Quenching of Photoactivity in Phthalocyanine Copper(II)-Titanate Nanotube Hybrid Systems

Titanate nanotubes (TiNTs) were obtained by hydrothermal treatment of anatase powder in aqueous NaOH solution and then modified with 2,9,16,23-tertracarboxyl phthalocyanine copper(H) (CuPc). This hybrid organic inorganic nanoscopic system was characterized by X-ray diffraction, microscopy, and spectroscopy. Transmission electron microscopy (TEM) images of pure and modified TiNTs revealed multiwall structures with an average outer diameter of 9 nm and a length of several hundred nanometers. The tubular morphology of the TiNTs was covered with CuPc-film. The amount of CuPc adsorbed onto the TiNTs was quantified by electron paramagnetic resonance (EPR). Using the same technique and spin-trapping methodology, the photogeneration of reactive oxygen species (ROS) from the TiNTs was systematically investigated. A drastic quenching of photoactivity was observed in the CuPc/TiNT hybrid system. Electron transfer from excited CuPc states to the TiNT conduction band followed by electron recombination may be the cause of this quenching.

Detection of Paraquat in Oral Fluid, Plasma, and Urine by Capillary Electrophoresis for Diagnosis of Acute Poisoning

FAPESP

Raman spectra of acetonitrile in imidazolium ionic liquids

Raman spectra of dilute solutions of acetonitrile in ionic liquids reveal the characteristic features of ionic liquids` polarity. This is accomplished by investigating the Raman bandshape of the nu (CN) band, corresponding to the CN stretching mode of CH(3)CN, which is a very sensitive probe of the local environment. The amphiphilic nature of the CH(3)CN molecule allows us to observe the effect of electron pair acceptor and electron pair donor characteristics on ionic liquids. It has been found that the overall polarity of nine different ionic liquids based on 1-alkyl-3-methylimidazolium cations is more dependent on the anion than cation. The observed wavenumber shift of the nu (CN) band of CH(3)CN in ionic liquids containing alkylsulfate anions agrees with the significant different values previously measured for the dielectric constant of these ionic liquids. The conclusions obtained from the analysis of the nu (CN) band were corroborated by the analysis of the symmetric nu(1) (CD(3)) stretching mode of deuterated acetonitrile in different ionic liquids. Copyright (C) 2010 John Wiley & Sons, Ltd.

Photocatalytic degradation of methylene blue by TiO(2)-Cu thin films: Theoretical and experimental study

In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO(2) films were studied. TiO(2) films of about 200 nn thickness were deposited on glass substrates on which a thin Cu layer (5 nm) was deposited. The films were annealed during 1 s to 100 degrees C and 400 degrees C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31 nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO(2), Cu(2)O and Cu(0) phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet-visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations. (C) 2010 Elsevier B.V. All rights reserved.

Photocatalyst TiO(2)-Co: the effect of doping depth profile on methylene blue degradation

In this work, we study the effect of doping depth profile on the photocatalytic and surface properties of TiO(2) films. Two thin film layers of TiO(2) (200 nm) and Co (5 nm), respectively, were deposited by physical evaporation on glass substrate. These films were annealed for 1 s at 100 and 400 A degrees C and the Co layer was removed by chemical etching. Atomic force microscopy (AFM) phase images showed changes in the surface in function of thermal treatment. The grazing-incidence X-ray fluorescence (GIXRF) measurements indicated that the thermal treatment caused migration of Co atoms to below the surface, the depths found were between 19 and 29 nm. The contact angle showed distinct values in function of the doped profile or Co surface concentration. The UV-vis spectra presented a red shift with the increasing of thermal treatment. Photocatalytical assays were performed by methylene blue discoloration and the higher activity was found for TiO(2)-Co treated at 400 A degrees C, the ESI-MS showed the fragments formed during the methylene blue decomposition.

