971 resultados para Round and square balers


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The electrochemical behaviour of propanil and related N-substituted amides (acetanilide and N,N-diphenylacetamide) was studied by cyclic and square wave voltammetry using a glassy carbon electrode. Propanil has been found to have chemical stability under the established analytical conditions and showed an oxidation peak at +1.27V versus Ag/AgCl at pH 7.5. N,N-diphenylacetamide has a higher oxidation potential than the other compounds of +1.49V versus Ag/AgCl. Acetanilide oxidation occurred at a potential similar to that of propanil, +1.24V versus Ag/AgCl. These results are in agreement with the substitution pattern of the nitrogen atom of the amide. A degradation product of propanil, 3,4-dichloroaniline (DCA), was also studied, and showed an oxidation peak at +0.66V versus Ag/AgCl. A simple and specific quantitative electroanalytical method is described for the analysis of propanil in commercial products that contain propanil as the active ingredient, used in the treatment of rice crops in Portugal.

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The electrochemical behaviour of the pesticide metam (MT) at a glassy carbon working electrode (GCE) and at a hanging mercury drop electrode (HMDE) was investigated. Different voltammetric techniques, including cyclic voltammetry (CV) and square wave voltammetry (SWV), were used. An anodic peak (independent of pH) at +1.46 V vs AgCl/Ag was observed in MTaqueous solution using the GCE. SWV calibration curves were plotted under optimized conditions (pH 2.5 and frequency 50 Hz), which showed a linear response for 17–29 mg L−1. Electrochemical reduction was also explored, using the HMDE. A well defined cathodic peak was recorded at −0.72 V vs AgCl/ Ag, dependent on pH. After optimizing the operating conditions (pH 10.1, frequency 150 Hz, potential deposition −0.20 V for 10 s), calibration curves was measured in the concentration range 2.5×10−1 to 1.0 mg L−1 using SWV. The electrochemical behaviour of this compound facilitated the development of a flow injection analysis (FIA) system with amperometric detection for the quantification of MT in commercial formulations and spiked water samples. An assessment of the optimal FIA conditions indicated that the best analytical results were obtained at a potential of +1.30 V, an injection volume of 207 μL and an overall flow rate of 2.4 ml min−1. Real samples were analysed via calibration curves over the concentration range 1.3×10−2 to 1.3 mg L−1. Recoveries from the real samples (spiked waters and commercial formulations) were between 97.4 and 105.5%. The precision of the proposed method was evaluated by assessing the relative standard deviation (RSD %) of ten consecutive determinations of one sample (1.0 mg L−1), and the value obtained was 1.5%.

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Electrochemical oxidation of propanil in deuterated solutions was studied by cyclic, differential pulse, and square wave voltammetry using a glassy carbon microelectrode. The oxidation of propanil in deuterated acid solutions occurs at the nitrogen atom of the amide at a potential of +1.15 V vs Ag/ AgCl. It was also found that, under the experimental conditions used, protonation at the oxygen atom of propanil occurs, leading to the appearance of another species in solution which oxidizes at +0.60 V. The anodic peak found at +0.79 V vs Ag/AgCl in deuterated basic solutions is related to the presence of an anionic species in which a negative charge is on the nitrogen atom. The electrochemical data were confirmed by the identification of all the species formed in acidic and basic deuterated solutions by means of NMR spectroscopy. The results are supported by electrochemical and spectroscopic studies of acetanilide in deuterated solutions.

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The oxidative behaviour of fluoxetine was studied at a glassy carbon electrode in various buffer systems and at different pH using cyclic, differential pulse and square wave voltammetry. A new square wave voltammetric method suitable for the quality control of fluoxetine in commercial formulations has been developed using a borate pH 9 buffer solution as supporting electrolyte. Under optimized conditions, a linear response was obtained in the range 10 to 16 μM with a detection limit of 1.0 μM. Validation parameters such as sensitivity, precision and accuracy were evaluated. The proposed method was successfully applied to the determination of fluoxetine in pharmaceutical formulations. The results were statistically compared with those obtained by the reference high-performance liquid chromatographic method. No significant differences were found between the methods.

