oliveira ON 《Langmuir : the ACS journal of surfaces and colloids》2004,20(9):3740-3745
Nanostructured films from two conducting polymers, poly(o-methoxyaniline) (POMA) and poly(3-thiopheneacetic acid) (PTAA), were fabricated with the layer-by-layer (LBL) technique. The electrochemical response of the LBL films differs from that of a POMA cast film, even in a potential range where PTAA is inactive. This is attributed to differences in the diffusion-controlled charge and mass transport, where distinct ionic species participate in the LBL films, as demonstrated by quartz crystal microbalance measurements. The results show that the transport properties of conducting polymers can be changed by alternation with layers of appropriate materials in LBL films. 相似文献
993.
Terriza A Álvarez R Borrás A Cotrino J Yubero F González-Elipe AR 《Journal of colloid and interface science》2012,376(1):274-282
The wetting behavior of fluorocarbon materials has been studied with the aim of assessing the influence of the surface chemical composition and surface roughness on the water advancing and receding contact angles. Diamond like carbon and two fluorocarbon materials with different fluorine content have been prepared by plasma enhanced chemical vapor deposition and characterized by X-ray photoemission, Raman and FT-IR spectroscopies. Very rough surfaces have been obtained by deposition of thin films of these materials on polymer substrates previously subjected to plasma etching to increase their roughness. A direct correlation has been found between roughness and water contact angles while a superhydrophobic behavior (i.e., water contact angles higher than 150° and relatively low adhesion energy) was found for the films with the highest fluorine content deposited on very rough substrates. A critical evaluation of the methods currently used to assess the roughness of these surfaces by atomic force microscopy (AFM) has evidenced that calculated RMS roughness values and actual surface areas are quite dependent on both the scale of observation and image resolution. A critical discussion is carried out about the application of the Wenzel model to account for the wetting behavior of this type of surfaces. 相似文献
994.
Bastida A Hidalgo A Chiara JL Torrado M Corzana F Pérez-Cañadillas JM Groves P Garcia-Junceda E Gonzalez C Jimenez-Barbero J Asensio JL 《Journal of the American Chemical Society》2006,128(1):100-116
The emergence of bacterial resistance to the major classes of antibiotics has become a serious problem over recent years. For aminoglycosides, the major biochemical mechanism for bacterial resistance is the enzymatic modification of the drug. Interestingly, in several cases, the oligosaccharide conformation recognized by the ribosomic RNA and the enzymes responsible for the antibiotic inactivation is remarkably different. This observation suggests a possible structure-based chemical strategy to overcome bacterial resistance; in principle, it should be possible to design a conformationally locked oligosaccharide that still retains antibiotic activity but that is not susceptible to enzymatic inactivation. To explore the scope and limitations of this strategy, we have synthesized several aminoglycoside derivatives locked in the ribosome-bound "bioactive" conformation. The effect of the structural preorganization on RNA binding, together with its influence on the aminoglycoside inactivation by several enzymes involved in bacterial resistance, has been studied. Our results indicate that the conformational constraint has a modest effect on their interaction with ribosomal RNA. In contrast, it may display a large impact on their enzymatic inactivation. Thus, the work presented herein provides a key example of how the conformational differences exhibited by these ligands within the binding pockets of the ribosome and of those enzymes involved in bacterial resistance can, in favorable cases, be exploited for designing new antibiotic derivatives with improved activity in resistant strains. 相似文献
995.
María José González-álvarez Antonio Di Marino Francisco Mendicuti 《Journal of fluorescence》2009,19(3):449-462
Steady-state, time-resolved fluorescence, Circular Dichroism and Molecular Mechanics techniques were used to study the complexation
of 1-methyl naphthalenecarboxylate (1MN) with the 2-hydroxylpropyl-α-, -β- and -γcyclodextrins (HPCDs). The emission spectrum of 1MN shows two bands whose intensity ratios (R) are sensitive to complexation. The stoichiometry, binding constants and thermodynamics parameters upon complexation were
obtained from the variation of fluorescence intensity, R, and lifetime averages, , with [HPCD] and temperature. They were then compared with the ones obtained for the complexation of 1MN with the non-substituted α-,
β- and γCDs. Like the 1MN:CD complexes, the 1MN:HPCD ones showed 1:1 stoichiometries, but they resulted relatively more stable. Molecular Mechanics calculations in the presence
of water allowed us to understand the structure of the complexes and the possible driving forces responsible for the complexation.
Geometry agrees with the experimental stoichiometry and the signs of enthalpy and entropy changes. R for the complexes, quenching, fluorescence depolarization measurements and induced circular dichroism spectra also supported
the proposed structures. 相似文献
996.
