Electrochemical and electrogenerated chemiluminescence of clay nanoparticles/Ru(bpy)(3)(2+) multilayer films on ITO electrodes

The electrochemical and electrogenerated chemiluminescence of Ru(bpy)(3)(2+) immobilized in {clay/Ru(bpy)(3)(2+)}(n) multilayer films by layer-by-layer assembly were investigated. The stable multilayer films of clay and Ru(bpy)(3)(2+) were assembled by alternate adsorption of negatively charged clay platelets and positively charged Ru(bpy)(3)(2+) from their aqueous dispersions. UV-vis spectroscopy, quartz crystal microbalance (QCM), cyclic voltammetry, and electrogenerated chemiluminescence (ECL) were used to monitor the immobilization of Ru( bpy)(3)(2+) and the regular growth of the {clay/Ru( bpy)(3)(2+)}(n) multilayer films. The multilayer films modified electrode was used for the ECL detection of tripropylamine ( TPA) and oxalate. The proposed novel immobilized method exhibited good stability, reproducibility and high sensitivity for the determination of TPA and oxalate, which mainly resulted from the contributing of clay nanoparticles with appreciable surface area, special structural features and unusual intercalation properties.

Sol-gel growth of Gd2MoO6 : Eu3+ nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6 : Eu3+) and their luminescent properties

SiO2@Gd2MoO6:EU3+ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy ITEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO2@Gd2MoO6:Eu3+ core-shell phosphors. The XRD results demonstrate that the Gd2MoO6:Eu3+ layers on the SiO2 spheres begin to crystallize after annealing at 600 degrees C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd2MoO6:Eu3+ shells on the SiO2 cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu3+ shows a strong PL luminescence (dominated by D-5(0)-F-7(2) red emission at 613 nm) under the excitation of 307 nm UV light.

Polyol-mediated synthesis of polyhedral silver clusters

Besides the spheres, polyhedral silver nanoclusters were prepared by the polyol process with 3-aminopropyl triethoxysilane (APTES). In the process, APTES acts as not only the stabilizer but also the template.

Formation of a supported hybrid bilayer membrane on gold: A sterically enhanced hydrophobic effect

Adsorption of a monolayer of didecanoyl-L-alpha-phosphatidylcholine (DDPC) from dispersions of small unilamellar vesicles onto hydrophobic surfaces was investigated by mean of cyclic voltammetry and impedance spectroscopy. The hydrophobic surfaces were self-assembled monolayers of 2-mereapto-3-n-octylthiophene (MOT) on gold. One characteristic of the MOT monolayer is its permeability to organic molecules in aqueous solution, thus providing a more energetically favorable hydrophobic surface for the addition of phospholipid vesicles. The kinetics of the lipid monolayer formation were followed by measuring the time-dependent interfacial capacitance. Unusual values of thickness and capacitance of the MOT/ DDPC bilayers were observed. An interdigitating conformation of the bilayer structure was proposed to interpret the experimental results, The horseradish peroxidase reconstituted into the bilayer demonstrated the expected protein activity, showing practical use in research and in biosensor application.

Preparation and characterization of poly(ethyl acrylate)/bentonite nanocomposites by in situ emulsion polymerization

Transparent poly(ethyl acrylate) (PEA)/bentonite nanocomposites containing intercalated-exfoliated combinatory structures of clay were synthesized by in situ emulsion polymerizations in aqueous dispersions containing bentonite. The samples for characterization were prepared through direct-forming films of the resulting emulsions without coagulation and separation. An examination with X-ray diffraction and transmission electron microscopy showed that intercalated and exfoliated structures of clay coexisted in the PEA/bentonite nanocomposites. The measurements of mechanical properties showed that PEA properties were greatly improved, with the tensile strength and modulus increasing from 0.65 and 0.24 to 11.16 and 88.41 MPa, respectively. Dynamic mechanical analysis revealed a very marked improvement of the storage modulus above the glass-transition temperature. In addition, because of the uniform dispersion of silicate layers in the PEA matrix, the barrier properties of the materials were dramatically improved. The permeability coefficient of water vapor decreased from 30.8 x 10(-6) to 8.3 x 10(-6) g cm/cm(2)s cmHg. (C) 2002 Wiley Periodicals, Inc.

Effect of the compatibilization of linear low-density polyethylene-g-acrylic acid on the morphology and mechanical properties of poly(butylene terephthalate)/linear low-density polyethylene blends

A poly(butylene terephthalate) (PBT)/linear low-density polyethylene (LLDPE) alloy was prepared with a reactive extrusion method, For improved compatibility of the blending system, LLDPE grafted with acrylic acid (LLDPE-g-AA) by radiation was adopted in place of plain LLDPE. The toughness and extensibility of the PBT/LLDPE-g-AA blends, as characterized by the impact strengths and elongations at break, were much improved in comparison with the toughness and extensibility of the PBT/LLDPE blends at the same compositions. However, there was not much difference in their tensile (or flexural) strengths and moduli. Scanning electron microscopy photographs showed that the domains of PBT/LLDPE-g-AA were much smaller and their dispersions were more homogeneous than the domains and dispersions of the PBT/ T,T PE blends. Compared with the related values of the PBT/LLDPE blends, the contents and melting temperatures of the usual spherulites of PBT in PBT/LLDPE-g-AA decreased.

