High specific surface area LaFeCo perovskites-Synthesis by nanocasting and catalytic behavior in the reduction of NO with CO

LaFe(1-x)CO(x)O(3) perovskites were conventionally or nanocasting synthesized. The nanocasting involved the preparation of a micro-mesoporous carbon mould using a Silica Aerosil 200 and a carbon source. Then, perovskites were carbon cast at 800 degrees C. The solids were characterized by XRD, N(2) sorption, FTIR, TGA/DTG, SEM and TEM. N(2) sorption evidenced that the nanocast perovskites did not show significant intraparticle porosity in despite of their enhanced (30-50 m(2)/g) specific surface area (SSA). Nevertheless, TEM images, XRD and Rietveld refinement data showed that the solids are constituted at least by 97 wt% of perovskite phase and by agglomerates smaller than 100 nm constituted by crystallites of about 6 nm. TGA/DTG results demonstrated carbon oxidation during the perovskite formation, thus eliminating the template effect and facilitating the occurrence of sintering, which limited the SSA increase. The nanocast perovskites were more active in the reduction of NO than the uncast ones, behavior that was attributed to the increase in their SSA that allows the exposure of a higher number of accessible active sites. However, the perovskite composition and the presence of impurities can reduce the effect of the improvement of the textural properties. The nanocast perovskites also showed high thermal and catalytic stability, corroborating their potential as catalysts for the studied reaction. (C) 2009 Elsevier B.V. All rights reserved.

Surface-enhanced Raman study of electrochemical and photocatalytic degradation of the azo dye Janus Green B

The photocatalytic degradation of Janus Green B azo dye over silver modified titanium dioxide films was investigated by surface-enhanced Raman spectroscopy (SERS). An optimized SERS-active substrate was employed to study the photodegradation reaction of Janus Green B. Considering that photocatalytic degradation processes of organic molecules adsorbed on TiO2 might involve either their oxidation or reduction reaction, the vibrational spectroelectrochemical study of the dye was also performed, in order to clarify the transformations involved in initial steps of its photochemical decomposition. In order to understand the changes in Raman spectra of Janus Green B after photodegradation and/or electrochemical processes, a vibrational assignment of the main Raman active modes of the dye was carried out, based on a detailed resonance Raman profile. Products formed by electrochemical and photochemical degradation processes were compared. The obtained results revealed that the first steps of the degradation process of Janus Green B involve a reductive mechanism. (C) 2007 Published by Elsevier B.V.

Surface-enhanced Raman scattering study of alizarin red S

This paper presents the application of surface-enhanced resonance Raman spectroscopy (SERRS) for the structural study of alizarin red S (ARS) and the nature of its interaction with silver nanoparticles. SERRS data for ARS over nanostructured silver electrodes suggest a surface-induced reaction of the adsorbed dye and the formation of an ion stabilized by the dye and alkali ions adsorbed at the metal surface. We found that precoating the SERS active substrate with 1-propanethiol inhibits the surface-induced modification of ARS. In addition to preventing structural modifications of ARS, the coating also concentrates the hydrophobic dye close enough to the SERS active interface enabling the observation of excellent Raman spectra of ARS in aqueous environment at ppm levels. The influence of resonance Raman effect and of the pH on the SERS spectra of ARS was also investigated. (C) 2010 Elsevier B.V. All rights reserved.

Electrochemical Control of the Time-Dependent Intensity Fluctuations in Surface-Enhanced Raman Scattering (SERS)

Time-dependent fluctuations in surface-enhanced Raman scattering (SERS) intensities were recorded from a roughened silver electrode immersed in diluted solutions of rhodamine 6G (R6G) and congo red (CR). These fluctuations were attributed to a small number of SERS-active molecules probing regions of extremely high electromagnetic field (hot spots) at the nanostructured surface. The time-dependent distribution of SERS intensities followed a tailed statistics at certain applied potentials, which has been linked to single-molecule dynamics. The shape of the distribution was reversibly tuned by the applied voltage. Mixtures of both dyes, R6G and CR, at low concentrations were also investigated. Since R6G is a cationic dye and CR is an anionic dye, the statistics of the SERS intensity distribution of either dye in a mixture were independently controlled by adjusting the applied potential. The potential-controlled distribution of SERS intensities was interpreted by considering the modulation of the surface coverage of the adsorbed dye by the interfacial electric field. This interpretation was supported by a two-dimensional Monte Carlo simulation that took into account the time evolution of the surface configuration of the adsorbed species and their probability to populate a hypothetical hot spot. The potential-controlled SERS dynamics reported here is a first step toward the spectroelectrochemical investigation of redox processes at the single-molecule level by SERS.

A surface-enhanced infrared absorption spectroscopic (SEIRAS) study of the oscillatory electro-oxidation of methanol on platinum

The oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems. (C) 2010 Elsevier B.V. All rights reserved.

Surface-enhanced raman scattering: metal nanostructures coated with langmuir-blodgett films

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

Preoperative warming combined with intraoperative skin-surface warming does not avoid hypothermia caused by spinal anesthesia in patients with midazolam premedication

CONTEXTO E OBJETIVO: Hipotermia inadvertida no perioperatório é freqüente durante anestesia subaracnóidea e após a administração de midazolam. O objetivo foi avaliar os efeitos do aquecimento da pele no intra-operatório, associado ou não ao aquecimento da pele durante o período de 45 minutos no pré-operatório, na prevenção de hipotermia intra- e pós-operatória determinada pela anestesia subaracnóidea em pacientes com medicação pré-anestésica com midazolam. TIPO DE ETUDO E LOCAL: Estudo prospectivo e aleatório, realizado no Hospital das Clínicas, Universidade Estadual Paulista (Unesp), Botucatu, SP. MÉTODOS: O estudo foi realizado em 30 pacientes com estado físico ASA (da Sociedade Norte-americana de Anestesiologistas) I e II submetidos à cirurgia eletiva do abdômen. Como medicação pré-anestésica, utilizou-se o midazolam, 7,5 mg via intramuscular (IM) e anestesia subaracnóidea padrão. em 10 pacientes (Gcontrole) utilizou-se isolamento térmico passivo; 10 pacientes (Gpré+intra) foram submetidos a aquecimento ativo no pré- e intra-operatório; e 10 pacientes (Gintra) foram aquecidos ativamente somente no intra-operatório. RESULTADOS: Após 45 minutos de aquecimento no pré-operatório, os pacientes do Gpré+intra apresentaram temperatura central mais elevada em relação aos dos grupos não aquecidos antes da anestesia (p < 0,05) mas não no início da cirurgia (p > 0,05). Os pacientes que receberam aquecimento no intra-operatório apresentaram temperatura central mais elevada no final da cirurgia em relação aos de Gcontrole (p < 0,05). Todos os pacientes estavam hipotérmicos na admissão da sala de recuperação pós-anestésica (temperatura central < 36º C). CONCLUSÕES: 45 minutos de aquecimento no pré-operatório combinado com aquecimento no intra- operatório não evita, mas minimiza a ocorrência de hipotermia determinada pela anestesia subaracnóidea em pacientes que receberam midazolam como medicação pré-anestésica.

Effects of Surface Hydration and Application Method on the Bond Strength of Self-Etching Adhesives to Dentin

The effect of application methods and dentin hydration on the bond strength of three self-etching adhesives (SEA) were evaluated; 195 extracted bovine incisors were used. The buccal surface was ground in order to expose the dentin, which remained 2-mm minimum thickness, measured by a thickness meter through an opening on the lingual surface. Adper Single Bond 2 (TM) was used for the control group. The SEA were applied following two modes of application: passive or active and two hydration states of the dentin surface-dry and wet. After light-curing, composite buildups were made using Grandio (TM) composite. The specimens were sectioned and tested with a microtensile bond strength test. The application method and the hydration state resulted in statistical differences (p = 0.000) making the values of active application for mu TBS to dentin higher than passive application. The wet surfaces showed higher mu TBS to dentin ratios than dry surfaces. There were no statistical differences in mu TBS among the SEA tested but there were differences regarding to control group.

Effects of Surface Hydration State and Application Method on the Bond Strength of Self-etching Adhesives to Cut Enamel

Purpose: To evaluate the effect of surface hydration state and application method on the microtensile bond strength of one-step self-etching adhesives systems to cut enamel.Materials and Methods: One hundred ninety-five bovine teeth were used. The enamel on the buccal side was flattened with 600-grit SiC paper. For the control group, 15 teeth received Adper Single Bond 2, applied according to manufacturer's recommendations. The other specimens were divided into three groups according to the adhesive system used: Futura Bond M (FM; Voco), Clearfil S-3 Bond (CS; Kuraray), and Optibond All in One (OA; Kerr). For each group, two hydration states were tested: D: blown dry with air; W: the excess of water was removed with absorbent paper. Two application methods were tested: P (passive): the adhesive was simply left on the surface; A (active): the adhesive was rubbed with an applicator point. A coat of Grandio composite resin (Voco) was applied on the surface. The teeth were sectioned to obtain enamel-resin sticks (1 x 1 mm), which underwent microtensile bond testing. The data in MPa were submitted to a three-way ANOVA and Tukey's test (alpha = 5%).Results: The ANOVA showed significant differences for application method and the type of adhesive, but not for hydration state. For the application method, the results of Tukey's test were: P: 31.46 (+/-7.09)a; A: 34.04 (+/-7.19)b. For the type of adhesive, the results were: OA: 31.29 (+/-7.05)a; CS: 32.28 (+/-7.14)a; FM: 34.68 (+/-7.17)b; different lower-case letters indicate statistically significant differences.Conclusion: Active application improved the bond strength to cut enamel. The adhesive Futurabond M showed the highest bond strength to cut enamel.

Evaluation of the photoelectrocatalytic method for oxidizing chloride and simultaneous removal of microcystin toxins in surface waters

The production of chlorine was investigated in the photoelectrocatalytic oxidation of a chloride-containing solution using a TiO(2) thin-film electrode biased at current density from 5 to 50 mA cm(-2) and illuminated by UV light. Such parameters as chloride concentrations from 0.001 to 0.10 mol L(-1), pH 2-12, and interfering salts were varied in this study in order to determine their effect on this oxidation process. At an optimum condition this photoelectrocatalytic method can produce active chlorine at levels compatible to water disinfections processes using a chloride concentration higher than 0.010 mol L(-1) at a pH of 4 and a current density of 30 mA cm(-2). The method was successfully applied to treat surface water collected from a Brazilian river. After 150 min of photoelectrocatalytic oxidation, we obtained a 90% reduction in total organic carbon removal, a 100% removal of turbidity, a 93% decrease in colour and a chemical oxygen demand (COD) removal of around 96% (N=3). The proposed technology based on photoelectrocatalytic oxidation was also tested in treating 250 mL of a solution containing 0.05 mol L(-1) NaCl and 50 mu g L(-1) of Microcystin aeruginosa. The bacteria is completely removed after 5 min of photoelectrocatalysis following an initial rate constant removal of -0.260 min(-1), suggesting that the present method could be considered as a promising alternative to chlorine-based disinfections. (C) 2008 Elsevier Ltd. All rights reserved.

Structural and surface properties of thermally prepared Ti/RhxTi(1-x)Oy electrodes: I - influence of preparation parameters

Electrodes of RhxTi(1-x) O-y nominal composition were prepared by thermal decomposition of the chloride or nitrate precursor salts dissolved in strongly acidic medium and applied by brush to both sides of a Tidegrees support. A systematic study of the influence of calcination temperature and time as well as oxygen flux was conducted. The coatings were characterised by SEM, EDAX, XRD, open circuit potential measurements and cyclic voltammetry (CV). Visible-ultraviolet spectrophotometry was employed to identify the chemical form of the precursor in solution while thermogravimetric analysis (TGA) was used to assess the decomposition temperature ranges. Optimisation of the coating preparation parameters showed coatings obtained from [Rh(H2O)(6)](NO3)(3) precursor dissolved in HNO3 1:2 (v/v) and fired at 430 degreesC for 2 h in a 5 1 min (-1) oxygen stream-furnished stable electrodes having the highest electrochemically active surface area. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Chemical structure, surface properties and biological activities of the biosurfactant produced by Pseudomonas aeruginosa LBI from soapstock

Pseudomonas aeruginosa LBI isolated from petroleum-contaminated soil produced rhamnolipids (RLLBI) when cultivated on soapstock as the sole carbon source. HPLC-MS analysis of the purified culture supernatant identified 6 RL homologues (%): R-2 C-10 C-10 28.9; R-2 C-10 C-12:1 23.0; R-1 C-10 C-10 23.4; R-2 C-10 C-12 11.3; R-2 C-10 C-12 7.9; R-2 C-10 C-12 C-12 5.5. To assess the potential antimicrobial activity of the new rhamnolipid product, RLLBI, its physicochemical properties were studied. RLLBI had a surface tension of 24 mN m(-1) and an interfacial tension 1.31 mN m(-1); the cmc was 120 mg l(-1). RLLBI produced stable emulsions with hydrocarbons and vegetable oils. This product showed good antimicrobial behaviour against bacteria: MIC for Bacillus subtilis, Staphylococcus aureus and Proteus vulgaris was 8 mg l(-1), for Streptococcus faecalis 4 mg l(-1), and for Pseudomonas aeruginosa 32 mg l(-1). RLLBI was active against phytopathogenic fungal species, MIC values of 32 mg l(-1) being found against Penicillium, Alternaria, Gliocadium virens and Chaetonium globosum. Due to its physicochemical properties and antimicrobial behaviour, RLLBI could be used in bioremediation treatment and in the food, cosmetic and pharmaceutical industries.

Active planar waveguides based on sol-gel Er3+-doped SiO2-ZrO2 for photonic applications: Morphological, structural and optical properties

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

Capacitance Spectroscopy: A Versatile Approach To Resolving the Redox Density of States and Kinetics in Redox-Active Self-Assembled Monolayers

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

Preoperative combined with intraoperative skin-surface warming avoids hypothermia caused by general anesthesia and surgery

Study Objectives: To evaluate the effects of intraoperative skin-surface warming with and without 1 hour of preoperative warming, in preventing intraoperative hypothermia, and postoperative hypothermia, and shivering, and in offering good conditions to early tracheal extubation. Design: Prospective, randomized, blind study. Setting: Teaching hospital. Patients: 30 ASA physical status I and II female patients scheduled for elective abdominal surgery. Interventions: Patients received standard general anesthesia. In 10 patients, no special precautions were taken to avoid hypothermia. Ten patients were submitted to preoperative and intraoperative active warming. Ten patients were only warmed intraoperatively. Measurements and Main Results: Temperatures were recorded at 15-minute intervals. The patients who were warmed preoperatively and intraoperatively had core temperatures significantly more elevated than the other patients during the first two hours of anesthesia. All patients warmed intraoperatively were normothermic only at the end of the surgery. The majority of the patients warmed preoperatively and intraoperatively or intraoperatively only were extubated early, and none had shivering. In contrast, five unwarmed patients shivered. Conclusions: One hour of preoperative warning combined with intraoperative skin-surface warming, not simply intraoperative warming alone, avoided hypothermia caused by general anesthesia during the first two hours of surgery. Both methods prevented postoperative hypothermia and shivering and offered good conditions for early tracheal extubation. © 2003 by Elsevier B.V.