We have incorporated rhodamine into polyamide membranes by additive manufacture selective laser sintering technology. Incorporation into 0.5 cm2 membranes was conducted at different pH values and constant temperature of 25 oC. The amounts of incorporated dye were determined by a calibration curve, and analyses showed rhodamine incorporation in the order of 10-6 mol L-1. The absorption spectra of the solutions and membranes after rhodamine incorporation showed maximum absorption at 553 nm and a shoulder at 522 nm, which indicated that a dimer was formed. Photoluminescence presented maximum emission at 575 nm for the sample incorporated with rhodamine in acid pH. The membranes that were treated with acid presented shorter adsorption time and demanded 180 min to reach equilibrium, whereas the non-treated membrane and the membranes that were treated with base required 1440 min to reach equilibrium. Polyamide membrane has proven to be an excellent material for the incorporation of dyes and compounds for application as luminescent sensors.

Lanthanide ions have special light emission, which can occur through descending and ascending energy conversion. Ascending energy conversion is especially interesting for bioapplications because excitation in the infrared region does not excite biomolecules and therefore does not interfere in detection, not to mention that it penetrates deeper in the skin. Here, we synthesized yttrium and aluminum oxide doped with Yb3+and Er3+ions via the non-hydrolytic sol-gel methodology. The doped matrix was incorporated and dispersed over a polyamide membrane obtained by Additive Manufacturing. X-ray diffraction revealed that a mixture of yttrium aluminum monoclinic and garnet phases emerged. Upon excitation at 980 nm in the Yb3+ion, the Er3+ presented more intense emission as a function of the laser power, which favored red emission. The intensities of the bands corresponding to the 4S3/2 → 4I15/2 (563 nm) and 5F9/2 → 4I15/2 (660 nm) transitions involved the absorption of two photons. The oxide incorporated into the polyamide membrane presented the same behavior. After coating with polyetherimide, the latter system was resistant to 5.1 W laser, which paves the way for new applications.

Additive manufacture is an effective technology to produce complex macrostructures from polymers. Sol-gel is a chemical process that affords multifunctional materials by functionalization of different substrates. This work reports on the use of acrylonitrile-butadiene-styrene polymer (ABS) as starting material to obtain a substrate by additive manufacture. Coating of ABS by the sol-gel methodology generated a multifunctional material. Sols with and without phosphate ions were prepared from silicon and calcium alkoxide. Based on X-ray diffraction patterns, a calcium phosphate crystalline structure emerged on ABS after contact of the substrate with simulated body fluid. Infrared analysis revealed that the peaks of the functionalized substrate shifted, indicating that ABS interacted with the sol-gel coating. According to thermal analysis, the maximum decomposition temperature of the coated samples was 20 ºC higher as compared to non-coated ABS. Sol-gel and additive manufacture are important technologies to produce materials with applications in biological medium.

Over the last decades, the combination of different technologies to search for systems with new properties and features has brought various segments of biological and earth sciences together. Additive manufacturing, known as rapid prototyping, combined with the sol-gel methodology enables the production of novel systems with applications in many scientific fields. In this work, flexible polyamide membranes were obtained by additive manufacturing, functionalized by the sol-gel methodology, and incorporated with the coordination compound between Eu(III) and 1,10-phenanthroline. The presence of vibrations at 1100 cm-1 in the FTIR spectrum of the material, which is a band typical of the Si-O-Si group in the alkoxide employed during the process, confirmed the polyamide membrane functionalization. The thermogravimetric curve showed that a residue remained after heating at 700 ºC, which was attributed to SiO2. The membrane was highly luminescent, which confirmed incorporation of the Eu3+ compound into the material and pointed to the possible application of this system as a topical medication for the treatment of skin diseases.

