891 resultados para Polimerização interfacial
Resumo:
This work aimed to develop a new therapeutic approach to increase the efficacy of 5-fluorouracil (5-FU) in the treatment of advanced or recurrent colon cancer. 5-FU-loaded biodegradable poly(ε-caprolactone) nanoparticles (PCL NPs) were combined with the cytotoxic suicide gene E (combined therapy). The SW480 human cancer cell line was used to assay the combined therapeutic strategy. This cell line was established from a primary adenocarcinoma of the colon and is characterized by an intrinsically high resistance to apoptosis that correlates with its resistance to 5-FU. 5-FU was absorbed into the matrix of the PCL NPs during synthesis using the interfacial polymer disposition method. The antitumor activity of gene E from the phage ϕX174 was tested by generating a stable clone (SW480/12/E). In addition, the localization of E protein and its activity in mitochondria were analyzed. We found that the incorporation of 5-FU into PCL NPs (which show no cytotoxicity alone), significantly improved the drug's anticancer activity, reducing the proliferation rate of colon cancer cells by up to 40-fold when compared with the nonincorporated drug alone. Furthermore, E gene expression sensitized colon cancer cells to the cytotoxic action of the 5-FU-based nanomedicine. Our findings demonstrate that despite the inherent resistance of SW480 to apoptosis, E gene activity is mediated by an apoptotic phenomenon that includes modulation of caspase-9 and caspase-3 expression and intense mitochondrial damage. Finally, a strongly synergistic antiproliferative effect was observed in colon cancer cells when E gene expression was combined with the activity of the 5-FU-loaded PCL NPs, thereby indicating the potential therapeutic value of the combined therapy.
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En el presente trabajo se ha desarrollado el primer aptasensor (biosensor de aptámero) en nuestro grupo de investigación, Grup de Sensors i Biosensors de la Universidad Autònoma de Barcelona. En concreto se han desarrollado dos aptasensores para la detección de la proteína trombina, uno basado en la inmovilización de aptámeros por adsorción física, y otro basado en la inmovilización de aptámeros por enlace covalente mediante la reacción EDAC-NHS. El aptasensor utiliza la afinidad específica de la cadena de DNA (aptámero) por la proteína con la que interacciona. Los cambios de carga y estéricos del complejo aptámero proteína alteran la capacidad y la resistencia de transferencia interfacial de electrones en la superficie del electrodo. El principio de detección se basa en la detección de cambios de estas propiedades de interfase del electrodo con el marcador redox [Fe(CN)6]3- / [Fe(CN)6]4-, utilizando mediciones de Espectroscopia Electroquímica de Impedancia. El aptasensor basado en adsorción física del aptámero mostró una respuesta lineal a trombina en el rango de 7.5 a 75 pM y un límite de detección de 5pM, después de optimizar todas las condiciones experimentales. Posteriormente se estudió la especificidad del sistema respecto proteínas potencialmente interferentes presentes en suero sanguíneo, obteniendo cierta interferencia por parte de fibrinógeno e inmunoglobulina G, pero no por parte de albúmina. El sensor demostró ser regenerable mediante la ruptura del complejo formado entre el aptámero y la trombina con una solución de NaCl 2.0 M, aumento de la temperatura y agitación. El segundo aptasensor, basado en enlace covalente del aptámero mostró una respuesta lineal a trombina y limite de detección mejor que el anterior sensor; de 2.5 a 100 pM y 1.5 pM respectivamente. Aunque cabe destacar que este aptasensor está siendo optimizado actualmente.