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Increased levels of plasma oxLDL, which is the oxidized fraction of Low Density Lipoprotein (LDL), are associated with atherosclerosis, an inflammatory disease, and the subsequent development of severe cardiovascular diseases that are today a major cause of death in modern countries. It is therefore important to find a reliable and fast assay to determine oxLDL in serum. A new immunosensor employing three monoclonal antibodies (mAbs) against oxLDL is proposed in this work as a quick and effective way to monitor oxLDL. The oxLDL was first employed to produce anti-oxLDL monoclonal antibodies by hybridoma cells that were previously obtained. The immunosensor was set-up by selfassembling cysteamine (Cyst) on a gold (Au) layer (4 mm diameter) of a disposable screen-printed electrode. Three mAbs were allowed to react with N-hydroxysuccinimide (NHS) and ethyl(dimethylaminopropyl)carbodiimide (EDAC), and subsequently incubated in the Au/Cys. Albumin from bovine serum (BSA) was immobilized further to ensure that other molecules apart from oxLDL could not bind to the electrode surface. All steps were followed by various characterization techniques such as electrochemical impedance spectroscopy (EIS) and square wave voltammetry (SWV). The analytical operation of the immunosensor was obtained by incubating the sensing layer of the device in oxLDL for 15 minutes, prior to EIS and SWV. This was done by using standard oxLDL solutions prepared in foetal calf serum, in order to simulate patient's plasma with circulating oxLDL. A sensitive response was observed from 0.5 to 18.0 mg mL 1 . The device was successfully applied to determine the oxLDL fraction in real serum, without prior dilution or necessary chemical treatment. The use of multiple monoclonal antibodies on a biosensing platform seemed to be a successful approach to produce a specific response towards a complex multi-analyte target, correlating well with the level of oxLDL within atherosclerosis disease, in a simple, fast and cheap way.

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During June 1997-June 1999 rotavirus infection was screened in infants aged up to 2 years and hospitalised with acute diarrhoea in São Luís, Northeastern Brazil. Altogether, 128 stool samples were collected from diarrhoeic patients and additional 122 faecal specimens from age- and- temporal matched inpatients without diarrhoea were obtained; rotavirus positivity rates for these groups were 32.0% (41/128) and 9.8% (12/122), respectively (p < 0.001). Both electropherotyping and serotyping could be performed in 42 (79.2%) of the 53 rotavirus-positive stool samples. Long and short electropherotypes were detected at similar rates - 38.1% and 40.5% of specimens, respectively. Overall, a G serotype could be assigned for 35 (83.3%) of specimens, the majority of them (66.7%) bearing G1-serotype specificity. Taking both electropherotypes and serotypes together, G1 rotavirus strains displaying long and short RNA patterns accounted for 30.9% and 19.0% of tested specimens, respectively; all G2 strains had short electropherotype. Rotavirus gastroenteritis was detected year-round and, in 1998, the incidence rates tended to be higher during the second semester than in the first semester: 45.2% and 26.1% (p = 0.13), respectively. Rotavirus infections peaked at the second semester of life with frequencies of 30.1% and 13.5% for diarrhoeic children and controls, respectively. While the six rotavirus strains bearing G2-type specificity were circulating throughout the whole study period, G1 serotypes (n = 27) emerged as from June 1998 onwards, 20 (74.1%) of which clustering in 1998. These data underscore the importance of rotaviruses in the aetiology of severe infantile gastroenteritis in Northeastern Brazil and sustain the concept that a future vaccine should confer protection against more than one serotype.

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For the first time, a glassy carbon electrode (GCE) modified with novel N-doped carbon nanotubes (CNT-N) functionalized with MnFe2O4 nanoparticles (MnFe2O4@CNT-N) has been prepared and applied for the electrochemical determination of caffeine (CF), acetaminophen (AC) and ascorbic acid (AA). The electrochemical behaviour of CF, AC and AA on the bare GCE, CNT-N/GCE and MnFe2O4@CNT-N/GCE were carefully investigated using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Compared to bare GCE and CNT-N modified electrode, the MnFe2O4@CNT-N modified electrode can remarkably improve the electrocatalytic activity towards the oxidation of CF, AC and AA with an increase in the anodic peak currents of 52%, 50% and 55%, respectively. Also, the SWV anodic peaks of these molecules could be distinguished from each other at the MnFe2O4@CNT-N modified electrode with enhanced oxidation currents. The linear response ranges for the square wave voltammetric determination of CF, AC and AA were 1.0 × 10−6 to 1.1 × 10−3 mol dm−3, 1.0 × 10−6 to 1.0 × 10−3 mol dm−3 and 2.0 × 10−6 to 1.0 × 10−4 mol dm−3 with detection limit (S/N = 3) of 0.83 × 10−6, 0.83 × 10−6 and 1.8 × 10−6 mol dm−3, respectively. The sensitivity values at the MnFe2O4@CNT-N/GCE for the individual determination of AC, AA and CF and in the presence of the other molecules showed that the quantification of AA and CF show no interferences from the other molecules; however, AA and CF interfered in the determination of AC, with the latter molecule showing the strongest interference. Nevertheless, the obtained results show that MnFe2O4@CNT-N composite material acted as an efficient electrochemical sensor towards the selected biomolecules.

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The purpose of this work was to develop a reliable alternative method for the determination of the dithiocarbamate pesticide mancozeb (MCZ) in formulations. Furthermore, a method for the analysis of MCZ's major degradation product, ethylenethiourea (ETU), was also proposed. Cyclic voltammetry was used to characterize the electrochemical behavior of MCZ and ETU, and square-wave adsorptive stripping voltammetry (SWAdSV) was employed for MCZ quantification in commercial formulations. It was found that both MCZ and ETU are irreversibly reduced (− 0.6 V and − 0.5 V vs Ag/AgCl, respectively) at the surface of a glassy carbon electrode in a mainly diffusion-controlled process, presenting maximum peak current intensities at pH 7.0 (in phosphate buffered saline electrolyte). Several parameters of the SWAdSV technique were optimized and linear relationships between concentration and peak current intensity were established between 10–90 μmol L− 1 and 10–110 μmol L− 1 for MCZ and ETU, respectively. The limits of detection were 7.0 μmol L− 1 for MCZ and 7.8 μmol L− 1 for ETU. The optimized method for MCZ was successfully applied to the quantification of this pesticide in two commercial formulations. The developed procedures provided accurate and precise results and could be interesting alternatives to the established methods for quality control of the studied products, as well as for analysis of MCZ and ETU in environmental samples.

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This work describes an electrochemical and quantum chemical investigation of the fipronil insecticide. Cyclic voltammetry (CV) and square wave voltammetry (SWV) experiments were performed over a graphite-polyurethane (GPU) composite electrode. The fipronil molecule presents an one?electron irreversible oxidation reaction. Profiting the SWV signal a square wave stripping voltammetry (SWSV) procedure to determine the fipronil molecule in a 0.10 mol L-1 Britton-Robinson buffer solution, pH 8.0 was developed with accumulation potential and time of 0.50 V and 120 s, respectively. The limits of detection and quantification were 0.80 and 2.67 ?g L-1, respectively. Recovery tests were performed in three natural waters samples with values ranging from 99.67 to 101.37%. Quantum chemical studies showed that the nitrogen atom of the pyrazole group is the most probable oxidation site of the fipronil molecule.

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Dissertação de mestrado em European and Transglobal Business Law

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A total of 797 specimens of wild adult triatomines, belonging to six species from the entomological collections of the Costa Rican National Biodiversity Institute, was studied from the standpoint of their relative abundance, as reflected by light traps, distribution in the country, seasonal variations and climatic and altitudinal preferences. Triatoma dimidiata was the most abundant species (32.9% of the total specimens), with a very extensive distribution in different ecological zones, being more common between 100 to 400 m above sea level mainly at the end of the dry season. T. dispar was the third in frequency (21.5%), with narrower distribution, more abundant between 600 to 800 m and scarce during the dry season. Panstrongylus geniculatus and P. rufotuberculatus, second and fourth in frequency (22.1% and 15.1%, respectively), were widely distributed on both the Pacific and Caribbean basins, the former being more common between 80 to 270 m all year round and the latter below 800 m mainly during the first semester. Eratyrus cuspidatus which represented only 4.9% of the insects, was also present on both basins mainly below 200 m with a tendency to be scarce during certain months of the year, and was found in all types of ecological zones. Finally, Rhodnius pallescens, the least abundant species (3.6%) was restricted to very humid areas below 20 m, on the north side and Caribbean basin. With the exception of R. pallescens, males were more commonly found than females. Some epidemiological implications related to the six species are discussed.

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OBJECTIVE: To determine the usefulness of computed tomography (CT), magnetic resonance imaging (MRI), and Doppler ultrasonography (US) in providing specific images of gouty tophi. METHODS: Four male patients with chronic gout with tophi affecting the knee joints (three cases) or the olecranon processes of the elbows (one case) were assessed. Crystallographic analyses of the synovial fluid or tissue aspirates of the areas of interest were made with polarising light microscopy, alizarin red staining, and x ray diffraction. CT was performed with a GE scanner, MR imaging was obtained with a 1.5 T Magneton (Siemens), and ultrasonography with colour Doppler was carried out by standard technique. RESULTS: Crystallographic analyses showed monosodium urate (MSU) crystals in the specimens of the four patients; hydroxyapatite and calcium pyrophosphate dihydrate (CPPD) crystals were not found. A diffuse soft tissue thickening was seen on plain radiographs but no calcifications or ossifications of the tophi. CT disclosed lesions containing round and oval opacities, with a mean density of about 160 Hounsfield units (HU). With MRI, lesions were of low to intermediate signal intensity on T(1) and T(2) weighting. After contrast injection in two cases, enhancement of the tophus was seen in one. Colour Doppler US showed the tophi to be hypoechogenic with peripheral increase of the blood flow in three cases. CONCLUSION: The MR and colour Doppler US images showed the tophi as masses surrounded by a hypervascular area, which cannot be considered as specific for gout. But on CT images, masses of about 160 HU density were clearly seen, which correspond to MSU crystal deposits.

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Tutkimuksessa selvitettiin kuumakuivauksen vaikutusta hirsiraaka-aineen ominaisuuksiin, käyttökelpoisia kuivauskaavoja sekä lämpötilatasoja. Kokeissa kuivattiin kuorittuja pyöreitä mäntytukkeja 130-180° C:n maksimilämpötilassa, sekä pelkaksi sahattuja hirsiaihioita 115-140° C:n maksimilämpötilassa. Kuivauksissa pyrittiin mahdollisimman lyhyeen aikaan laadun siitä kuitenkaan kärsimättä. Laadussa kiinnitettiin erityisesti huomiota sisä- ja pintahalkeamiin sekä värimuutoksiin. Korkeita lämpötiloja käytettäessä kuivausaika oli huomattavasti nopeampi kuin lämminilmakuivauksessa. Koekuivaukset kestivät 1-4 vuorokautta, kun vastaavaa puutavaraan lämminilmakuivaus kestää 7-20 vuorokautta. Korkeimmilla lämpötiloilla suoritetuissa kokeissa koekappaleisiin muodostui paljon pieniä halkeamia kun taas alhaisemmilla lämpötiloilla halkeamien kappalemäärä väheni, mutta lähes joka kappaleessa oli vähintään yksi suuri (yli 5 mm leveä) halkeama. Sisähalkeamien määrä oli pyöreillä tukeilla suoritetuissa kokeissa kohtuullisen pieni. Pelkaksi sahatuilla aihioilla sitä vastoin sisähalkeamien määrä oli huomattavasti suurempi. Vain 100 mm x 175 mm aihioilla onnistuttiin yhdessä kuivauksessa pitämään sisähalkeaminen pienenä. Kuumakuivaus aiheuttaa väistämättä värimuutoksia puuhun. Mitä korkeammilla lämpötiloilla ja pidemmillä kaavoilla kuivataan sitä enemmän väri tummenee. Värin vaikutus lopputuotteessa riippuu kuitenkin käyttökohteesta ja asiakkaan mieltymyksistä. Tutkimuksen perusteella varsinkin pyöreiden tukkien kuumakuivaus näyttää onnistuvan laadul-lisesti hyvin ja huomattavasti lämminilmakuivausta nopeammin. Pelkaksi sahattujen hirsiaihioiden kuivauksessa prosessin hallinta havaittiin vaikeaksi ja toimivien kaavojen kehittäminen vaatii jatkotutkimuksia.