Development of a fast capillary electrophoresis method to determine inorganic cations in biodiesel samples

The aim of this study was to develop a fast capillary electrophoresis method for the determination of inorganic cations (Na(+), K(+), Ca(2+), Mg(2+)) in biodiesel samples, using barium (Ba(2+)) as the internal standard. The running electrolyte was optimized through effective mobility curves in order to select the co-ion and Peakmaster software was used to determine electromigration dispersion and buffer capacity. The optimum background electrolyte was composed of 10 mmol L(-1) imidazole and 40 mmol L(-1) of acetic acid. Separation was conducted in a fused-silica capillary (32 cm total length and 23.5 cm effective length, 50 mu m I.D.), with indirect UV detection at 214 nm. The migration time was only 36 s. In order to obtain the optimized conditions for extraction, a fractional factorial experimental design was used. The variables investigated were biodiesel mass, pH, extractant volume, agitation and sonication time. The optimum conditions were: biodiesel mass of 200 mg, extractant volume of 200 mu L. and agitation of 20 min. The method is characterized by good linearity in the concentration range of 0.5-20 mg kg(-1) (r > 0.999), limit of detection was equal to 0.3 mg kg(-1), inter-day precision was equal to 1.88% and recovery in the range of 88.0-120%. The developed method was successfully applied to the determination of cations in biodiesel samples. (c) 2010 Elsevier B.V. All rights reserved.

Development of a fast capillary electrophoresis method for the determination of propranolol-Total analysis time reduction strategies

The aim of this study was to develop a fast capillary electrophoresis method for the determination of propranolol in pharmaceutical preparations. In the method development the pH and constituents of the background electrolyte were selected using the effective mobility versus pH curves. Benzylamine was used as the internal standard. The background electrolyte was composed of 60 mmol L(-1) tris(hydroxymethyl)aminomethane and 30 mmol L(-1) 2-hydroxyisobutyric acid,at pH 8.1. Separation was conducted in a fused-silica capillary (32 cm total length and 8.5 cm effective length, 50 mu m I.D.) with a short-end injection configuration and direct UV detection at 214 nm. The run time was only 14 s. Three different strategies were studied in order to develop a fast CE method with low total analysis time for propranolol analysis: low flush time (Lflush) 35 runs/h, without flush (Wflush) 52 runs/h, and Invert (switched polarity) 45 runs/h. Since the three strategies developed are statistically equivalent, Mush was selected due to the higher analytical frequency in comparison with the other methods. A few figures of merit of the proposed method include: good linearity (R(2) > 0.9999); limit of detection of 0.5 mg L(-1): inter-day precision better than 1.03% (n = 9) and recovery in the range of 95.1-104.5%. (C) 2009 Elsevier B.V. All rights reserved.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Characterization and Identification of Proteolytic Bacteria From the Gut of the Velvetbean Caterpillar (Lepidoptera: Noctuidae)

The characterization and identification of proteolytic bacteria from the gut of the velvetbean caterpillar (Anticarsia gemmatalis) were the objectives of this study. Twelve aerobic and anaerobic isolates of proteolytic bacteria were obtained from the caterpillar gut in calcium caseinate agar. The number of colony forming units (CFUs) of proteolytic bacteria was higher when the bacteria were extracted from caterpillars reared on artificial diet rather than on soybean leaves (1.73 +/- 0.35 X 10(3) and 0.55 +/- 0.22 X 10(3) CFU/mg gut, respectively). The isolated bacteria were divided into five distinct groups, according to their polymerase chain reaction restriction fragment-length polymorphism profiles. After molecular analysis, biochemical tests and fatty acid profile determination, the bacteria were identified as Bacillus subtilis, Bacillus cereus, Enterococcus gallinarum, Enterococcus mundtii, and Staphylococcus xylosus. Bacterial proteolytic activity was assessed through in vitro colorimetric assays for (general) proteases, serine proteases, and cysteine proteases. The isolated bacteria were able of hydrolyzing all tested substrates, except Staphylococcus xylosus, which did not exhibit serine protease activity. This study provides support for the hypothesis that gut proteases from velvetbean caterpillar are not exclusively secreted by the insect cells but also by their symbiotic gut bacteria. The proteolytic activity from gut symbionts of the velvetbean caterpillar is suggestive of their potential role minimizing the potentially harmful consequences of protease inhibitors from some of this insect host plants, such as soybean, with implications for the management of this insect pest species.