Morphologies and physical properties of PA1010/HIPS/HIPS-g-MA ternary blends

The effect of the content of a copolymer consisting of high impact polystyrene grafted with maleic anhydride (HIPS-g-MA) on morphological and mechanical properties of PA1010/HIPS blends has been studied. Blend morphologies were controlled by adding HIPS-g-MA during melt processing, thus the dispersion of the HIPS phase and interfacial adhesion between the domains and matrices in these blends were changed obviously. The weight fractions of HIPS-g-MA in the blends increased from 2.5 to 20, then much finer dispersions of discrete HIPS phase with average domain sizes decreased from 6.1 to 0.1 mu m were obtained. It was found that a compatibilizer, a graft copolymer of HIPS-g-MA and PA1010 was synthesized in situ during the melt mixing of the blends. The mechanical properties of compatibilized blends were obviously better than those of uncompatibilized PA1010/HIPS blends. These behaviors could be attributed to the chemical interactions between the two components of PA1010 and HIPS-g-MA and good dispersion in PA1010/HIPS/HIPS-g-MA blends. Evidence of reactions in the blends was seen in the morphology and mechanical behaviour of the solid. The blend containing 5 wt % HIPS-g-MA component exhibited outstanding toughness. (C) 1999 Kluwer Academic Publishers.

Partial oxidation of methane to synthesize gas over Ni/alpha-Al2O3 catalyst promoted by noble metals

The production of synthesis gas by partial oxidation bf methane in oxygen has been examined over Ni/alpha-Al2O3 catalyst promoted by noble metals(Rh, Ru, Pt and Pd), especially with Pt. The reactivity is considered in conjunction with the result of H-2-TPR, CO-TPD, SEM and XRD. It is found that small amount of Pt results in a great improvement of activity for the Ni/alpha-Al2O3 catalyst. The activity order is : Rh-Ni>Pt-Ni approximate to Ru-Ni>Pd-Ni, meantime the Pt improves the stability of Ni/alpha-Al2O3 catalyst except for Pd which is easy to he deactivated by carbon deposition. The results of TPD, SEM and XRD indicate that there is an interaction between Ni and Pt metals in the catalyst. The interaction increases the dispersions of Pt and Nit the presence of Pt suppresses the growth and the migration of Ni grains over the surface of the catalyst.

Morphological, thermal, and mechanical properties of polypropylene/polycarbonate blend

This work deals with the effect of compatibilizer on the morphological, thermal, rheological, and mechanical properties of polypropylene/polycarbonate (PP/ PC) blends. The blends, containing between 0 to 30 vol % of polycarbonate and a compatibilizer, were prepared by means of a twin-screw extruder. The compatibilizer was produced by grafting glycidyl methacrylate (GMA) onto polypropylene in the molten state. Blend morphologies were controlled by adding PP-g-GMA as compatibilizer during melt processing, thus changing dispersion and interfacial adhesion of the polycarbonate phase. With PP-g-GMA, volume fractions increased from 2.5 to 20, and much finer dispersions of discrete polycarbonate phase with average domain sizes decreased from 35 to 3 mu m were obtained. The WAXD spectra showed that the crystal structure of neat PP was different from that in blends. The DSC results suggested that the degree of crystallization of PP in blends decreased as PC content and compatibilizer increased. The mechanical properties significantly changed after addition of PP-g-GMA. (C) 1997 John Wiley & Sons, Inc.

THE EFFECTS OF LANTHANIDE IONS AND THEIR COMPLEXES ON THE PHASE-TRANSITION PROPERTY OF DIPALMITOYLPHOSPHATIDYLETHANOLAMINE LIPOSOMES

The effects of metal ions and lanthanide complexes on the gel-to-liquid crystal phase transition temperature T-m of dipalmitoylphosphatidylethanolamine liposomes have been studied by differential scanning calorimetry (DSC) method. The results show that the addition of metal ions to the dipalmitoylphosphatidylethanolamine (DPPE) liposomes dispersions increases the main phase transition temperature T-m in the order of monovalent< divalent< trivalent cations. The enhancement of T-m is not large as increasing the lanthanide ions concentration. The enhancement of Pr3+ is larger than that of La3+. Remarkable differences were observed between La-citrate and La-lactate complexes at different pH solutions. At pH 7.0, La-citrate complex has no effect on the T-m, La-lactate complex, however, increases the T-m value, and the increase is larger than that of free lanthanide ions at the same concentration. The decrease of pH of complexes solutions lowers the phase transition temperature. We have preliminarily discussed the mechanism of the enhancements of lanthanide ions and the synergism of lanthanide ion and lactate ligand follow the ion induced dehydration of lipid and the potential effects of ion-lipid interaction.

