Desenvolvimento e validação do método QuEChERS na determinação de resíduos de medicamentos veterinários em leite e carne de búfalo

Analytical methods were developed and validated to determine residues of veterinary drugs in buffalo milk and meat, using the QuEChERS method and gas chromatography-mass spectrometry. Both milk and meat, at 2 g of sample, 4 mL of acetonitrile, 0.8 g of MgSO4 and 0.2 g of NaCl, were used in the liquid-liquid partition, whereas 50 mg of C18, 50 mg of PSA and 150 mg of MgSO4 were employed in the dispersive solid-phase extraction (d-SPE). The methods showed sensitivity, precision and accuracy. The quantitation limits were in agreement with the maximum residue limit established by the Codex Alimentarius, FAO and WHO.

Modificação e caracterização do resíduo pó de aciaria elétrica (PAE) para aplicação em reações de redução de cromo (VI)

In this study, electric arc furnace dust (EAFD) was thermally modified at different temperatures under H2 flow or charcoal in order to obtain reduced iron phases (Fe3O4, FeO and Fe0). The formation of these phases was confirmed by powder X-ray diffraction. The tests performed for reducing Cr (VI) using resultant materials obtained after thermal treatment of the EAFD showed excellent results, with PAE600H (EAFD reduced at 600 ºC under H2 flow) decreasing around 100% of the Cr (VI) in only 10 minutes of reaction. These results indicate the possibility of adding value to the residue, obtaining materials that offer great potential for environmental applications.

Inovação para a sustentabilidade

The transition to sustainable standards of production and consumption within a scenario of decreased availability of natural resources, growing population and climate change is essential to meet current challenges facing mankind. A strategy to meet these challenges should contain elements different from current approaches for industrial production. This work concentrates on the possibilities for the intensive use of sustainable biomass, abundant minerals and every type of residue, a task that can largely benefit from the application of nanotechnology and biotechnology platforms for material design and transformation. This strategy cannot be solely based on existing knowledge and requires new science, new knowledge including supposedly well-known themes, like the tribochemistry of electrostatic charging and friction. It is especially relevant within the Brazilian context, where many recent successful innovations are related to biomass production and transformation. Implementation of this strategy requires converging efforts by personnel from many different organizations and professions, while making sound risk assessment to produce significant innovation leading to sustainable development.

Otimização e validação da extração sólido-líquido e purificação em baixa temperatura de HPAs em lodo de esgoto

In this study, a method of solid-liquid extraction and purification at low temperature (SLE-PLT) to determine 16 polycyclic aromatic hydrocarbons (PAHs) in sewage sludge was optimized and validated. The analyses were performed by HPLC-UV. The extraction phase, homogenization procedure, influence of pH, ionic strength and clean-up of the extracts were optimized. Recoveries were higher than 63.4% for 11 PAHs. The correlation coefficients were greater than 0.99 and limits of detection and quantitation were less than 0.060 and 0.15 µg g-1, respectively. These values were lower than the maximum residue limits of PAHs established by European legislation. SLE-PLT proved a more practical, economical method with fewer steps compared to Soxhlet extraction (reference method) for PAHs in sewage sludge.

MONITORAMENTO DE RESÍDUOS DE AGROTÓXICOS DA CLASSE DOS ORGANOFOSFORADOS POR CGDFC EM AMOSTRAS DE LEITE FLUÍDO E EM PÓ

Samples of whole fluid pasteurized, UHT and powdered milk were analyzed for the presence of organophosphorus pesticide residues (OPR) using the QuEChERS method with detection by GC-FPD and confirmation by UPLC-MS/MS. A total of 23% of fluid milk samples and 27% of powdered milk samples contained at least one organophosphorus residue. The OPR found in the samples showed these can reach the milk and remain even after pasteurization, sterilization and drying processes. Some domestic sanitary residues were also present in the powdered milk samples. These residues have no LMR in Brazilian food legislation and are therefore not taken into account in food intake evaluations. There was an unidentified chromatographic peak in 30% of all the liquid and powdered milk samples, indicating the presence of some other contaminant.

MONITORING OF ORGANOPHOSPHOROUS PESTICIDE RESDUES IN SAMPLES OF BANANA, PAPAYA, AND BELL PEPPER

The objective of this study was to monitor 11 organophosphorus pesticides in samples of papaya, bell pepper, and banana, commercialized in the metropolitan area of Vitória (ES, Brazil). The pesticides were determined by an optimized and validated method using high performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). All three samples exhibited a matrix effect for most of the pesticides, mainly with signal suppression, and therefore the calibration curves were produced in matrices. Linearity revealed coefficients of determination (r2) greater than 0.9895 for all pesticides and recovery results ranged from between 76% and 118% with standard deviation no greater than 16%. Precision showed relative standard deviation values lower than 19% and HorRat values lower than 0.7, considering all pesticides. Limits of quantification were less than 0.01 mg/kg for all pesticides. Regarding analysis of the samples (50 of each), none of the pesticides exceeded the maximum residue limit determined by Brazilian legislation.