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The deterioration of surface waters is one of the most important issues in the environmental management of the European Union. Thus, the EU Water Framework Directive 2000/60/EC (WFD) requires “good ecological and chemical status” of surface waters by 2015 allowing only a slight departure from ecological reference conditions characterized by the biological communities typical for the conditions of minimal anthropogenic impact. The WFD requires the determination of ecological reference conditions and the present ecological status of surface waters. To meet this legislative demand, sedimentary diatom assemblages were used in these studies with various methods 1) to assess natural and human activity induced environmental changes, 2) to characterize background conditions 3) to evaluate the present ecological status and 4) to predict the future of the water bodies in the light of palaeolimnological data. As the WFD refers to all surface waters, both coastal and inland sites were included. Two long and two short sediment cores from the Archipelago Sea in the northern Baltic Sea were examined for their siliceous microfossils in order to assess (1) the Holocene palaeoenvironmental history and (2) the recent eutrophication of the area. The diatom record was divided into local diatom assemblage zones (LDAZ, long cores) and diatom assemblage zones (DAZ, short cores). Locally weighted weighted averaging regression and calibration (LWWA) was applied for the quantitative reconstruction of past TN concentrations (short cores). An age model for the long cores was constructed by using independent palaeomagnetic and AMS-14C methods. The short cores were dated using radiometric (210Pb, 226Ra and 137Cs) methods. The long cores date back to the early history of the Archipelago Sea, which was freshwater – no salinity increase referable to the brackish phase of the Yoldia Sea is recognized. The nutrient status of the lacustrine phase was slightly higher in the Archipelago Sea than in the Baltic Proper. Initial brackish-water influence is observed at 8 150 ±80 cal. BP (LDAZ4), but fully brackish conditions were established at 7 700 ±80 cal. BP (LDAZ5). The diatom assemblages indicate increasing salinity, warming climate and possible eutrophic conditions during the lacustrine to brackish-water transition. The decreasing abundance of Pseudosolenia calcar-avis (Schultze) Sundström and the increasing abundance of the ice-cover indicator species Pauliella taeniata (Grunow) Round and Basson indicate decreasing salinity and climatic cooling after ca. 5 000 cal. BP. Signs of eutrophication are visible in the most recent diatom assemblage zones of both short cores. Diatom-inferred total nitrogen (DI-TN) reconstructions partially fail to trace the actual measured total nitrogen concentrations especially from the late 1980s to the mid 1990s. This is most likely due to the dominating diatom species Pauliella taeniata, Thalassiosira levanderi Van Goor and Fragilariopsis cylindrus (Grunow) W. Krieger being more influenced by factors such as the length of the ice-season rather than nutrient concentrations. It is concluded that the diatom assemblages of the study sites are principally governed by climate fluctuations, with a slight influence of eutrophication visible in the most recent sediments. There are indications that global warming, with reduced ice cover, could impact the spring blooming diatom species composition in the Archipelago Sea. In addition, increased sediment accumulation in the early 90s coincides with the short ice-seasons suggesting that warming climate with decreasing ice-cover may increase sedimentation in the study area. The diverse diatom assemblages dominated by benthic species (54 %) in DAZ1 in the Käldö Fjärd core can be taken as background diatom assemblages for the Archipelago Sea. Since then turbidity has increased and the diatom assemblages have been dominated by planktonic diatoms from around the mid 