M. Fernanda P. Costa Ana Maria A. C. Rocha Rogério B. Francisco Edite M. G. P. Fernandes 《Optimization》2016,65(5):1085-1104
In this article, we aim to extend the firefly algorithm (FA) to solve bound constrained mixed-integer nonlinear programming (MINLP) problems. An exact penalty continuous formulation of the MINLP problem is used. The continuous penalty problem comes out by relaxing the integrality constraints and by adding a penalty term to the objective function that aims to penalize integrality constraint violation. Two penalty terms are proposed, one is based on the hyperbolic tangent function and the other on the inverse hyperbolic sine function. We prove that both penalties can be used to define the continuous penalty problem, in the sense that it is equivalent to the MINLP problem. The solutions of the penalty problem are obtained using a variant of the metaheuristic FA for global optimization. Numerical experiments are given on a set of benchmark problems aiming to analyze the quality of the obtained solutions and the convergence speed. We show that the firefly penalty-based algorithm compares favourably with the penalty algorithm when the deterministic DIRECT or the simulated annealing solvers are invoked, in terms of convergence speed. 相似文献
997.
Carrique F Ruiz-Reina E Arroyo FJ Jiménez ML Delgado AV 《Langmuir : the ACS journal of surfaces and colloids》2008,24(20):11544-11555
In this paper the complex dielectric constant of a concentrated colloidal suspension in a salt-free medium is theoretically evaluated using a cell model approximation. To our knowledge this is the first cell model in the literature addressing the dielectric response of a salt-free concentrated suspension. For this reason, we extensively study the influence of all the parameters relevant for such a dielectric response: the particle surface charge, radius, and volume fraction, the counterion properties, and the frequency of the applied electric field (subgigahertz range). Our results display the so-called counterion condensation effect for high particle charge, previously described in the literature for the electrophoretic mobility, and also the relaxation processes occurring in a wide frequency range and their consequences on the complex electric dipole moment induced on the particles by the oscillating electric field. As we already pointed out in a recent paper regarding the dynamic electrophoretic mobility of a colloidal particle in a salt-free concentrated suspension, the competition between these relaxation processes is decisive for the dielectric response throughout the frequency range of interest. Finally, we examine the dielectric response of highly charged particles in more depth, because some singular electrokinetic behaviors of salt-free suspensions have been reported for such cases that have not been predicted for salt-containing suspensions. 相似文献
998.
Giacomo Quaranta Clara Argerich Martin Ruben Ibañez Jean Louis Duval Elias Cueto Francisco Chinesta 《Comptes Rendus Mecanique》2019,347(5):445-454
The present paper analyzes different integration schemes of solid dynamics in the frequency domain involving the so-called Proper Generalized Decomposition – PGD. The last framework assumes for the solution a parametric dependency with respect to frequency. This procedure allowed introducing other parametric dependences related to loading, geometry, and material properties. However, in these cases, affine decompositions are required for an efficient computation of separated representations. A possibility for circumventing such difficulty consists in combining modal and harmonic analysis for defining an hybrid integration scheme. Moreover, such a procedure, as proved in the present work, can be easily generalized to address nonlinear parametric dynamics, as well as to solve problems with non-symmetric stiffness matrices, always operating in the domain of low frequencies. 相似文献
999.
Juan Diego Pizarro Francisco Molina Dr. Manuel R. Fructos Prof. Dr. Pedro J. Pérez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10330-10335
A family of phosphine ligands containing a five-membered ring similar to the popular N-heterocyclic carbene ligands and an alkoxy third substituent has been developed. These alkoxydiaminophosphine ligands (ADAP) can be generated in one pot and reacted with a copper(I) source leading to the high yield isolation of complexes [(ADAP)CuX]2 (X=Cl, Br). The dinuclear nature of these compounds has been established by means of X-ray studies and DOSY experiments. A screening of the catalytic properties of these complexes toward carbene-transfer reactions from diazocompounds to C−H bonds (alkane, arene), olefins or N−H bonds, as well as in CuAAC or nitrene transfer reactions have shown a performance at least similar, if not better, than their (NHC)CuCl analogues, opening a new window in copper catalysis with these readily tunable ADAP ligands. 相似文献
1000.
Francisco Gabriel Santos Silva Raildo Alves Fiuza Junior Jefferson Santos da Silva Carlos Magno S. R. de Brito Heloysa Martins Carvalho Andrade Jardel Pereira Gonçalves 《Journal of Thermal Analysis and Calorimetry》2014,116(1):287-293
The pozzolanic properties of the equilibrium catalyst (Ecat), an abundant waste from fluid catalytic cracking units of oil refineries, have been studied in cementitious matrices. The consumption of calcium hydroxide is usually taken as a means to assess the pozzolanicity of a material, ignoring the formation of C–S–H and other hydrates, the main product of the pozzolanic reaction. The use of thermal analysis methods allows the identification and quantification of the products of the hydration reaction, based on the loss of chemically combined water of phases present in a cementitious matrix. In the present study, TG/DTG techniques were used to quantify the amount of C–S–H + ettringite, C–A–S–H + C–A–H, and calcium hydroxide in cement–Ecat pastes, containing 0–40 % Ecat, aged for 1–28 days. The influence of the content of these phases on the mechanical properties of the resulting samples was also investigated by axial compression. The results further confirmed the pozzolanic activity of Ecat, so that the production of C–S–H and C–A–S–H increased with the aging time, but in a smaller amount than in the reference paste. The compressive strength test showed that the pastes containing 10 % Ecat, aged for 14 and 28 days, presented improved properties as compared to the corresponding references. 相似文献