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The main objective of this study was the management of corn stalk waste as reinforcement for polypropylene (PP) injection moulded composites as an alternative to wood flour and fibers. In the first step, corn stalk waste was subjected to various treatments, and four different corn stalk derivatives (flour and fibers) able to be used as reinforcement of composite materials were prepared and characterized. These derivatives are corn stalk flour, thermo-mechanical, semi-chemical, and chemical fibers. They were characterized in terms of their yield, lignin content, Kappa number, fiber length/diameter ratio, fines, coarseness, viscosity, and the length at the break of a standard sheet of paper. Results showed that the corn stalk derivatives have different physico-chemical properties. In the second step, the prepared flour and fibers were explored as a reinforcing element for PP composites. Coupled and non-coupled PP composites were prepared and tested for tensile properties. For overall trend, with the addition of a coupling agent, tensile properties of composites significantly improved, as compared with non-coupled samples. In addition, a morphological study revealed the positive effect of the coupling agent on the interfacial bonding. The composites prepared with semichemical fiber gave better results in comparison with the rest of the corn stalk derivatives due to its chemical characteristics
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Stone groundwood (SGW) is a fibrous matter commonly prepared in a high yield process, and mainly used for papermaking applications. In this work, the use of SGW fibers is explored as reinforcing element of polypropylene (PP) composites. Due to its chemical and superficial features, the use of coupling agents is needed for a good adhesion and stress transfer across the fiber-matrix interface. The intrinsic strength of the reinforcement is a key parameter to predict the mechanical properties of the composite and to perform an interface analysis. The main objective of the present work was the determination of the intrinsic tensile strength of stone groundwood fibers. Coupled and non-coupled PP composites from stone groundwood fibers were prepared. The influence of the surface morphology and the quality at interface on the final properties of the composite was analyzed and compared to that of fiberglass PP composites. The intrinsic tensile properties of stone groundwood fibers, as well as the fiber orientation factor and the interfacial shear strength of the current composites were determined
Resumo:
The interfacial micromotion is closely associated to the long-term success of cementless hip prostheses. Various techniques have been proposed to measure them, but only a few number of points over the stem surface can be measured simultaneously. In this paper, we propose a new technique based on micro-Computer Tomography (μCT) to measure locally the relative interfacial micromotions between the metallic stem and the surrounding femoral bone. Tantalum beads were stuck at the stem surface and spread at the endosteal surface. Relative micromotions between the stem and the endosteal bone surfaces were measured at different loading amplitudes. The estimated error was 10μm and the maximal micromotion was 60μm, in the loading direction, at 1400N. This pilot study provided a local measurement of the micromotions in the 3 direction and at 8 locations on the stem surface simultaneously. This technique could be easily extended to higher loads and a much larger number of points, covering the entire stem surface and providing a quasi-continuous distribution of the 3D interfacial micromotions around the stem. The new measurement method would be very useful to compare the induced micromotions of different stem designs and to optimize the primary stability of cementless total hip arthroplasty.
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Realizou-se o estudo micromorfológico de oito solos da Zona da Mata Mineira, incluindo um Latossolo Una, dois Podzólicos Vermelho-Escuros, dois Brunizéns Avermelhados, uma Terra Roxa Estruturada, um Vertissolo e um Podzólico Vermelho-Amarelo câmbico. Após coleta, impregnação, polimerização e preparo de seções finas, estas foram analisadas por microscopia óptica para estudo micropedológico, caracterizando a microestrutura, porosidade, esqueleto, organização do plasma e estruturas associadas, com destaque para a argila iluviada. Em adição, análises em microscópio eletrônico de varredura da superfície de agregados foram realizadas em agregados individualizados. O horizonte B do Latossolo estudado apresenta forte microestrutura com influência de atividade biológica, que tende a coalescer intensamente em profundidade e torna-se apédico no saprolito, separado por cascalheiro de quartzo. Nódulos de hematita em processo de degradação foram observados, indicando o processo atual de goethização dos solos, notadamente no Vertissolo e no Latossolo Una. O estudo micromorfológico evidenciou solos com Bt que apresentaram cerosidade forte em observação macroscópica e não a evidenciaram claramente em microscópio, sendo esse fato mais marcante nos solos mais vermelhos. Solos com Bt mais amarelados mostraram cerosidade fraca no campo, com correspondente detecção de cutãs iluviais em microscopia óptica. O Podzólico Vermelho-Amarelo câmbico, com cerosidade fraca e comum no campo, não teve sua presença confirmada em nível microscópico, evidenciando seu caráter câmbico. Esse solo evidencia nódulos de hematita circundados por gibbsita, o que poderia contribuir para explicar a manutenção dos altos teores de óxidos de ferro desses solos. A não-confirmação, ao microscópio, da cerosidade descrita em campo nos solos com Bt indica a necessidade da intensificação de estudos (descrição x micropedologia) na tentativa de melhor aferição e consistência de resultados.
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Hidrogéis produzidos a partir de poliacrilamida (PAAm) foram sintetizados e suas eficiências para liberação controlada de NH4+ e K+ contidos em fertilizantes foram avaliadas. Os hidrogéis foram sintetizados em solução aquosa a partir da polimerização do monômero acrilamida (AAm) em duas concentrações (3,6 e 21,7 %), em presença do agente de reticulação N', N-metileno-bis-acrilamida (MBAAm) e catalisador N, N, N', N'-tetrametil etilenodiamina (TEMED). A fixação de nutrientes ocorreu submetendo-se os hidrogéis à solução aquosa com concentrações de 86 e 82 mg L-1 de K+ e NH4+. As propriedades hidrofílicas, espectroscópicas e morfológicas foram investigadas por meio de medidas de grau de intumescimento (Q), por espectroscopia no infravermelho com transformada de Fourier (FTIR) e por meio de imagens obtidas por microscopia eletrônica de varredura (MEV). Os teores de NH4+ e K+ liberados em meio aquoso foram monitorados em intervalos de tempo de 1, 2, 4, 18, 26 e 50 h por espectrofotometria com análise por injeção em fluxo e por fotometria de chama. Os resultados de grau de intumescimento mostraram que hidrogéis com nutrientes fixados são mais hidrofóbicos. Observações em MEV revelaram decréscimo no tamanho médio dos poros para os hidrogéis com maior quantidade de acrilamida. A cinética de liberação controlada de NH4+ e K+ permitiu inferir que o hidrogel sintetizado com 21,7 % de AAm apresentou maior potencial na liberação controlada dos nutrientes, principalmente NH4+.
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We report on the study of the structural, magnetic, and electronic properties of SrTiO3 capped La2/3Ca1/3MnO3 electrodes grown on (001) and (110) SrTiO3 substrates. Magnetic properties of the (001) and (110) capped electrodes evolve differently when the capping layer thickness increases, revealing a reduction of the saturation magnetization for the (001) ones. Electronic properties are studied combining 55Mn nuclear magnetic resonance (NMR) and x-ray photoemission spectroscopy (XPS). NMR experiments highlight that electronic phase separation in the (001) electrodes is enhanced by the presence of the SrTiO3 capping layer and XPS measurements show that the electronic state of interfacial Mn ions from (001) electrode is more sensitive to the capping layer.
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By an analysis of the exchange of carriers through a semiconductor junction, a general relationship for the nonequilibrium population of the interface states in Schottky barrier diodes has been derived. Based on this relationship, an analytical expression for the ideality factor valid in the whole range of applied bias has been given. This quantity exhibits two different behaviours depending on the value of the applied bias with respect to a critical voltage. This voltage, which depends on the properties of the interfacial layer, constitutes a new parameter to complete the characterization of these junctions. A simple interpretation of the different behaviours of the ideality factor has been given in terms of the nonequilibrium charging properties of interface states, which in turn explains why apparently different approaches have given rise to similar results. Finally, the relevance of our results has been considered on the determination of the density of interface states from nonideal current-voltage characteristics and in the evaluation of the effects of the interfacial layer thickness in metal-insulator-semiconductor tunnelling diodes.
