A novel hybrid composite formed by reaction of 4,5-diphenyl-2-imidazolethiol with hexacyanoferrate (iii) and subsequent reaction with copper (ii): preparation, characterization and a voltammetric application for determination of l-glutatione

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of different finishing and polishing techniques on the surface roughness of microfilled, hybrid and packable composite resins

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of hybridizing micron-sized Ti with nano-sized SiC on the microstructural evolution and mechanical response of Mg-5.6Ti composite

In this work, the effect of hybridizing micro-Ti with nano-SiC particulates on the microstructural and the mechanical behaviour of Mg-5.6Ti composite were investigated. Mg materials containing micron-sized Ti particulates hybridized with different amounts of nano-size SiC particulates were synthesized using the disintegrated melt deposition method followed by hot extrusion. The microstructural and mechanical behaviour of the developed Mg hybrid composites were studied in comparison with Mg-5.6Ti. Microstructural characterization revealed grain refinement attributed to the presence of uniformly distributed micro-Ti particles embedded with nano-SiC particulates. Electron back scattered diffraction (EBSD) analyses of Mg-(5.6Ti + 1.0SiC)(BM) hybrid composite showed relatively more localized recrystallized grains and lesser tensile twin fraction, when compared to Mg-5.6Ti. The evaluation of mechanical properties indicated that the best combination of strength and ductility was observed in the Mg-(5.6Ti + 1.0SiC)(BM) hybrid composites. The superior strength properties of the Mg-(5.6Ti + x-SiC)(BM) hybrid composites when compared to Mg-5.6Ti is attributed to the presence of nano-reinforcements, the uniform distribution of the hybridized particles and the better interfacial bonding between the matrix and the reinforcement particles, achieved by nano-SiC addition.

Antimicrobial and conducting polymer substrate derived from hybrid structures of silver nanoparticles and multiwall carbon nanotubes

Hybrid nanocomposites of polycaprolactone (PCL) with multiwall carbon nanotubes (MWNTs) and silver nanoparticles (nAg) were prepared by melt mixing. Synergetic effect of the two nanofillers (MWNT and nAg) in PCL matrix was evaluated for dielectric and antibacterial properties. Dielectric results showed that the addition of nAg as filler in PCL matrix (PCL/nAg) had no effect on conductivity, whereas addition of MWNT in PCL matrix (PCL/MWNT) caused a sharp increase in conductivity of PCL. Interestingly, the hybrid nanocomposite (PCL/MWNT/nAg) incorporating MWNT and nAg also exhibited high electrical conductivity. The hybrid composite was found to have antibacterial property similar to that of PCL/nAg composite for lower loading of nAg. This study demonstrates that the synergetic interaction of the nanofillers in the hybrid nanocomposite improves both electrical conductivity and antibacterial properties of PCL.

Bioorganic/inorganic hybrid composition of sponge spicules: Matrix of the giant spicules and of the comitalia of the deep sea hexactinellid Monorhaphis

The giant basal spicules of the siliceous sponges Monorhaphis chuni and Monorhaphis intermedia (Hexactinellida) represent the largest biosilica structures on earth (up to 3 m long). Here we describe the construction (lamellar organization) of these spicules and of the comitalia and highlight their organic matrix in order to understand their mechanical properties. The spicules display three distinct regions built of biosilica: (i) the outer lamellar zone (radius: >300 mu m), (ii) the bulky axial cylinder (radius: <75 mu m), and (iii) the central axial canal (diameter: <2 mu m) with its organic axial filament. The spicules are loosely covered with a collagen net which is regularly perforated by 7-10 mu m large holes; the net can be silicified. The silica layers forming the lamellar zone are approximate to 5 mu m thick; the central axial cylinder appears to be composed of almost solid silica which becomes porous after etching with hydrofluoric acid (HF). Dissolution of a complete spicule discloses its complex structure with distinct lamellae in the outer zone (lamellar coating) and a more resistant central part (axial barrel). Rapidly after the release of the organic coating from the lamellar zone the protein layers disintegrate to form irregular clumps/aggregates. In contrast, the proteinaceous axial barrel, hidden in the siliceous axial cylinder, is set up by rope-like filaments. Biochemical analysis revealed that the (dominant) molecule of the lamellar coating is a 27-kDa protein which displays catalytic, proteolytic activity. High resolution electron microscopic analysis showed that this protein is arranged within the lamellae and stabilizes these surfaces by palisade-like pillars. The mechanical behavior of the spicules was analyzed by a 3-point bending assay, coupled with scanning electron microscopy. The load-extension curve of the spicule shows a biphasic breakage/cracking pattern. The outer lamellar zone cracks in several distinct steps showing high resistance in concert with comparably low elasticity, while the axial cylinder breaks with high elasticity and lower stiffness. The complex bioorganic/inorganic hybrid composition and structure of the Monorhaphis spicules might provide the blueprint for the synthesis of bio-inspired material, with unusual mechanical properties (strength, stiffness) without losing the exceptional properties of optical transmission. (C) 2007 Elsevier Inc. All rights reserved.