Antifungal activity of tri- and tetra-thioureido amino derivatives against different Candida species

The in vitro antifungal activity of six thioureido substituted amines (P1-P6) was evaluated against Candida species, including Candida albicans, C. glabrata, C. krusei and C. parapsilosis. These tri- and tetra-thioureido amino derivatives with different methylation levels were synthesised through easy synthetic routes to evaluate their antifungal properties against Candida species. Among all studied derivatives, the tri-(2-thioureido-ethyl)-amine (P1) was the most active compound inhibiting C. albicans and C. glabrata at a concentration of 0.49 mu g ml(-1); P3, the N,N `,N ``,N ```-hexamethyl-derivative, also showed inhibitory activity against C. albicans and C. glabrata, but in higher concentrations (250 mu g ml(-1)). The N,N `,N ``,N ```-tetramethylated amine (P5) only inhibited the growth of C. glabrata, but its corresponding N,N `,N ``,N ```-octamethyl derivative (P6) was also active against C. glabrata (125 mu g ml(-1)) and it was the only compound active against C. parapsilosis. P2 and P4 showed no significant antifungal activity. The structure-activity relationship of the thioureido-substituted derivatives indicates that the molecular branching and the alkylation levels can influence the antifungal activity. This study demonstrated that thioureido derivatives exhibited significant antifungal activity against Candida species and that they can be considered as a very promising bioactive lead compound to develop novel antifungal agents.

Removal of Zn(2+) from Electroplating Wastewater Using Modified Wood Sawdust and Sugarcane Bagasse

This paper describes the preparation of new adsorbents derived from sugarcane bagasse and wood sawdust (Manilkara sp.) to remove zinc (II) ions from electroplating wastewater. The first part deals with the chemical modification of sugarcane bagasse and wood sawdust, using succinic anhydride to introduce carboxylic acid functions into the material. The obtained materials (modified sugarcane bagasse MB2 and modified wood sawdust MS2) were then characterized by infrared spectroscopy (IR) and used in adsorption experiments. The adsorption experiments evaluates Zn(2+) removal from aqueous single metal solution and real electroplating wastewater on both batch and continuous experiments using fixed-bed columns prepared in laboratorial scale with the obtained adsorbents. Adsorption isotherms were then developed using Langmuir model and the Thomas kinetic model. The calculated Zn(2+) adsorption capacities were found to be 145 mg/g for MS2 and 125 mg/g for MB2 in single metal aqueous solution, whereas for the industrial wastewater these values were 61 mg/g for MS2 and 55 mg/g for MB2.

O estilo gerencial do executivo público catarinense

The purpose of this study was make an utterance of the managerial style of the public executive from Santa Catarina and compare it with public executives from Minas Gerais and United States, considering their capacity in giving and receiving feedback and their opening or auto-expositions in the interrelations with subordinates. It began with a review of the literature about functions and managerial style from several contributions that exist in the theory of the organizations. The theoric countersignement used in this essay was stablished in “Johari’s Window”, of Luft, that brought the possibility of the analysis of the interpersonal relations, considering the feedback variants and opening. The research is descriptive and still comparative, being applied to public executives from Santa Catarina, between the occupants of the first and the second hierarchic rungs. The instrument used was the questionnaire “Personel Relations Surwey”, of John Hall and Martha Williams, the same was applied at the researches that had been made in Minas Gerais and in United States. It was evident, by the statistic analysis in coherence with the theoric model, several conclusions, among them we detach: a) The unexistence of a standart managerial style between public executives from Santa Catarina; b) Executives from this state use more feedback than executives from Minas Gerais and the same as north-americans; c) The executives from Santa Catarina have more opening (overture) than mineiros and north-americans; d) Some personel variants interfere in the managerial style of the public executive from Santa Catarina.