ISOLATION AND CHARACTERIZATION OF NANOFIBRILLATED CELLULOSE FROM OAT HULLS

The objectives of this work were to investigate the microstructure, crystallinity and thermal stability of nanofibrillated cellulose obtained from oat hulls using bleaching and acid hydrolysis at a mild temperature (45 ºC) followed by ultrasonication. The oat hulls were bleached with peracetic acid, and after bleaching, the compact structure around the cellulosic fibers was removed, and the bundles became individualized. The extraction time (30 or 60 min) did not affect the properties of the nanofibrillated cellulose, which presented a higher crystallinity index and thermal stability than the raw material (oat hulls). The nanocellulose formed interconnected webs of tiny fibers with diameters of 70-100 nm and lengths of several micrometers, producing nanofibers with a relatively high aspect ratio, thus indicating that these materials are suitable for polymer reinforcement.

PARÂMETROS TERMODINÂMICOS DA CASCA DE LARANJA DESIDRATADA

The global energy scenario is currently a widely discussed topic, with growing concern about the future supplies. Thus, much attention has been dedicated to the utilization of biomass as an energy resource. In this respect, orange peel has become a material of great interest, especially to Brazil, which generates around 9.5 million tons of this waste per year. To this end, the authors studied the kinetics of the thermal processing of dried orange peel in inert and oxidizing atmosphere. The thermodynamic parameters were determined by the Ozawa-Flynn-Wall method for the global process observed during heating from the 25°C up to 800°C. The thermal analysis in air and nitrogen showed 3-2 stages of mass loss, respectively, with approximately 20% residual mass under a nitrogen atmosphere. The increase in the values of activation energy for the conversion points between 20% and 60% for thermal effects in air and nitrogen atmosphere was observed. The activation energy obtained in an oxidizing atmosphere was higher than that obtained under a nitrogen atmosphere. The fourier-transform infrared spectroscopy and X-ray diffraction analysis showed that the material has a high level of complexity with the presence of alkali and alkaline earth groups as well as phosphate, plus substances such as pectin, cellulose and lignin.

COMPARISON BETWEEN ASPHALTENES (SUB)FRACTIONS EXTRACTED FROM TWO DIFFERENT ASPHALTIC RESIDUES: CHEMICAL CHARACTERIZATION AND PHASE BEHAVIOR

Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (sub)fractions were extracted from an asphaltic residue (AR02), characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01) described in a previous article. The (sub)fractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN), presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

Evolution of Bioaffinity Reagents by Phage Display

Antibodies are natural binding proteins produced in vertebrates as a response to invading pathogens and foreign substances. Because of their capability for tight and specific binding, antibodies have found use as binding reagents in research and diagnostics. Properties of cloned recombinant antibodies can be further improved by means of in vitro evolution, combining mutagenesis with subsequent phage display selection. It is also possible to isolate entirely new antibodies from vast naïve or synthetic antibody libraries by phage display. In this study, library techniques and phage display selection were applied in order to optimise binding scaffolds and antigen recognition of antibodies, and to evolve new and improved bioaffinity reagents. Antibody libraries were generated by random and targeted mutagenesis. Expression and stability were mainly optimised by the random methods whereas targeted randomisation of the binding site residues was used for optimising the binding properties. Trinucleotide mutagenesis allowed design of defined randomisation patterns for a synthetic antibody library. Improved clones were selected by phage display. Capture by a specific anti- DHPS antibody was exploited in the selection of improved phage display of DHPS. Efficient selection for stability was established by combining phage display selection with denaturation under reducing conditions. Broad-specific binding of a generic anti-sulfonamide antibody was improved by selection with one of the weakest binding sulfonamides. In addition, p9 based phage display was studied in affinity selection from the synthetic library. A TIM barrel protein DHPS was engineered for efficient phage display by combining cysteinereplacement with random mutagenesis. The resulting clone allows use of phage display in further engineering of DHPS and possibly use as an alternative-binding scaffold. An anti-TSH scFv fragment, cloned from a monoclonal antibody, was engineered for improved stability to better suite an immunoassay. The improved scFv tolerates 8 – 9 °C higher temperature than the parental scFv and should have sufficient stability to be used in an immunoanalyser with incubation at 36 °C. The anti-TSH scFv fragment was compared with the corresponding Fab fragment and the parental monoclonal antibody as a capturing reagent in a rapid 5-min immunoassay for TSH. The scFv fragment provided some benefits over the conventionally used Mab in anayte-binding capacity and assay kinetics. However, the recombinant Fab fragment, which had similar kinetics to the scFv, provided a more sensitive and reliable assay than the scFv. Another cloned scFv fragment was engineered in order to improve broad-specific recognition of sulfonamides. The improved antibody detects different sulfonamides at concentrations below the maximum residue limit (100 μg/kg in EU and USA) and allows simultaneous screening of different sulfonamide drug residues. Finally, a synthetic antibody library was constructed and new antibodies were generated and affinity matured entirely in vitro. These results illuminate the possibilities of phage display and antibody engineering for generation and optimisation of binding reagents in vitro and indicate the potential of recombinant antibodies as affinity reagents in immunoassays.

Visualization of communication system testing logs

During the past decades testing has matured from ad-hoc activity into being an integral part of the development process. The benefits of testing are obvious for modern communication systems, which operate in heterogeneous environments amongst devices from various manufacturers. The increased demand for testing also creates demand for tools and technologies that support and automate testing activities. This thesis discusses applicability of visualization techniques in the result analysis part of the testing process. Particularly, the primary focus of this work is visualization of test execution logs produced by a TTCN-3 test system. TTCN-3 is an internationally standardized test specification and implementation language. The TTCN-3 standard suite includes specification of a test logging interface and a graphical presentation format, but no immediate relationship between them. This thesis presents a technique for mapping the log events to the graphical presentation format along with a concrete implementation, which is integrated with the Eclipse Platform and the OpenTTCN Tester toolchain. Results of this work indicate that for majority of the log events, a visual representation may be derived from the TTCN-3 standard suite. The remaining events were analysed and three categories relevant in either log analysis or implementation of the visualization tool were identified: events indicating insertion of something into the incoming queue of a port, events indicating a mismatch and events describing the control flow during the execution. Applicability of the results is limited into the domain of TTCN-3, but the developed mapping and the implementation may be utilized with any TTCN-3 tool that is able to produce the execution log in the standardized XML format.

Thermal behavior of alginic acid and its sodium salt

An evaluation of hydration and thermal decomposition of HAlg and its sodium salt is described using thermogravimetry (TG) and differential scanning calorimetry (DSC). TG curves in N2 and air, were obtained for alginic acid showed two decomposition steps attributed to loss of water and polymer decomposition respectively. The sodium alginate decomposed in three steps. The first attributed to water loss, followed by the formation of a carbonaceous residue and finally the Na2CO3. DSC curves presented peaks in agreement with the TG data. In the IR alginic acid presented bands at 1730 and 1631 cm-1, while sodium alginate presented a doublet at 1614 e 1431 cm-1, evidencing the presence of salified carboxyl groups.

Photo-Fenton process for treating biological laboratory wastewater containing formaldehyde

Laboratories consume great amounts of hazardous chemicals substances and consequently generate wastewater containing them, for example formaldehyde. This substance is widely utilized to preserve biological samples generating many liters of this residue every year. The present work proposes the use of the photo-Fenton process to treat formaldehyde wastewater using sunlight irradiation. Some aspects were investigated such as the iron source, sample and hydrogen peroxide concentration and also the use of stirred systems. The use of ferrioxalate (0.5 mmol L-1) improved the efficiency of the process in relation to the use of iron nitrate, while at least 1.0 mol L-1 H2O2 is necessary to treat the sample of the 500 mg C L-1. Under these conditions, every formaldehyde detectable was degradeted and 89% of the dissolved organic carbon was removed in two hours of exposure to sunlight. These results are satisfaction considerate for São Paulo State Environmental Agency.

Optimization of NMP extraction in 1, 3-butadiene production line

N-methylpyrrolidone is a powerful solvent for variety of chemical processes due to its vast chemical properties. It has been used in manufacturing processes of polymers, detergents, pharmaceuticals rubber and many more chemical substances. However, it creates large amount of residue in some of these processes which has to be dealt with. Many well known methods such as BASF in rubber producing units have tried to regenerate the solvent at the end of each run, however, there is still discarding of large amount of residue containing NMP, which over time, could cause environmental concerns. In this study, we have tried to optimize regeneration of the NMP extraction from butadiene production. It is shown that at higher temperatures NMP is separated from the residue with close to 90% efficiency, and the solvent residue proved to be the most effective with a 6: 1 ratio.