Synthesis, Characterization and Applications of Hybrid Nanocomposites of TiO2 With Conducting Polymers

A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material. In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Conducting polymers have attracted much attention due to high electrical conductivity, ease of preparation, good environmental stability and wide variety of applications in light-emitting, biosensor chemical sensor, separation membrane and electronic devices. The most widely studied conducting polymers are polypyrrole, polyaniline, polythiophene etc. Conducting polymers provide tremendous scope for tuning of their electrical conductivity from semiconducting to metallic region by way of doping and are organic electro chromic materials with chemically active surface. But they are chemically very sensitive and have poor mechanical properties and thus possessing a processibility problem. Nanomaterial shows the presence of more sites for surface reactivity, they possess good mechanical properties and good dispersant too. Thus nanocomposites formed by combining conducting polymers and inorganic oxide nanoparticles possess the good properties of both the constituents and thus enhanced their utility. The properties of such type of nanocomposite are strongly depending on concentration of nanomaterials to be added. Conducting polymer composites is some suitable composition of a conducting polymer with one or more inorganic nanoparticles so that their desirable properties are combined successfully. The composites of core shell metal oxide particles-conducting polymer combine the electrical properties of the polymer shell and the magnetic, optical, electrical or catalytic characteristics of the metal oxide core, which could greatly widen their applicability in the fields of catalysis, electronics and optics. Moreover nanocomposite material composed of conducting polymers & oxides have open more field of application such as drug delivery, conductive paints, rechargeable batteries, toners in photocopying, smart windows, etc.The present work is mainly focussed on the synthesis, characterization and various application studies of conducting polymer modified TiO2 nanocomposites. The conclusions of the present work are outlined below, Mesoporous TiO2 was prepared by the cationic surfactant P123 assisted hydrothermal synthesis route and conducting polymer modified TiO2 nanocomposites were also prepared via the same technique. All the prepared systems show XRD pattern corresponding to anatase phase of TiO2, which means that there is no phase change occurring even after conducting polymer modification. Raman spectroscopy gives supporting evidence for the XRD results. It also confirms the incorporation of the polymer. The mesoporous nature and surface area of the prepared samples were analysed by N2 adsorption desorption studies and the mesoporous ordering can be confirmed by low angle XRD measurementThe morphology of the prepared samples was obtained from both SEM & TEM. The elemental analysis of the samples was performed by EDX analysisThe hybrid composite formation is confirmed by FT-IR spectroscopy and X-ray photoelectron spectroscopyAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systemsAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systems Polyaniline modified TiO2 nanocomposite systems were found to have good antibacterial activity. Thermal diffusivity studies of the polyaniline modified systems were carried out using thermal lens technique. It is observed that as the amount of polyaniline in the composite increases the thermal diffusivity also increases. The prepared systems can be used as an excellent coolant in various industrial purposes. Nonlinear optical properties (3rd order nonlinearity) of the polyaniline modified systems were studied using Z scan technique. The prepared materials can be used for optical limiting Applications. Lasing studies of polyaniline modified TiO2 systems were carried out and the studies reveal that TiO2 - Polyaniline composite is a potential dye laser gain medium.

Promoted water transport across graphene oxide-poly(amide) thin film composite membranes and their antibacterial activity

Hybrid composite membranes have great potential for desalination applications since water transport can be favorably promoted by selective diffusion at the interface between matrix and reinforcement materials. In this paper, graphene oxide nano-sheets were successfully incorporated across 200nm thick poly(amide) films by interfacial polymerization to form novel thin-film composite membranes. The impact of the graphene oxide on the morphology, chemistry, and surface charge of the ultra-thin poly(amide) layer, and the ability to desalinate seawater was investigated. The graphene oxide nano-sheets were found to be well dispersed across the composite membranes, leading to a lower membrane surface energy and an enhanced hydrophilicity. The iso-electric point of the samples, key to surface charge repulsion during desalination, was found to be consistently shifted to higher pH values with an increasing graphene oxide content. Compared to a pristine poly(amide) membrane, the pure water flux across the composite membranes with 0.12wt.% of graphene oxide was also found to increase by up to 80% from 0.122 to 0.219L·μm·m-2·h-1·bar-1 without significantly affecting salt selectivity. Furthermore, the inhibitory effects of the composite membrane on microbial growth were evaluated and the novel composite membranes exhibited superior anti-microbial activity and may act as a potential anti-fouling membrane material.

Effect of light-curing units on microleakage under dental composite resins

The aim of this study was to determine the effect of two light-curing units (QTH and LED) on microleakage of Class II composite resin restorations with dentin cavosurface margins. Twenty extracted mandibular first premolars, free of caries and fractures were prepared two vertical slot cavities in the occluso-mesial and -destal surfaces (2 mm buccal-lingually, 2 mm proximal-axially and cervical limit in enamel) and divided into 4 equal groups (n = 8): GI and GII: packable posterior composite light-activated with LED and QTH, respectively; GIII and GIV: micro-hybrid composite resin light-activated with LED and QTH, respectively. The composite resins were applied following the manufacturer's instructions. After 24 h of water storage specimens were subjected to thermocycling for a total of 500 cycles at 5 and 55A degrees C and the teeth were then sealed with impermeable material. Teeth were immersed in 0.5% Basic fuchsin during 24 h at room temperature, and zero to three levels of penetration score were attributed. The Mann-Whitney and Kruskal-Wallis tests showed significant statistically similar (P > 0.05) from GI to GII and GIII to GIV, which the GII (2.750) had the highest mean scores and the GIII and GIV (0.875) had lowest mean scores. The use of different light-curing units has no influence on marginal integrity of Class II composite resin restorations and the proprieties of composite resins are important to reduce the microleakage.

Influence of beveling and ultrasound application on marginal adaptation of box-only Class II (slot) resin composite restorations

A laboratory study was performed to assess the influence of beveling the margins of cavities and the effects on marginal adaptation of the application of ultrasound during setting and initial light curing. After minimal access cavities had been prepared with an 80 microm diamond bur, 80 box-only Class II cavities were prepared mesially and distally in 40 extracted human molars using four different oscillating diamond coated instruments: (A) a U-shaped PCS insert as the non-beveled control (EMS), (B) Bevelshape (Intensiv), (C) SonicSys (KaVo) and (D) SuperPrep (KaVo). In groups B-D, the time taken for additional bevel finishing was measured. The cavities were filled with a hybrid composite material in three increments. Ultrasound was also applied to one cavity per tooth before and during initial light curing (10 seconds). The specimens were subjected to thermomechanical stress in a computer-controlled masticator device. Marginal quality was assessed by scanning electron microscopy and the results were compared statistically. The additional time required for finishing was B > D > C (p < or = 0.05). In all groups, thermomechanical loading resulted in a decrease in marginal quality. Beveling resulted in higher values for "continuous" margins compared with that of the unbeveled controls. The latter showed better marginal quality at the axial walls when ultrasound was used. Beveling seems essential for good marginal adaptation but requires more preparation time. The use of ultrasonic vibrations may improve the marginal quality of unbeveled fillings and warrants further investigation.

Síntese e caracterização de microesferas poliméricas reticuladas à base de poli(ácido metacrílico) contendo nanopartículas magnéticas de ferritas de manganês

As nanopartículas de ferritas de manganês (MnFe2O4) tem sido de grande interesse por causa de suas notáveis propriedades magnéticas doces (baixa coercividade e moderada magnetização de saturação) acompanhada com boa estabilidade química e dureza mecânica. A formação de materiais híbridos/compósito estabiliza as nanopartículas magnéticas (NPMs) e gera funcionalidades aos materiais. Entretanto, não foi encontrada na literatura uma discussão sobre a síntese e as propriedades de polímeros polares reticulados à base de ácido metacrílico contendo ferritas de manganês na matriz polimérica. Assim, o objetivo desta Dissertação foi produzir partículas esféricas poliméricas reticuladas, com boas propriedades magnéticas, à base de ácido metacrílico, estireno, divinilbenzeno e ferritas de manganês. Neste trabalho, foram sintetizados compósitos de ferrita de manganês (MnFe2O4) dispersa em copolímeros de poli(ácido-metacrílico-co-estireno-co-divinilbenzeno), via polimerização em suspensão e em semi-suspensão. Foram variados os teores de ferrita (1% e 5%) e a concentração do agente de suspensão (0,2% e 5%). Além disso, foram testadas sínteses contendo a fase orgânica pré-polimerizada, e também a mistura da ferrita na fase orgânica (FO), antes da etapa da polimerização em suspensão. Os copolímeros foram analisados quanto as suas morfologias - microscopia óptica; propriedades magnéticas e distribuição das ferritas na matriz polimérica - VSM, SEM e EDS-X; propriedades térmicas TGA; concentração de metais presentes na matriz polimérica absorção atômica. As ferritas foram avaliadas quanto à cristalografia XRD. A matriz polimérica foi avaliada pela técnica de FTIR. As amostras que foram pré-polimerizadas e as que além de pré-polimerizadas foram misturadas as ferritas de manganês na FO, apresentaram as melhores propriedades magnéticas e uma incorporação maior da ferrita na matriz polimérica. Essas rotas sintéticas fizeram com que os copolímeros não apresentassem aglomeração, e também minimizou a presença de ferritas na superfície das microesferas. Em geral, todos os copolímeros obtidos apresentaram as características de materiais magneticamente doces além do superparamagnetismo. Foi constatado que o aumento da concentração do PVA e a diminuição da concentração da ferrita fazem com que os diâmetros das microesferas decresçam. Os resultados de TGA e DTG mostraram que ao misturar as ferritas na FO, a concentração de material magnético na matriz polimérica aumenta cerca de 10%. Entretanto, somente a amostra PM2550, pré-polimerizada e com as ferritas misturadas na FO (5% de ferrita e 0,2% de PVA), apresentou potencial aplicação. Isso porque as ferritas não ficaram expostas na superfície das microesferas, ou seja, o material magnético fica protegido de qualquer ação externa

Controlling dispersed state and exfoliation process of clay in polymer matrix

In the present review, the authors do not try to provide a comprehensive review of researches on polymer/clay nanocomposites (PCNs), but some examples to demonstrate different exfoliation processes of the clay in various polymer matrixes and the dispersed state of clay. Interaction between polymers and layered silicates plays an important role in adjusting the exfoliation process of layered silicates and the microstructure of polymer nanocomposites. Properties of polymer/layered silicate nanocomposites mainly depend on the dispersed state of layered silicates. The authors will also address the outline of the present research in the direction of PCNs including the discussion of technical problems and their possible solutions.

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.

Avaliação das propriedades mecânicas e microestrutura de um ionómero de vidro experimental reforçado com nano partículas

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

Maurice Sand, un créateur fantastique méconnu : la transversalité, brisant d’une œuvre au 19e siècle

Sauf par des regards fugitifs et distraits sur son travail d’illustrateur et son théâtre de marionnettes, l’histoire culturelle et littéraire n’a en général retenu de Maurice Sand que son état de fils bien-aimé de la plus célèbre écrivaine du 19e siècle. Étudiée pour elle-même, son œuvre multidisciplinaire - qui allie peinture, dessin, illustration, théâtre, histoire de l’art, sciences naturelles - se propose pourtant avec cohérence, marque d’une création soutenue plutôt que du dilettantisme où son souvenir s’est incrusté. Maurice Sand apparaît alors comme un de ces individus situés aux interstices des récits majeurs de la littérature et des arts qui, bien qu’ayant figure de minores, amènent à des réflexions nuancées sur la constitution de ces récits. Explorer son cas permet ainsi de scruter de plus près les mécanismes de la méconnaissance qui a pu et peut encore affecter un créateur et une œuvre soumis aux arbitrages mémoriels. Discrets angles morts de l’histoire, certains de ces mécanismes jalonnent clairement son parcours et les aléas de sa trace posthume. D’une part le vaste corpus des études sur George Sand, notamment des écrits biographiques et autobiographiques, fait voir à l’œuvre le mode déformant de la constitution de la mémoire d’un être saisi à partir des positions d’autrui : son existence devient cliché, elle se réduit peu à peu au rôle d’adjuvant dans des débats, passés ou actuels, qui font l’impasse sur le cours autonome de sa carrière, voire de sa vie. D’autre part la mise au jour de son œuvre, enfin vue comme un ensemble, dévoile une cause encore plus déterminante de sa méconnaissance. Presque tous les travaux de Maurice Sand sont traversés par une ligne de fantastique, au surplus connotée par son intérêt pour les sciences liées à la métamorphose, de l’ethnogénie à l’entomologie. Réinvention constante du passé, sa démarche cognitive et créatrice ignore les frontières disciplinaires, son objet est hybride et composé. L’œuvre se constitue ainsi par transversalité, trait et trame irrecevables en un siècle qui n’y perçut que dispersion, mais paradoxalement marque supérieure de qualité dans le champ éclaté où se déploient les arts de notre temps.