Activated Copper Cathodes as Sensors for Nitrite Analysis

The increased surface area of copper electrodes upon applying a suitable potential protocol was characterized by atomic force microscopy images. Scanning electrochemical microscopy was used to demonstrate the enhanced reactivity of the generated surface. The modified electrode showed excellent catalytic activity towards nitrite reduction in acidic medium (pH 2). This new platform was used in the development of a fast and simple voltammetric method for nitrite determination. Commercial and rainwater spiked samples were analyzed and the data showed an excellent agreement with those obtained with a reference spectrophotometric method (Griess reaction) at a confidence level of 95% (Student`s t-test).

Diagnoses of fipronil resistance in Brazilian cattle ticks (Rhipicephalus (Boophilus) microplus) using in vitro larval bioassays

Fipronil is a phenylpyrazolic insecticide that is widely used in agriculture and has been recently used to control the cattle tick, Rhipicephalus (Boophilus) microplus. Because of the serious problems associated with resistance to the available acaricides, this product has been used as an important alternative to control acaricide-resistant ticks. The objective of this work was to analyse the fipronil sensitivity of ticks that were collected from farms with a history of fipronil use by larval bioassays. A total of 11 Brazilian tick populations were studied: one population from Rio Grande do Sul, one population from Mato Grosso do Sul and nine populations from Sao Paulo. To validate the assays, susceptible reference strains, POA (Porto Alegre, Brazil) and Mozo (Dilave, Uruguay), and ticks from six different farms that never used fipronil were tested. The resistance of various tick populations to technical grade fipronil (95.3%) was primarily evaluated using the larvae immersion test (LIT) and the larval packet test (LPT), when a sufficient number of larvae was collected. Using the LIT, the resistance ratios (RR(50)) of the tick populations from Rio Grande do Sul and Mato Grosso do Sul were 14.9 and 2.6, respectively, and the populations derived from Sao Paulo had RR(50)s ranging from 2.5 to 6.9. Four populations were evaluated with the LPT, and two populations displayed lower RR(50), while other populations displayed higher RR(50) than those determined by the LIT. This article reports the first cases of fipronil resistance in Brazil and highlights the LIT as a more sensitive technique for the evaluation of fipronil resistance in R. (B) microplus ticks. We suggest the use of the LIT as an evaluation tool for monitoring fipronil resistance in the control programmes of R. (B) microplus. (C) 2010 Elsevier B.V. All rights reserved.

Approaches for multicopper oxidases in the design of electrochemical sensors for analytical applications

We report an effective approach for the construction of a biomimetic sensor of multicopper oxidases by immobilizing a cyclic-tetrameric copper(II) species, containing the ligand (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist), in the Nafion (R) membrane on a vitreous carbon electrode surface. This complex provides a tetranuclear arrangement of copper ions that allows an effective reduction of oxygen to water, in a catalytic cycle involving four electrons. The electrochemical reduction of oxygen was studied at pH 9.0 buffer solution by using cyclic voltammetry, chronoamperometry, rotating disk electrode voltammetry and scanning electrochemical microscopy techniques. The mediator shows good electrocatalytic ability for the reduction of O(2) at pH 9.0, with reduction of overpotential (350 mV) and increased current response in comparison with results obtained with a bare glassy carbon electrode. The heterogeneous rate constant (k(ME)`) for the reduction of O(2) at the modified electrode was determined by using a Koutecky-Levich plot. In addition, the charge transport rate through the coating and the apparent diffusion coefficient of O(2) into the modifier film were also evaluated. The overall process was found to be governed by the charge transport through the coating, occurring at the interface or at a finite layer at the electrode/coating interface. The proposed study opens up the way for the development of bioelectronic devices based on molecular recognition and self-organization. (C) 2010 Elsevier Ltd. All rights reserved.