In this work, a new and sensitive electroanalytical methodology was developed and validated to quantify sulfentrazone in soil samples. Sulfentrazone was initially characterized qualitatively using cyclic voltammetry (CV). Its oxidation occurred by diffusion (mass transport) on a glassy carbon electrode (GCE) via irreversible transfer of one electron close to a peak potential of +0.936 V vs. Ag|AgCl, 3.0 mol L-1 KCl, in 0.10 mol L-1 KOH. Differential-pulse voltammetry (DPV) was the most sensitive and selective technique, with limits of detection (LOD) of 1.94 and 2.19 mmol L-1 and limits of quantification (LOQ) of 6.46 and 7.31 mmol L-1, in the absence and presence of soil matrix, respectively. The reproducibility of the method ranged between 2.65 and 4.2%, with intermediate precision between 5.32 and 10.9%. The recovery rate ranged between 88.5 and 103%. Additionally, the accuracy of the electroanalytical method was validated by comparing the results with data from a standard analytical methodology of high-performance liquid chromatography (HPLC/UV-Vis).

A maconha é uma das drogas ilícitas mais consumidas no mundo. Sendo assim, os traficantes têm procurado novos meios para mascarar o teste preliminar (colorimétrico) atualmente utilizado. Este trabalho descreve uma metodologia para detecção de delta-9-tetraidrocanabinol (Δ9-THC) por voltametria de onda quadrada (SWV) em meio orgânico N,N-dimetilformamida utilizando tetrafluoroborato de tetrabutilamônio (TBATFB) como eletrólito de suporte e eletrodos de trabalho de disco de carbono vítreo e platina. Aplicando-se um potencial de -0,5 ± 0,01 V vs. Ag/AgCl, KCl(sat), verifica-se um pico de corrente anódica após etapa de pré-concentração. Utilizando eletrodo de disco de carbono vítreo como eletrodo de trabalho, obteve-se uma dependência linear na faixa de concentração entre 1,0 × 10-9 mol L-1 a 2,2 × 10-8 mol L-1, com um coeficiente de correlação linear em 0,999 e um limite de detecção de 6,2 × 10-10 mol L-1. Tais resultados apontam que a técnica SWV, utilizando eletrodo de trabalho de disco de carbono vítreo, permite a análise qualitativa de Δ9-THC em concentrações maiores que 1,0 nmol L-1.

Marijuana is a widely consumed illicit drug. Therefore, drug dealers have sought new ways to mask its forensic (spot test) analysis. In this article we describe a methodology for delta-9-tetrahydrocannabinol (Δ9-THC) detection by square-wave voltammetric (SWV) analysis in organic medium (N,N-dimethylformamide) using tetrabutylammonium tetrafluoroborate (TBATFB) as supporting electrolyte, and glassy carbon and platinum disc as working electrode. Applying a potential of -0.5 ± 0.01 V vs. Ag/AgCl, KCl(sat), we detected a well-defined anodic peak current after the pre-concentration step; Δ9-THC detection presented linear dependence at concentrations ranging from 1.0 × 10-9 mol L-1 to 2.2 × 10-8 mol L-1, with a linear correlation coefficient 0.999 and a detection limit of 6.2 × 10-10 mol L-1, using the glassy carbon disc working electrode. These results confirm that optimized SWV technique using glassy carbon disc working electrode enables qualitative analysis of Δ9-THC at concentrations higher than 1.0 nmol L-1.

O açúcar é amplamente consumido em todo o mundo e o Brasil é o maior produtor, consumidor e exportador deste produto. Para garantir o bom desenvolvimento e produtividade das culturas de cana de açúcar, é necessário aplicar grandes quantidades de agrotóxicos, principalmente herbicidas e pesticidas. O herbicida tebuthiuron (TBH) impede a pré e pós-emergência das plantas daninhas infestantes nas culturas de cana de açúcar. Considerando que é importante para garantir a segurança alimentar da população, este trabalho propõe um método confiável para analisar TBH em matrizes de açúcar (mascavo e cristal), usando voltametria de onda quadrada (SWV) e voltametria de pulso diferencial (DPV) em eletrodo de carbono vítreo e investigar o comportamento eletroquímico do herbicida por voltametria cíclica (CV). Os nossos resultados sugerem que TBH ou o produto da sua reação com o eletrólito de suporte é oxidado através da transferência irreversível de um elétron entre o analito e eletrodo de trabalho, a um potencial de cerca de +1,16 V vs. Ag|AgCl sat em 0,10 mol L-1 KOH como solução de eletrólito de suporte. Tanto DPV quanto SWV são satisfatórios para a análise quantitativa do analito. DPV é mais sensível e seletiva, com limites de detecção de 0,902, 0,815 e 0,578 mg kg-1, e limite de quantificação de 0,009, 0,010 e 0,008 mg kg-1, na ausência da matriz, e na presença de matriz de açúcar cristal e mascavo, respectivamente. Reprodutibilidade situou-se entre 0,53 e 13,8%, a precisão variou entre 4,14 e 15,0%, e a recuperação manteve-se entre 84,2 e 113% para DPV conduzido na ausência e na presença da matriz de açúcar cristal, respectivamente.

Sugar is widely consumed worldwide and Brazil is the largest producer, consumer, and exporter of this product. To guarantee proper development and productivity of sugar cane crops, it is necessary to apply large quantities of agrochemicals, especially herbicides and pesticides. The herbicide tebuthiuron (TBH) prevents pre- and post-emergence of infesting weed in sugarcane cultures. Considering that it is important to ensure food safety for the population, this paper proposes a reliable method to analyse TBH in sugar matrixes (brown and crystal) using square wave voltammetry (SWV) and differential pulse voltammetry (DPV) at bare glassy carbon electrode and investigate the electrochemical behavior of this herbicide by cyclic voltammetry (CV). Our results suggest that TBH or the product of its reaction with a supporting electrolyte is oxidized through irreversible transfer of one electron between the analyte and the working electrode, at a potential close to +1.16 V vs. Ag |AgCl sat in 0.10 mol L-1 KOH as supporting electrolyte solution. Both DPV and SWV are satisfactory for the quantitative analysis of the analyte. DPV is more sensitive and selective, with detection limits of 0.902, 0.815 and 0.578 mg kg-1, and quantification limits of 0.009, 0.010 and 0.008 mg kg-1 in the absence of the matrix and in the presence of crystal and brown sugar matrix, respectively. Repeatability lay between 0.53 and 13.8%, precision ranged between 4.14 and 15.0%, and recovery remained between 84.2 and 113% in the case of DPV conducted in the absence of matrix and in the presence of the crystal sugar matrix, respectively.

Um método eletroanalítico foi desenvolvido para determinação simultânea de íons cobre e chumbo em cachaça empregando eletrodo de pasta de carbono modificado com ácido ascórbico e nanotubos de carbono (CPE-AaCNT). A técnica de voltametria de onda quadrada (SWV) com redissolução anódica foi empregada e otimizada com relação aos seguintes parâmetros: frequência (50 Hz), amplitude (100 mV) e incremento de varredura (9 mV). As curvas analíticas apresentaram intervalo linear de 0,09 a 7,00 mg L- 1 para o chumbo e para o cobre. Os limites de detecção foram de 48,5 e 23,9 µg L- 1 para o chumbo e o cobre, respectivamente. O método desenvolvido foi aplicado na determinação simultânea de chumbo e cobre em cinco amostras comerciais de cachaça. Os resultados apresentaram-se concordantes com os obtidos por F AAS/GF AAS (espectrometria de absorção atômica com chama/espectrometria de absorção atômica com forno de grafite) e revelaram que CPE-AaCNT podem ser empregados com êxito na quantificação de cobre e chumbo em amostras comerciais de cachaça.

The development of an electroanalytical method for simultaneous determination of copper and lead ions in sugar cane spirit (cachaça) using carbon paste electrode modified with ascorbic acid and carbon nanotubes (CPE-AaCNT) is described. Squarewave voltammetry (SWV) with anodic stripping was employed, and this technique was optimized with respect to the following parameters: frequency (50 Hz), amplitude (100 mV) and scan increment (9 mV). The analytical curves were linear in the range from 0.0900 to 7.00 mg L- 1 for lead and copper. The limits of detection were 48.5 and 23.9 µg L- 1 for lead and copper, respectively. The developed method was applied to the simultaneous determination of copper and lead in five commercial samples of sugar cane spirit. The results were in good agreement with those obtained by F AAS/GF AAS (flame atomic absorption spectrometry/graphite furnace atomic absorption spectrometry) and showed that CPE-AaCNT can be successfully employed in the simultaneous determination of these metals in real sugar cane spirit samples.

Nanocompósitos de poliamida 6 e argila organofílica claytone 40 foram preparados por intercalação por fusão, utilizando misturador de câmara interna equipado com rotores do tipo Roller. A adição de teores crescentes de claytone 40 na matriz de PA6 foi avaliada quanto ao grau de dispersão, cristalinidade, propriedades térmicas e as propriedades mecânicas. As composições obtidas foram caracterizadas por difração de raios X (DRX), calorimetria diferencial de varredura (DSC), microscopia eletrônica de varredura (MEV) e propriedades mecânicas. Os difratogramas e as micrografias sugeriram a ocorrência de formação de estruturas parcialmente esfoliadas e/ ou intercaladas, fato que foi associado com o aumento nos valores de tensão e o módulo elástico. A comparação entre os resultados de DSC e DRX das misturas revelaram alterações estruturais na cristalinidade em relação à PA6 correlacionando a cristalinidade à variação nas propriedades mecânicas.

Nanocomposites of polyamide 6 and Claytone 40 organoclay were prepared with the melt intercalation technique using an internal mixer chamber coupled with roller type rotors. The addition of increasing amounts of Claytone 40 into the PA6 matrix was evaluated for the degree of dispersion, crystallinity, thermal and mechanical properties. The compositions were characterized with X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and mechanical properties. The diffraction patterns and microscope images suggest the formation of partially exfoliated or intercalated structures, which was associated with an increase in stress values and elastic modulus. The comparison of DSC and XRD results from the mixtures revealed changes in the behavior of crystalline structures, thus indicating that the PA6 crystallinity is correlated with the mechanical properties.

Objetivou-se, com este trabalho, construir protótipos de microaspersores, com boa uniformidade de distribuição para irrigações com sobreposição em hortas agrícolas, utilizando-se os processos de prototipagem rápida e torneamento mecânico. O estudo foi conduzido na ESALQ/USP e no Centro de Tecnologia da Informação Renato Archer (CTI). Utilizou-se o coeficiente de uniformidade de Christiansen na avaliação do desempenho dos emissores. O PVC e o tecnyl foram os materiais que apresentaram mais facilidade na construção dos protótipos no processo de torneamento mecânico, porém o PVC foi o escolhido devido ao melhor acabamento. Os protótipos construídos com torneamento mecânico apresentaram resultados satisfatórios ressaltando tratar-se de um processo bastante artesanal e laborioso; já com a prototipagem rápida se construíram protótipos com melhores acabamentos e mais rapidez. A utilização da prototipagem rápida no desenvolvimento de equipamentos de irrigação é algo totalmente inovador e de caráter pioneiro, além de uma ferramenta de grande utilidade na área de inovação de produtos no setor de Engenharia Agrícola.

The present study had the objective of developing prototypes of microsprinkler with good distribution uniformity to irrigate with overlap in vegetable crops, by rapid prototyping and mechanic tournament. The work was carried out in the Hydraulic Laboratory of the Escola Superior de Agricultura "Luiz de Queiroz", University of Sao Paulo, Brazil, and in the Centro de Tecnologia da Informação Renato Archer (CTI). Two processes were tested in the development of the microsprinkler prototypes rapid prototype and mechanical lathing. Christiansen Uniformity Coefficient was used as indicator to evaluate the distribution uniformity. Among the tested materials, the PVC and the technyl showed more facility in the prototype development in the mechanical lathing process, however, the PVC was chosen due to better finishing. The prototypes built by mechanical lathing showed satisfactory results, but were hard work and handmade. On the other hand, with the rapid prototyping, prototypes were built with better finishing and were quicker. The utilization of rapid prototyping in the development of irrigation devices is something completely innovative and pioneering, besides being a tool of great utility in the product innovation in the Agricultural Engineering sector.