TENSILE PROPERTIES OF BLENDS OF POLY(ETHER SULFONE) WITH A POLY(ETHER IMIDE)

Blends of poly(ether sulphone) (PES) with a poly(ether imide) (PEI) in various proportions were prepared by the coprecipitation method. Mechanical properties and morphology of the blends were studied using tensile tests and scanning electron microscopy (SEM). The tensile moduli exhibit positive deviations from simple additivity. Marked positive deviations were also observed for ultimate strength. These results suggest that the PEI/PES blends are mechanically compatible. SEM study revealed that the blends are not homogeneous and the polymers are immiscible on the segmental level. However, the dispersions of the blends are rather fine. The interfaces between the two phases are excellently bonded; PEI and PES appear to interact well.

Effective thermal conductivity of graded nonlinear composites with heat contact resistance

The perturbation expansion method is used to find the effective thermal conductivity of graded nonlinear composites having thermal contact resistance on the inclusion surface. As an example, we have studied the graded composites with cylindrical inclusions immersed in a homogeneous matrix. The thermal conductivity of the cylindrical inclusion is assumed to have a power-law profile of the radial distance r measured from its origin. For weakly nonlinear constitutive relations between the heat flow density q and the temperature field T, namely, q = -mu del T - chi vertical bar del T vertical bar(2) del T, in both the inclusion and the matrix regions, we have derived the temperature distributions using the perturbation expansion method. A nonlinear effective medium approximation of graded composites is proposed to estimate the effective linear and nonlinear thermal conductivities. by considering the temperature singularity on the inclusion surface due to the heat contact resistance. (c) 2006 Elsevier B.V. All rights reserved.

青藏高原及邻区面波频散反演--岩石圈-软流层体系结构研究

The Qinghai-Tibet Plateau lies in the place of the continent-continent collision between Indian and Eurasian plates. Because of their interaction the shallow and deep structures are very complicated. The force system forming the tectonic patterns and driving tectonic movements is effected together by the deep part of the lithosphere and the asthenosphere. It is important to study the 3-D velocity structures, the spheres and layers structures, material properties and states of the lithosphere and the asthenosphere for getting knowledge of their formation and evolution, dynamic process, layers coupling and exchange of material and energy. Based on the Rayleigh wave dispersion theory, we study the 3-D velocity structures, the depths of interfaces and thicknesses of different layers, including the crust, the lithosphere and the asthenosphere, the lithosphere-asthenosphere system in the Qinghai-Tibet Plateau and its adjacent areas. The following tasks include: (1)The digital seismic records of 221 seismic events have been collected, whose magnitudes are larger than 5.0 over the Qinghai-Tibet Plateau and its adjacent areas. These records come from 31 digital seismic stations of GSN , CDSN、NCDSN and part of Indian stations. After making instrument response calibration and filtering, group velocities of fundamental mode of Rayleigh waves are measured using the frequency-time analysis (FTAN) to get the observed dispersions. Furthermore, we strike cluster average for those similar ray paths. Finally, 819 dispersion curves (8-150s) are ready for dispersion inversion. (2)From these dispersion curves, pure dispersion data in 2°×2° cells of the areas (18°N-42°N, 70°E-106°E) are calculated by using function expansion method, proposed by Yanovskaya. The average initial model has been constructed by taking account of global AK135 model along with geodetic, geological, geophysical, receiving function and wide-angle reflection data. Then, initial S-wave velocity structures of the crust and upper mantle in the research areas have been obtained by using linear inversion (SVD) method. (3)Taking the results of the linear inversion as the initial model, we simultaneously invert the S wave velocities and thicknesses by using non-linear inversion (improved Simulated Annealing algorithm). Moreover, during the temperature dropping the variable-scale models are used. Comparing with the linear results, the spheres and layers by the non-linear inversion can be recognized better from the velocity value and offset. (4)The Moho discontinuity and top interface of the asthenosphere are recognized from the velocity value and offset of the layers. The thicknesses of the crust, lithosphere and asthenosphere are gained. These thicknesses are helpful to studying the structural differentia between the Qinghai-Tibet Plateau and its adjacent areas and among geologic units of the plateau. The results of the inversion will provide deep geophysical evidences for studying deep dynamical mechanism and exploring metal mineral resource and oil and gas resources. The following conclusions are reached by the distributions of the S wave velocities and thicknesses of the crust, lithosphere and asthenosphere, combining with previous researches. (1)The crust is very thick in the Qinghai-Tibet Plateau, varying from 60 km to 80 km. The lithospheric thickness in the Qinghai-Tibet Plateau is thinner (130-160 km) than its adjacent areas. Its asthenosphere is relatively thicker, varies from 150 km to 230 km, and the thickest area lies in the western Qiangtang. India located in south of Main Boundary thrust has a thinner crust (32-38 km), a thicker lithosphere of about 190 km and a rather thin asthenosphere of only 60 km. Sichuan and Tarim basins have the crust thickness less than 50km. Their lithospheres are thicker than the Qinghai-Tibet Plateau, and their asthenospheres are thinner. (2)The S-wave velocity variation pattern in the lithosphere-asthenosphere system has band-belted distribution along east-westward. These variations correlate with geology structures sketched by sutures and major faults. These sutures include Main Boundary thrust (MBT), Yarlung-Zangbo River suture (YZS), Bangong Lake-Nujiang suture (BNS), Jinshajiang suture (JSJS), Kunlun edge suture (KL). In the velocity maps of the upper and middle crust, these sutures can be sketched. In velocity maps of 250-300 km depth, MBT, BNS and JSJS can be sketched. In maps of the crustal thickness, the lithospheric thickness and the asthenospheric thickness, these sutures can be still sketched. In particular, MBT can be obviously resolved in these velocity maps and thickness maps. (3)Since the collision between India and Eurasian plate, the “loss” of surface material arising from crustal shortening is caused not only by crustal thickening but also by lateral extrusion material. The source of lateral extrusion lies in the Qiangtang block. These materials extrude along the JSJS and BNS with both rotation and dispersion in Daguaiwan. Finally, it extends toward southeast direction. (4)There is the crust-mantle transition zone of no distinct velocity jump in the lithosphere beneath the Qiangtang Terrane. It has thinner lithosphere and developed thicker asthenosphere. It implies that the crust-mantle transition zone of partial melting is connected with the developed asthenosphere. The underplating of asthenosphere may thin the lithosphere. This buoyancy might be the main mechanism and deep dynamics of the uplift of the Qinghai-Tibet hinterland. At the same time, the transport of hot material with low velocity intrudes into the upper mantle and the lower crust along cracks and faults forming the crust-mantle transition zone.