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The correlation between the structural (average size and density) and optoelectronic properties [band gap and photoluminescence (PL)] of Si nanocrystals embedded in SiO2 is among the essential factors in understanding their emission mechanism. This correlation has been difficult to establish in the past due to the lack of reliable methods for measuring the size distribution of nanocrystals from electron microscopy, mainly because of the insufficient contrast between Si and SiO2. With this aim, we have recently developed a successful method for imaging Si nanocrystals in SiO2 matrices. This is done by using high-resolution electron microscopy in conjunction with conventional electron microscopy in dark field conditions. Then, by varying the time of annealing in a large time scale we have been able to track the nucleation, pure growth, and ripening stages of the nanocrystal population. The nucleation and pure growth stages are almost completed after a few minutes of annealing time at 1100°C in N2 and afterward the ensemble undergoes an asymptotic ripening process. In contrast, the PL intensity steadily increases and reaches saturation after 3-4 h of annealing at 1100°C. Forming gas postannealing considerably enhances the PL intensity but only for samples annealed previously in less time than that needed for PL saturation. The effects of forming gas are reversible and do not modify the spectral shape of the PL emission. The PL intensity shows at all times an inverse correlation with the amount of Pb paramagnetic centers at the Si-SiO2 nanocrystal-matrix interfaces, which have been measured by electron spin resonance. Consequently, the Pb centers or other centers associated with them are interfacial nonradiative channels for recombination and the emission yield largely depends on the interface passivation. We have correlated as well the average size of the nanocrystals with their optical band gap and PL emission energy. The band gap and emission energy shift to the blue as the nanocrystal size shrinks, in agreement with models based on quantum confinement. As a main result, we have found that the Stokes shift is independent of the average size of nanocrystals and has a constant value of 0.26±0.03 eV, which is almost twice the energy of the Si¿O vibration. This finding suggests that among the possible channels for radiative recombination, the dominant one for Si nanocrystals embedded in SiO2 is a fundamental transition spatially located at the Si¿SiO2 interface with the assistance of a local Si-O vibration.
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Epitaxial Fe/MgO heterostructures have been grown on Si(001) by a combination of sputtering and laser ablation deposition techniques. The growth of MgO on Si(001) is mainly determined by the nature of the interface, with large lattice mismatch and the presence of an amorphous layer of unclear origin. Reflection high energy electron diffraction patterns of this MgO buffer layer are characteristic of an epitaxial, but disordered, structure. The structural quality of subsequent Fe and MgO layers continuously improves due to the better lattice match and the burial of defects. A weak uniaxial in-plane magnetic anisotropy is found superimposed on the expected cubic biaxial anisotropy. This additional anisotropy, of interfacial nature and often found in Fe/MgO and Fe/MgO/GaAs(001) systems, is less intense here due to the poorer MgO/Si interface quality compared with that of other systems. From the evolution of the anisotropy field with film thickness, magnetic anisotropy is also found to depend on the crystal quality. Kerr measurements of a Fe/MgO multilayered structure grown on Si show two different switching fields, suggesting magnetic coupling of two of the three Fe layers. Nevertheless, due to the little sensitivity to the bottom Fe film, independent switching of the three layers cannot be ruled out.
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We have studied domain growth during spinodal decomposition at low temperatures. We have performed a numerical integration of the deterministic time-dependent Ginzburg-Landau equation with a variable, concentration-dependent diffusion coefficient. The form of the pair-correlation function and the structure function are independent of temperature but the dynamics is slower at low temperature. A crossover between interfacial diffusion and bulk diffusion mechanisms is observed in the behavior of the characteristic domain size. This effect is explained theoretically in terms of an equation of motion for the interface.
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We study the interfacial modes of a driven diffusive model under suitable nonequilibrium conditions leading to possible instability. The external field parallel to the interface, which sets up a steady-state parallel flux, enhances the growth or decay rates of the interfacial modes. More dramatically, asymmetry in the model can introduce an oscillatory component into the interfacial dispersion relation. In certain circumstances, the applied field behaves as a singular perturbation.
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We show that, at high densities, fully variational solutions of solidlike types can be obtained from a density functional formalism originally designed for liquid 4He . Motivated by this finding, we propose an extension of the method that accurately describes the solid phase and the freezing transition of liquid 4He at zero temperature. The density profile of the interface between liquid and the (0001) surface of the 4He crystal is also investigated, and its surface energy evaluated. The interfacial tension is found to be in semiquantitative agreement with experiments and with other microscopic calculations. This opens the possibility to use unbiased density functional (DF) methods to study highly nonhomogeneous systems, like 4He interacting with strongly attractive impurities and/or substrates, or the nucleation of the solid phase in the metastable liquid.
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We investigate adsorption of helium in nanoscopic polygonal pores at zero temperature using a finite-range density functional theory. The adsorption potential is computed by means of a technique denoted as the elementary source method. We analyze a rhombic pore with Cs walls, where we show the existence of multiple interfacial configurations at some linear densities, which correspond to metastable states. Shape transitions and hysterectic loops appear in patterns which are richer and more complex than in a cylindrical tube with the same transverse area.