Prototipagem rápida (PR) é uma expressão que designa um conjunto de tecnologias que tem em comum a construção de protótipos físicos a partir de seus análogos virtuais. A construção camada a camada permite a obtenção de formas de alta complexidade, não possíveis de serem obtidas por técnicas convencionais de usinagem, baseadas em subtração de material. Um resumo sobre PR e suas aplicações na área da saúde é apresentado. Menção especial é dedicada ao PROMED (Prototipagem Rápida na Medicina) - um projeto de cunho social que realiza pesquisa e desenvolvimento envolvendo aplicações de PR na área médica e que difunde no Brasil e no exterior os benefícios trazidos pela PR no planejamento e ensaio cirúrgico e, também, na construção de implantes de alto desempenho anatômico. Também é feita uma revisão bibiográfica acerca da aplicação de SLS - Selective Laser Sintering - em scaffolds para engenharia tecidual e das mais recentes tecnologias de prototipagem direta em metal para construção de implantes personalizados. Finalmente são apresentados resultados preliminares de experimentos para construção de scaffods com o biomaterial PHB - poli (hidroxi butirato) e nylon usando um equipamento SLS.

Rapid Prototyping (RP) is an expression that is used for defining a set of technologies that have as a common characteristic the building of 3D physical prototypes, layer-by-layer, from their analogue virtual prototypes. The layer-by-layer building approach allows obtaining high complex shapes which cannot be obtained by the current most usual technologies based on material subtraction. A brief review about RP and its applications in the health domain is presented. A special mention is dedicated to the PROMED (PR in Medicine) - a non-profit research, development and knowledge diffusion project - focused on RP applied to medicine. Also it is reviewed the application of SLS - Selective Laser Sintering - for tissue engineering scaffolds and the most recent technologies for direct metal prototyping for building metal customized implants. Finally it is shown preliminary results of experiments to build scaffolds with PHB poly (hidroxy butirate) and nylon utilizing a SLS machine.

Durante o governo FHC buscou-se substituir a agenda reativa da política externa brasileira, dominada pela lógica da autonomia pela distância, por uma nova agenda internacional proativa, determinada pela lógica da autonomia pela integração. Segundo essa agenda, o país deveria ampliar o poder de controle sobre o seu destino e resolver seus problemas com uma adesão ativa à elaboração das normas e das pautas de conduta da gestão da ordem mundial. No entanto, essa política de integração, adesão e participação não foi plenamente acompanhada de tomadas de posições que implicassem responsabilidades práticas, em virtude de debilidades estruturais. As responsabilidades teriam como função preparar tanto o governo como a sociedade civil para uma inserção internacional de perfil mais elevado no pós-Guerra Fria. Os ganhos ocorridos nos governos FHC não foram suficientes para alterar significativamente o peso brasileiro no contexto mundial.

During the FHC government there was an attempt to substitute the reactive Brazilian foreign policy agenda, dominated by the logic of autonomy via distance, by a new proactive international agenda, determined by the logic of autonomy through integration. According to this agenda, the country should increase its power over the control of its destiny and sort out its problems by actively adhering to the elaboration of norms and guidelines for the conduct of the administration of global order. However, this integration, adhesion and participation policy was not fully followed up by the taking of standpoints that implied practical responsibilities because of structural disabilities. The responsibilities would prepare both government and civil society for an international insertion at a higher level, in the post-Cold War era. The gains achieved during the FHC terms in office were not sufficient to significantly alter the Brazilian position within the world context.