青藏高原横波速度与各向异性结构及其壳幔形变印迹

As the most spectacular and youngest case of continental collision on the Earth, to investigate the crust and mantle of Tibetan plateau, and then to reveal its characters of structure and deformation, are most important to understand its deformation mechanism and deep process. A great number of surface wave data were initially collected from events occurred between 1980 and 2002, which were recorded by 13 broadband digital stations in Eurasia and India. Up to 1,525 source-station Rayleigh waveforms and 1,464 Love wave trains were analysed to obtain group velocity dispersions, accompanying with the detail and quantitative assessment of the fitness of the classic Ray Theory, errors from focal and measurements. Assuming the model region covered by a mesh of 2ox2o-sized grid-cells, we have used the damped least-squares approach and the SVD to carry out tomographic inversion, SV- and SH-wave velocity images of the crust and upper mantle beneath the Tibetan Plateau and surroundings are obtained, and then the radial anisotropy is computed from the Love-Rayleigh discrepancy. The main results demonstrate that follows, a) The Moho beneath the Tibetan Plateau presents an undulating shape that lies between 65 and 74 km, and a clear correlation between the elevations of the plateau and the Moho topography suggests that at least a great part of the highly raised plateau is isostatically compensated. b) The lithospheric root presents a depth that can be substantiated at ~140 km (Qiangtang Block) and exceptionally at ~180 km (Lhasa Block), and exhibits laterally varying fast velocity between 4.6 and 4.7 km/s, even ~4.8 km/s under northern Lhasa Block and Qiangtang Block, which may be correlated with the presence of a shield-like upper mantle beneath the Tibetan Plateau and therefore looked as one of the geophysical tests confirming the underthrusting of India, whose leading edge might have exceeded the Bangong-Nujiang Suture, even the Jinsha Suture. c) The asthenosphere is depicted by a low velocity channel at depths between 140 and 220 km with negative velocity gradient and velocities as low as 4.2 km/s; d) Areas in which transverse radial anisotropy is in excess of ~4% and 6% on the average anisotropy are found in the crust and upper mantle underlying most of the Plateau, and up to 8% in some places. The strength, spatial configuration and sign of radial anisotropy seem to indicate the existence of a regime of horizontal compressive forces in the frame of the convergent orogen at the same time that laterally varying lithospheric rheology and a differential movement as regards the compressive driving forces. e) Slow-velocity anomalies of 12% or more in southern Tibet and the eastern edge of the Plateau support the idea of a mechanically weak middle-to-lower crust and the existence of crustal flow in Tibet.

Anfotericina B e suas formulações lipídicas

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas