Electroactive LbL films of metallic phthalocyanines and poly(O-methoxyaniline) for sensing

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.

Preparation, characterization and taste sensing properties of Langmuir-Blodgett Films from mixtures of polyaniline and a ruthenium complex

Langmuir-Blodgett (LB) films from a ruthenium complex, mer-[RuCl3(dppb)(py)] (dppb = PPh2(CH2)(4)PPh2; py = pyridine) (Rupy), and from mixtures with varied amounts of polyaniline (PANi) were fabricated. Molecular-level interactions between the two components are investigated by surface potential, dc conductivity and Raman spectroscopy measurements, particularly for the mixed film with 10% of Rupy. For the latter, the better miscibility led to an interaction with Rupy inducing a decrease in the conducting state of PANi, as observed in the Raman spectra and conductivity measurement. The interaction causes the final film properties to depend on the concentration of Rupy, and this was exploited to produce a sensor array made up of sensing units consisting of 11-layer LB films from pure PANi, pure Rupy and mixtures with 10 and 30% of Rupy. It is shown that the combination of only four non-specific sensing units allows one to distinguish the basic tastes detected by biological systems, viz. saltiness, sweetness, sourness and bitterness, at the muM level. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Nanostructured films employed as sensing units in an electronic tongue system

Nanostructured films of lignin (macromolecule extracted from sugar cane bagasse), polypyrrole (conducting polymer) and bis butylimido perylene (organic dye) were used in the detection of trace levels of fluorine (from H2SiF6), chlorine (from NaCIO), Pb+2, Cu+2, and Cd+2 in aqueous solutions. Langmuir monolayers on ultrapure water were characterised by surface pressure-mean molecular area (II-A) isotherms. Langmuir-Blodgett (LB) films were transferred onto gold interdigitated electrodes and used as individual sensing units of an electronic tongue system. Impedance spectroscopy measurements were taken with the sensor immersed into aqueous solutions containing the ions described above in different molar concentrations. Fourier transform infrared absorption (FTIR) was employed to identify possible interactions between the LB films and the analytes in solution, and no significant changes could be observed in the FTIR spectra of BuPTCD and Ppy. Therefore, the results for lignin point to an interaction involving the electronic cloud of the phenyl groups with the metallic ions.

Characterization of ZnO-degraded varistors used in high-tension devices

The effects of the degradation process on the structural, microstructural and electrical properties of ZnO-based varistors were analyzed. Rietveld refinement showed that the BiO2-x phase is affected by the degradation process. Besides the changes in the spinel phase, the degradation process also affects the lattice microstrain in the ZnO phase. Scanning electron microscopy analysis showed electrode-melting failure, while wavelength dispersive X-ray spectroscopy qualitative analysis showed deficiency of oxygen species at the grain boundaries in the degraded samples. Atomic force microscopy using electrostatic mode force illustrated a decrease in the charge density at the grain boundaries of the degraded sample. Transmission electron microscopy showed submicrometric spinel grains embedded in a ZnO matrix, but their average grain size is smaller in the degraded sample than in the standard one. Long pulses appeared to be more harmful for the varistors' properties than short ones, causing higher leakage current values. The electrical characteristics of the degraded sample are partially restored after heat treatment in an oxygen-rich atmosphere. (C) 2006 Elsevier Ltd. All rights reserved.

A study of habitat fragmentation in Southeastern Brazil using remote sensing and geographic information systems (GIS)

The purpose of this work was to study fragmentation of forest formations (mesophytic forest, riparian woodland and savannah vegetation (cerrado)) in a 15,774-ha study area located in the Municipal District of Botucatu in Southeastern Brazil (São Paulo State). A land use and land cover map was made from a color composition of a Landsat-5 thematic mapper (TM) image. The edge effect caused by habitat fragmentation was assessed by overlaying, on a geographic information system (GIS), the land use and land cover data with the spectral ratio. The degree of habitat fragmentation was analyzed by deriving: 1. mean patch area and perimeter; 2. patch number and density; 3. perimeter-area ratio, fractal dimension (D), and shape diversity index (SI); and 4. distance between patches and dispersion index (R). In addition, the following relationships were modeled: 1. distribution of natural vegetation patch sizes; 2. perimeter-area relationship and the number and area of natural vegetation patches; 3. edge effect caused by habitat fragmentation, the values of R indicated that savannah patches (R = 0.86) were aggregated while patches of natural vegetation as a whole (R = 1.02) were randomly dispersed in the landscape. There was a high frequency of small patches in the landscape whereas large patches were rare. In the perimeter-area relationship, there was no sign of scale distinction in the patch shapes, In the patch number-landscape area relationship, D, though apparently scale-dependent, tends to be constant as area increases. This phenomenon was correlated with the tendency to reach a constant density as the working scale was increased, on the edge effect analysis, the edge-center distance was properly estimated by a model in which the edge-center distance was considered a function of the to;al patch area and the SI. (C) 1997 Elsevier B.V. B.V.

Fabrication of novel light-emitting devices based on green-phosphor/conductive-polymer composites

We report on light-emitting devices based on a green-phosphor compound (Mn-doped zinc silicate, Zn2SiO4: Mn) dispersed in a conductive polymeric blend (poly-o-methoxyaniline/polyvinylene fluoride, POMA/PVDF-TrFE). The devices exhibited high luminance in the green, good stability and homogeneous brilliance over effective areas up to 5 cm(2). The electroluminescence (EL) spectrum presented essentially the same characteristics as the photoluminescence (PL) and cathodoluminescence spectra, indicating that the light emission originates from decay of the same excited species, regardless of the excitation source. Operating characteristics were analyzed with current density - voltage (J - V) and luminance voltage ( L - V) curves to investigate the nature of the electroluminescence of the active material, which is still not completely understood.

Nanoscale processing of polyaniline and phthalocyanines for sensing applications

Nanostructured polyaniline-modified electrodes were fabricated via the electrostatic layer-by-layer (LbL) technique where polyaniline (PANI) was assembled with one of three tetrasulfonated metallic phthalocyanines, viz. iron (FeTsPc), nickel (NiTsPc) and copper (CuTsPc). The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the 800 run absorption band due to PANI. Infrared spectroscopy in the transmission mode suggested specific interactions between PANI and the phthalocyanines, such as those between SO3- groups from the phthalocyanines and the protonated NH group from PANI. The films were employed to detect dopamine (DA) using cyclic voltammetry. In the presence of dopamine the PANI-based LbL films showed additional redox peaks at ca. 230 and 190 mV the oxidation peak increased linearly with the concentration of DA in the electrolytic solution. Films comprising PANI/FeTsPc were able to distinguish between DA and ascorbic acid (AA), which acts as a natural interferent in biological fluids. (c) 2005 Elsevier B.V. All rights reserved.

Qualitative evaluation of active potential barriers in SnO2-based polycrystalline devices by electrostatic force microscopy

This paper discuss the qualitative use of electrostatic force microscopy to study the grain boundary active potential barrier present in dense SnO2-based polycrystalline semiconductors. The effect of heat treatment under rich- and poor-oxygen atmospheres was evaluated while especially considering the number of active barriers at grain boundary regions. The results show that the number of active barriers decrease after heat treatment in an oxygen-poor atmosphere and increase after heat treatment in oxygen-rich atmospheres. The observed effect was explained by considering the presence of oxidized transition metal elements segregated at grain boundary regions which leads to the p-type character of this region, in agreement with the atomic barrier formation mechanism in metal oxide varistor systems.

PROLACTIN INDUCES MATURATION OF GLUCOSE SENSING MECHANISMS IN CULTURED NEONATAL RAT ISLETS

The effects of PRL treatment on insulin content and secretion, and Rb-86 and Ca-45 fluxes from neonatal rat islets maintained in culture for 7-9 days were studied. PRL treatment enhanced islet insulin content by 40% and enhanced early insulin secretion evoked by 16.7 mm glucose. Insulin release stimulated by oxotremorine-M, a muscarinic agonist, in the presence of glucose (8.3 or 16.7 mm) was unchanged by PRL treatment. However, PRL treatment potentiated phorbol 12,13-dibutyrate-stimulated insulin secretion in the presence of the above glucose concentrations. PRL treatment potentiated the reduction in Rb-86 efflux induced by glucose or tolbutamide and enhanced the increase in Rb-86 efflux evoked by diazoxide. PRL treatment slightly potentiated the increment in Ca-45 uptake induced by high concentrations of K+, but failed to affect the increment evoked by 16.7 mm glucose. Since glucose-induced Ca-45 uptake was not affected by PRL, we suggest that the enhancement in first phase insulin secretion evoked by glucose in the PRL-treated islets occurs at a step in the secretory process that may involve protein kinase-C. These data further support observations that PRL treatment increases islet sensitivity to glucose.

Remote sensing techniques applied to slope failure analysis

The paper evaluates the applicability of products of remote sensing in studies related to the structural conditionings of slope stability in saprolites, usually conducted through field surveys. In this article we use a regional approach concentrating on an area of lane duplication of a major highway. In that area, resistance reduction to stress and the low cohesions of muscovite saprolites - schists and gneiss which are associated to geological discontinuities, all result in inumerous instabilities. The joints and foliations were extracted from satellite images as well as aerial photographs. Following that, the study area was divided into various sectors based on the directions and dips of the foliation. Different relationships between the structures and the slopes were analyzed in order to indicate the most feasible type of slope failure in each sector of analysis. The aim of the study is to subsidize further detailed future research.

The failure analyses on ZnO varistors used in high tension devices

The main purpose of this work is to evaluate the failure caused by electrical discharge on commercial ZnO varistor doped with oxide of Bi, Sb, Si, Cr, Co utilized in electric transmission systems. In order to observe the effect of electrical discharge over the microstructure and electrical properties of the varistors, two kinds of pulses were applied: long pulse (2000 ms) and short pulse (8/20 mu s). In both cases, a decrease in grain size and increase in micropores and leakage current were observed. The degraded samples present oxygen defficiency mainly in the grain boundary and phase tranformation from the bismuth oxide phase. (c) 2005 Springer Science+ Business Media, Inc.

An ultra stable glass system for optical fiber devices

In this paper a modified chalcogenide glass was studied by X-ray powder diffraction, differential thermal analysis, infrared and Raman scattering spectroscopies. The study of this new matrix opens new perspectives to fabricate Pr3+-doped fibers to operate as an optical amplifier in the 1.3 mum telecommunications window. The Pr3+-doped 70Ga(2)S(3)-30La(2)S(3) glass was modified through the substitution of La2S3 by La2O3, which improves the thermal stability of these glasses without any modification of phonon energy. The possibility to pull a fiber from this glass system without any devitrification is easily achieved.

Natural gum-assisted phthalocyanine immobilization in electroactive nanocomposites: Physicochemical characterization and sensing applications

Natural gums have been traditionally applied in cosmetics and the food industry, mainly as emulsification agents. Due to their biodegradability and excellent mechanical properties, new technological applications have been proposed involving their use with conventional polymers forming blends and composites. In this study, we take advantage of the polyelectrolyte character exhibited by the natural gum Chicha (Sterculia striata), extracted in the Northeastern region of Brazil, to produce electroactive nanocomposites. The nanocomposites were fabricated in the form of ultrathin films by combining a metallic phthalocyanine (nickel tetrasulfonated phthalocyanine, NiTsPc) and the Chicha gum in a tetralayer architecture, in conjunction with conventional polyelectrolytes. The presence of the gum led to an efficient adsorption of the phthalocyanine and enhanced the electrochemical response of the films. Upon combining the electrochemical and UV-vis absorption data, energy diagrams of the Chicha/NiTsPc-based system were obtained. Furthermore, modified electrodes based on gum/phthalocyanine films were able to detect dopamine at concentrations as low as 10(-5) M.

Immobilization of humic acid in nanostructured layer-by-layer films for sensing applications

Humic acids (HAs), naturally occurring biomacromolecules, were incorporated into nanostructured polymeric films using the layer-by-layer (LbL) technique, in which HA layers were alternated with layers of poly(allylamine hydrochloride) (PAH). Atomic force microscopy (AFM) revealed very smooth films, with mean roughness varying from 0.89 to 1.19 nm for films containing 5 and 15 PAH/HA bilayers, respectively. The films displayed electroactivity, with the presence of only one reduction peak at ca. 0.675 V (vs Ag/AgCl). Such a well-defined electroactivity allowed the films to be used as highly sensitive pesticide sensors, with detection of pentachlorophenol (PCP) in solutions at concentrations as low as 10(-9) mol L(-1).