1800s onwards. The reconstructed reference conditions for the total nitrogen concentrations fluctuate around 400 μg l-1. Altogether two short sediment cores and eight short cores for top-bottom analysis were retrieved from Lake Orijärvi and Lake Määrjärvi to assess the impact of the acid mine drainage (AMD) derived metals from the Orijärvi mine tailings on the diatom communities of the lakes. The Cu (Pb, Zn) mine of Orijärvi (1757 – 1956) was the first one in Finland where flotation techniques (1911 – 1955) were used to enrich ore and large quantities of tailings were produced. The AMD derived metal impact to the lakes was found to be among the heaviest thus far recorded in Finland. Concentrations of Cu, Pb and Zn in Lake Orijärvi sediments are two to three orders of magnitude higher than background values. The metal inputs have affected Lake Orijärvi and Lake Määrjärvi diatom communities at the community levels through shifts in dominant taxa (both lakes) and at the individual level through alteration in frustule morphology (Lake Orijärvi). At present, lake water still has elevated heavy metal levels, indicating that the impact from the tailings area continues to affect both lakes. Lake Orijärvi diatom assemblages are completely dominated by benthic species and are lacking planktonic diatoms. In Lake Määrjärvi the proportion of benthic and tychoplanktonic diatoms has increased and the planktonic taxa have decreased in abundance. Achnanthidium minutissimum Kützing and Brachysira vitrea (Grun.) R. Ross in Hartley were the most tolerant species to increased metal concentrations. Planktonic diatoms are more sensitive to metal contamination than benthic taxa, especially species in the genus Cyclotella (Kützing) Brébisson. The ecological reference conditions assessed in this study for Lake Orijärvi and Lake Määrjärvi comprise diverse planktonic and benthic communitites typical of circumneutral oligotrophic lakes, where the planktonic diatoms belonging to genera Cyclotella , Aulacoseira Thwaites, Tabellaria Ehrenberg and Asterionella Hassall dominate in relative abundances up to ca. 70%. The benthic communities are more diverse than the planktonic consisting of diatoms belonging to the genera Achnanthes Bory, Fragilaria Lyngbye and Navicula St. Vincent. This study clearly demonstrates that palaeolimnological methods, especially diatom analysis, provide a powerful tool for the EU Water Frame Work Directive for defining reference conditions, natural variability and current status of surface waters. The top/bottom approach is a very useful tool in larger-scale studies needed for management purposes. This “before and after” type of sediment sampling method can provide a very time and cost effective assessment of ecological reference conditions of surface waters.

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Caesalpinia leiostachya (Benth.) Ducke (Caesalpiniaceae) is a Brazilian legumenous tree whose seeds present different sizes and shapes, with dormancy imposed by a waterproof coat. In order to improve that quality of lot, seeds were classified by width in sieves of circular meshes (13, 14, 15, 16 and 17) and manually separated by shape in elongate, round and angular. Masses of 1000 seeds were determined and the thickness of each width and shape seedclass was measured, and coat permeability of the seeds classified by the width was investigated. Seeds were scarified in concentrated sulphuric acid and submitted to the germination test. Both final percentage and speed of germination index were evaluated. The classification of the seeds improved the quality of the lot, and the coat permeability was not affected by seed width. Elongated-flat seeds are of low physiological quality and should be discarded. Masses of 1000 seeds, percentage final and speed of germination increased with the width of the seeds. Both elongated and angular seeds had similar germinative behavior, and round seeds are of greater thickness and of superior physiological quality.