O outro lado de cá: histórias e memórias de Cachoeira da Prata

O principal objetivo dessa dissertação é analisar, através de um estudo caso, como a questão do “preconceito intergrupal” pode ser percebida no desenvolvimento histórico de pequenos municípios brasileiros. Escolhendo a história da memória da cidade de Cachoeira da Prata como objeto central, buscamos discutir como ocorreu o processo de diferenciação social da pequena comunidade formada pelos descendentes do ex-escravo Nicolau Teixeira do restante da cidade. Para tanto, dividimos a dissertação em duas partes. A primeira é formada pelos três primeiros capítulos, nos quais apresentamos a vila fabril de Cachoeira de Macacos como o cenário, no qual o cel. Américo Teixeira é identificado como o líder maior de um projeto de domínio político e industrial que deixou marcas duradouras na memória da população mais antiga da cidade. Nesse contexto, buscamos discutir como o fenômeno do pós-emancipação da escravidão se manifestou na localidade, analisando parte da trajetória de vida do ex-escravo Nicolau Teixeira, um leal apoiador do projeto político do cel. Américo, que se tornou, na primeira metade do século XX, o patriarca de uma comunidade criada nas imediações da antiga vila fabril. Na segunda parte, composta exclusivamente pelo quarto capítulo, discutimos de maneira conjugada, a história da diferenciação social da comunidade e diferentes posicionamentos políticos e metodológicos que adotamos ao longo da pesquisa. Após essa análise, concluímos que só é possível entender os meandros do processo que levou os descendentes de Nicolau Teixeira à condição de exclusão social após percebê-los como atores capazes de elaborar narrativas e representações que auxiliam a população de Cachoeira da Prata a conhecer um “outro lado” da história local.

Impactos da política de ICMS ecológico - uma análise qualitativa sob o enfoque do federalismo fiscal

Este estudo teve por objetivo identificar os principais impactos, sob a ótica do federalismo fiscal, da política do ICMS ecológico nos municípios mineiros, conciliando as bases teóricas que fundamentam o mecanismo do ICMS ecológico e suas características mais evidentes, como o impacto redistributivo e o impacto compensatório, descritos nos estudos analisados. A irradiação da política do ICMS ecológico por vários estados da federação reflete o esforço de construção de políticas públicas de conservação e proteção dos recursos naturais e de saneamento, traduzindo-se na ampliação de indicadores físicos associados, como o incremento no número de unidades de conservação e nos indicadores de saneamento. Entretanto, a adoção do ICMS ecológico sobre o mecanismo de repartição de receitas do ICMS envolve algumas questões teóricas de federalismo fiscal, descentralização e sistema tributário, exigindo ponderação e cautela quanto a seu efeito irradiador, sendo esta reflexão o objetivo final deste estudo.

Processo de escolha de bancos de imagens: aplicações no marketing business to business

The general objective of this research is to verify which attributes are most relevant to a stock photography agency that represent the purchaser's standards of choice. For this objective to be accomplished, qualitative interviews with the customers of stock photography agencies had been made in order to raise the attributes considered with relevance in the process of choice for the Brazilian stock photography agency market. The levels of each attribute to be tested had arisen through the mapping of the products and services offered by the competition and the relative weight assigned to each one of the attributes related to the research in the choices for a stock photography agency. A transversal study was made with a sample of stock photography agencies customers from Brazil¿s Southeastern region. For the analysis of this data, a survey method was used, that, according to MALHOTRA (2006: 182), involves a structuralized questionnaire to be answered by an interview that elucidates specific information, in which the questions had a predetermined order. This questionnaire was presented through interviews on the Internet. The method adopted for this analysis was a joint analysis. A sampling of 1000 customer stock photography agencies were selected, which were represented by a didactic book editor, advertising agencies, editorial companies, etc., in the states of Rio de Janeiro, São Paulo, Espírito Santo and Minas Gerais. They had been obtained by 16 stimulations, or cards, for the application of the companies. Of the sample of 1000 customers of stock photography agencies, 7,8% responded to the research. The attribute most relevant in accordance with the presented results is the availability of images in high resolution for layout. Its relative importance was 40,78%. At the end of the study, the management implications were propitiated to the stock photography agencies managers inabling them to be more competitive.