Fast batch injection analysis of H(2)O(2) using an array of Pt-modified gold microelectrodes obtained from split electronic chips

A fast and robust analytical method for amperometric determination of hydrogen peroxide (H(2)O(2)) based on batch injection analysis (BIA) on an array of gold microelectrodes modified with platinum is proposed. The gold microelectrode array (n = 14) was obtained from electronic chips developed for surface mounted device technology (SMD), whose size offers advantages to adapt them in batch cells. The effect of the dispensing rate, volume injected, distance between the platinum microelectrodes and the pipette tip, as well as the volume of solution in the cell on the analytical response were evaluated. The method allows the H(2)O(2) amperometric determination in the concentration range from 0.8 mu mol L(-1) to 100 mu mol L(-1). The analytical frequency can attain 300 determinations per hour and the detection limit was estimated in 0.34 mu mol L(-1) (3 sigma). The anodic current peaks obtained after a series of 23 successive injections of 50 mu L of 25 mu mol L(-1) H(2)O(2) showed an RSD < 0.9%. To ensure the good selectivity to detect H(2)O(2), its determination was performed in a differential mode, with selective destruction of the H(2)O(2) with catalase in 10 mmol L(-1) phosphate buffer solution. Practical application of the analytical procedure involved H(2)O(2) determination in rainwater of Sao Paulo City. A comparison of the results obtained by the proposed ampermetric method with another one which combines flow injection analysis (FIA) with spectrophotometric detection showed good agreement. (C) 2011 Elsevier B.V. All rights reserved.

Photoswitches and Luminescent Rigidity Sensors Based on fac-[Re(CO)(3)(Me(4)phen)(L)](+)

The fac-[Re(CO)(3)(Me(4)phen)(trans-L)](+) complexes, Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline and L = 4-styrylpyridine, stpy, or 1,2-bis(4-pyridyl)ethylene, bpe, were synthesized and characterized by their spectroscopic, photochemical, and photophysical properties. The complexes exhibit trans-to-cis isomerization upon 313, 334, 365, and 404 nm irradiation, and the true quantum yields can be efficiently determined by absorption changes combined with (1)H NMR data. For fac-[Re(CO)(3)(Me(4)phen)(trans-bpe)](+) similar quantum yields were determined at all wavelengths investigated. However, a lower value (phi(true) = 0.35) was determined for fac-[Re(CO)(3)(Me(4)phen)(trans-stpy)](+) at 404 nm irradiation, which indicates different pathways for the photoisomerization process. The photoproducts, fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+), exhibit luminescence at room temperature with two maxima ascribed to the (3)IL(Me4phen) and (3)MLCT(Re -> Me4phen) excited states. The luminescence properties were investigated in different media, and the behavior in glassy EPA at 77 K showed that the contribution of each emissive state is dependent on the excitation wavelength. The photochemical and photophysical behavior of the complexes were rationalized in terms of the energy gap of excited states and can be exploited in photoswitchable luminescent rigidity sensors.

New hydrazine sensors based on electropolymerized meso-tetra (4-sulphonatephenyl)porphyrinate manganese (III)/silver nanomaterial

A new electrocatalytic active porphyrin nanocomposite material was obtained by electropolymerization of meso-tetra(4-sulphonatephenyl) porphyrinate manganese(III) complex (MnTPPS) in alkaline solutions containing sub-micromolar concentrations of silver chloride. The modified glassy carbon electrodes efficiently oxidize hydrazine at 10 mV versus Ag/AgCl, dramatically decreasing the overpotential of conventional carbon electrodes. The analytical characteristics of this amperometric sensor coupled with batch injection analysis (BIA) technique were explored. Wide linear dynamic range (2.5 x 10(-7) to 2.5 x 10(-4) mol L-1), good repeatability (R.S.D. = 0.84%, n = 30) and low detection (3.1 x 10(-8) mol L-1) and quantification (1.0 x 10(-7) mol L-1) limits, as well as very fast sampling frequency (60 determinations per hour) were achieved. (c) 2007 Elsevier B.V. All rights reserved.

The electrochemical effect of acid functionalisation of carbon nanotubes to be used in sensors development

The electrochemical behaviour of multi-walled carbon nanotubes was compared with that of glassy carbon, and the differences were investigated by cyclic voltammetry and electrochemical impedance spectroscopy before and after acid pre-treatment. The electrochemical techniques showed that acid functionalisation significantly improves the electrocatalytic properties of carbon nanotubes. These electrocatalytic properties enhance the analytical signal, shift the oxidation peak potential to a less positive value, and the charge-transfers rate increase of both dopamine and K(4)[Fe(CN)(6)]. The functionalisation step and the resulting appearance of edge planes covered with different chemical groups were confirmed by FTIR measurements. Carbon nanotubes after acid pre-treatment are a potentially powerful analytical tool for sensor development. (C) 2010 Elsevier B.V. All rights reserved.

Processos produtivos e trabalho-educação: a incorporação do caboclo catarinense na indústria madeireira

The object theme of the present study is a population of caboclos that absorbed as manual workers in the saw-mills which were mounted in the highland region of Santa Catarina since 1950. The abundance of araucaria (native kind of pine) the opening of markets, and the corroboration of other industrial exploration conditions encouraged a great crowd of small en.- trepreneurs, coming basically from the state of Rio Grande do Sul, to migrate and settle down, building up a lot of saw-mills near rich forests and fields. The saw-mills started aprosperous production of timber sawn in planks. The process of industriali zation was so intensive, the destruction of pine woods soviolent that, in less than three decades, the forests ran out of tree reserves. The caboclos, absorbed as manual workers in production of timber, lived traditionally in an system of subsistense, either from the cultivation of pine the economic their land (planter caboclo) or as labourers in cattle-growing farms (farm hand caboclos). Nevertheless, the 'advantages' that were offered them by the new-comer entrepreneurs (a salary paid in money, a new house in a village, and other favours) helped the great majority of caboclos to abandon their traditional work and enlist as "workmen" in saw-mills. The new job, besides being a novelty, was an opportunity for a change in status. Subsequently, the running out of forests of araucaria and the resultant progressive shut-down of saw-mills caused the crowd of workmen to be out of imployment and to form to form a migratory flood toward the most important town of the region, Lages. The town of Lages, however, having made of the timber i ts main economic support wi thout the implantation of an alternative industry, was unable to offer the migrantssufficient 'work places'. In this way, the 'marginal crowd' began to settle down in the suburbs of the city. This study, in the context of the object theme, analyses two main questions related to the reality 'WOlLQ' and to the economic exploitation forms: ~) the relations of production in the economic regime of subsistence and in the capitalist regime of industrial production with the consequent 'positions' of the workman in the productive processj ~~) the deriving educative effects of the productive process, either in the economic regime of subsistence, or in the capitalist industrial regime. The two questions are theoretically debated andconfro~ ted with the proposed reality, giving origin to conclusions that, in a general formulation, can be summarized as follows: a) the caboclos of the highland region of Santa Catari na, when under an economic regime of subsistence, held in fee the productive processj there was a social division of the work and aclimate of freedom which made possible the development of knowledge from their life and work experience, the production of most of their tools, and the making of necessary manufactures adapted to their own surrounding ditionsi -- - --- other con- ------ b) however, these same caboclos, when absorbed by the capitalist industrial process of production - tipified by the work in saw-mills - lost the control of the productive processj this was caused by the technologic division of the work, since each man began to perform a dull and repeti tive action, directed by the speed of the 'major-saw' j man resigned form his skill and inventive power and surrendered to an executive authority which turned him into a 'collective worker'j the new productive process, besides rnaking each rnan a copy of a pattern, put the caboclos in a situation in which the daily work experiencedidn't add anything in terrns of autogenesis of knowledgei and even the environrnental educative rneans were reduced to new forrns of adaptation to the productive process, relegating rnan's inventive power to inertia.

Design of boundary-scan testing in CMOS image sensors for industrial applications: internship repor

Tests on printed circuit boards and integrated circuits are widely used in industry,resulting in reduced design time and cost of a project. The functional and connectivity tests in this type of circuits soon began to be a concern for the manufacturers, leading to research for solutions that would allow a reliable, quick, cheap and universal solution. Initially, using test schemes were based on a set of needles that was connected to inputs and outputs of the integrated circuit board (bed-of-nails), to which signals were applied, in order to verify whether the circuit was according to the specifications and could be assembled in the production line. With the development of projects, circuit miniaturization, improvement of the production processes, improvement of the materials used, as well as the increase in the number of circuits, it was necessary to search for another solution. Thus Boundary-Scan Testing was developed which operates on the border of integrated circuits and allows testing the connectivity of the input and the output ports of a circuit. The Boundary-Scan Testing method was converted into a standard, in 1990, by the IEEE organization, being known as the IEEE 1149.1 Standard. Since then a large number of manufacturers have adopted this standard in their products. This master thesis has, as main objective: the design of Boundary-Scan Testing in an image sensor in CMOS technology, analyzing the standard requirements, the process used in the prototype production, developing the design and layout of Boundary-Scan and analyzing obtained results after production. Chapter 1 presents briefly the evolution of testing procedures used in industry, developments and applications of image sensors and the motivation for the use of architecture Boundary-Scan Testing. Chapter 2 explores the fundamentals of Boundary-Scan Testing and image sensors, starting with the Boundary-Scan architecture defined in the Standard, where functional blocks are analyzed. This understanding is necessary to implement the design on an image sensor. It also explains the architecture of image sensors currently used, focusing on sensors with a large number of inputs and outputs.Chapter 3 describes the design of the Boundary-Scan implemented and starts to analyse the design and functions of the prototype, the used software, the designs and simulations of the functional blocks of the Boundary-Scan implemented. Chapter 4 presents the layout process used based on the design developed on chapter 3, describing the software used for this purpose, the planning of the layout location (floorplan) and its dimensions, the layout of individual blocks, checks in terms of layout rules, the comparison with the final design and finally the simulation. Chapter 5 describes how the functional tests were performed to verify the design compliancy with the specifications of Standard IEEE 1149.1. These tests were focused on the application of signals to input and output ports of the produced prototype. Chapter 6 presents the conclusions that were taken throughout the execution of the work.

Estimates of genetic parameters for visual scores and their correlation with production and reproductive traits in Brahman cattle

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

Anthelmintic efficacy of oral trichlorfon solution against ivermectin resistant nematode strains in cattle

Infected calves from two different rural estates in Brazil were studied to assess the anthelmintic efficacy of oral trichlorfon against naturally occurring ivermectin resistant parasitic nematode strains. In experiment 1, infected animals were from a region where ivermectin resistant populations of Haemoncus placei, Cooperia punctata,Cooperia spatulata and Trichuris discolor have recently been identified. Six calves with natural gastrointestinal nematode infections were treated with 48.5 mg/kg aqueous trichlorfon administered orally and six calves acted as a non-treated control group. In experiment 11 24 naturally infected calves were selected to enter one of four treatment groups, six animals each received: 48.5 mg/kg oral trichlorfon; 200 mu g/kg subcutaneous 1% ivermectin; 630 mu g/kg subcutaneous 3.15% ivermectin; or no treatment (control group). Gastrointestinal helminths were counted and identified post-mortem at 7 days (trichlorfon and 1% ivermectin treated and untreated animals) or 14 days (3.15% ivermectin treated and untreated animals) after administration of the test agents. Experiment I identified a high level efficacy for oral trichlorfon against four helminth species that have previously been shown to be ivermectin resistant in this geographical region: percentage efficacy was 99.82% against adult H. placei, 99.18% against C. punctata, 99.33% against C. spatulata, 81.06% against T. axei, 98.46% against Oesophagostomum radiatum and 100% against T. discolor. Trichlorfon also showed activity against the ivermectin (1% and 3.15%) resistant helminth species identified in experiment 11, attaining efficacy levels of 99.17% against H. placei, 98.46% against C punctata and 100.00% against T. discolor. These findings indicate that oral trichlorfon is an effective treatment option in the management of cattle infected with ivermectin resistant helminths. (C) 2009 Elsevier B.V. All rights reserved.

Preferential infection sites of Cysticercus bovis in cattle experimentally infected with Taenia saginata eggs

The preferential sites of infection of Cysticercus bovis were evaluated in the skeletal muscle and entrails of 25 cattle that were experimentally infected with Taenia saginata (2 x 10(4) eggs). Two other animals were not inoculated (control). Ninety days after inoculation, all the cattle were euthanized. The carcasses were deboned and dissected into 26 anatomical sections (masseter muscles, brain, tongue, esophagus, heart, diaphragm, lungs, liver, kidneys, spleen, top sirloin butt, bottom sirloin butt, outside round, top (inside) round, transversus abdominus, top sirloin cap, strip loin, full tenderloin, eye of round, knuckle, shoulder clod, foreshank, shank, chuck, back ribs, and tail muscles). The dissected tissues were sliced into 5 mm sections. From the 25 cattle, 9258 C. bovis (cysticerci) were recovered; 75.02% (6946) of these were recovered from skeletal muscles and 24.98% (2312) from the entrails. A high parasitism level was found in the shoulder clod (12.55%), heart (11.02%), liver (9.48%), masseter muscles (8.51%), chuck (8.25%), strip loin and full tenderloin (7.26%), knuckle (6.63%), and back ribs (5.53%), totaling 69.23% (5738) of all of the detected cysticerci. on the other hand, there was a low C. bovis parasitism level in the brain, spleen, tail muscles, kidneys, esophagus, and diaphragm, representing just 3.9% of the total number of cysticerci. Given these results, we conclude that specific skeletal musculature regions, such as the shoulder blade, chuck, strip loin and full tenderloin, knuckle, back ribs and top round, which are not officially examined in many countries, are effective sites to efficiently screen C. bovis infection. To date, these regions have not been considered as preferential sites of C. bovis infection. Based on our work, however, these regions deserve greater attention from health inspectors because they contained a greater number of Cysticercus than the other regions of carcasses that are parasitized by T. saginata larvae. (c) 2010 Elsevier Ltd. All rights reserved.

Toxoplasma gondii: Infection natural congenital in cattle and an experimental inoculation of gestating cows with oocysts

Two studies, of a natural infection and an experimental infection, were performed in order to study congenital transmission of Toxoplasma gondii in cattle. In the first study, 50 fetuses were harvested from gestating cows that were eutanasied at a municipal slaughterhouse in Jaboticabal, São Paulo state, Brazil. In the second study, 11 gestating cows were divided into four groups for inoculation with T. gondii: GI consisted of three cows inoculated with 1.0 x 10(5) oocysts during their first trimester of gestation; GII consisted of three cows inoculated with 1.0 x 10(5) oocysts during their second trimester of gestation; GIII consisted of three cows inoculated with 1.0 x 10(5) oocysts during their last trimester of gestation; and GIV consisted of two control cows, one during its first and the other during its second trimester of gestation. In both studies, the presence of T. gondii was confirmed both indirectly by immunofluorescence assay (IFAT). In the natural infection experiment, 18% (9/50) of the gestating cows were confirmed to have specific antibodies (IFAT - 1:64) against T. gondii. The bioassay was able to diagnose the presence of T. gondii in the tissue samples from three calves. In the second experiment, the nine cows from groups I, II and III presented with specific antibodies (IFAT) against T. gondii. In contrast, T. gondii could not be detected by IFAT, histopathological examination or the bioassay in any of the nine calves born to cows experimentally infected with T. gondii oocysts. Based on the results from both studies, we conclude that congenital infection of T. gondii in cattle, while infrequent, does occur naturally. The pathogenicity of the strain of T. gondii may influence the likelihood of this route of transmission. (C) 2010 Elsevier B.V. All rights reserved.

Organic matter fractions and soil fertility under the influence of liming, vermicompost and cattle manure

Os efeitos do vermicomposto de esterco de curral associado à calagem em atributos da fertilidade do solo foram avaliados através de experimento em vasos empregando um Latossolo Vermelho, distrófico, textura média. Cinco doses do vermicomposto (equivalentes a 0; 28; 42; 56 e 70 t ha-1, peso seco) e cinco doses de calcário (visando elevar a saturação por bases a: 20; 30; 40; 50 e 60%) foram combinadas em esquema fatorial, sendo as amostras de solo incubadas por 180 dias. Para comparação entre o vermicomposto e o esterco de curral, amostras do mesmo solo receberam o equivalente a 70 t ha-1 do esterco de curral que originou o vermicomposto e as cinco doses de calcário listadas anteriormente. Através do cálculo do Índice de Eficiência Agronômica, foi verificado que o potencial de fornecimento de K e de Mg pelo esterco é maior do que o do vermicomposto, e que o de P, é semelhante. O vermicomposto aumentou os teores de Ca2+ e de matéria orgânica (MO), os valores de pH em CaCl2 e a CTC a pH 7. Com o aumento das doses de vermicomposto houve diminuição do C-ácidos húmicos e aumento do C-humina e com a calagem o C-total não aumentou mas houve diminuição do C-ácidos húmicos.