Desenvolvimento de métodos para quantificação de benzilpenicilina em medicamentos veterinários e seus resíduos em leite bovino e caprino por UFLC-DAD

The Benzylpenicillin (PENG) have been as the active ingredient in veterinary medicinal products, to increase productivity, due to its therapeutic properties. However, one of unfortunate quality and used indiscriminately, resulting in residues in foods exposed to human consumption, especially in milk that is essential to the diet of children and the ageing. Thus, it is indispensable to develop new methods able to detect this waste food, at levels that are toxic to human health, in order to contribute to the food security of consumers and collaborate with regulatory agencies in an efficient inspection. In this work, were developed methods for the quality control of veterinary drugs based on Benzylpenicillin (PENG) that are used in livestock production. Additionally, were validated methodologies for identifying and quantifying the antibiotic residues in milk bovine and caprine. For this, the analytical control was performed two steps. At first, the groups of samples of medicinal products I, II, III, IV and V, individually, were characterized by medium infrared spectroscopy (4000 – 600 cm-1). Besides, 37 samples, distributed in these groups, were analyzed by spectroscopy in the ultraviolet and near infrared region (UV VIS NIR) and Ultra Fast Liquid Chromatograph coupled to linear arrangement photodiodes (UFLC-DAD). The results of the characterization indicated similarities, between PENG and reference standard samples, primarily in regions of 1818 to 1724 cm-1 of ν C=O that shows primary amides features of PENG. The method by UFLC-DAD presented R on 0.9991. LOD of 7.384 × 10-4 μg mL-1. LOQ of 2.049 × 10-3 μg mL-1. The analysis shows that 62.16% the samples presented purity ≥ 81.21%. The method by spectroscopy in the UV VIS NIR presented medium error ≤ 8 – 12% between the reference and experimental criteria, indicating is a secure choice for rapid determination of PENG. In the second stage, was acquiring a method for the extraction and isolation of PENG by the addition of buffer McIlvaine, used for precipitation of proteins total, at pH 4.0. The results showed excellent recovery values PENG, being close to 92.05% of samples of bovine milk (method 1). While samples of milk goats (method 2) the recovery of PENG were 95.83%. The methods for UFLC-DAD have been validated in accordance with the maximum residue limit (LMR) of 4 μg Kg-1 standardized by CAC/GL16. Validation of the method 1 indicated R by 0.9975. LOD of 7.246 × 10-4 μg mL-1. LOQ de 2.196 × 10-3 μg mL-1. The application of the method 1 showed that 12% the samples presented concentration of residues of PENG > LMR. The method 2 indicated R by 0.9995. LOD 8.251 × 10-4 μg mL-1. LOQ de 2.5270 × 10-3 μg mL-1. The application of the method showed that 15% of the samples were above the tolerable. The comparative analysis between the methods pointed better validation for LCP samples, because the reduction of the matrix effect, on this account the tcalculs < ttable, caused by the increase of recovery of the PENG. In this mode, all the operations developed to deliver simplicity, speed, selectivity, reduced analysis time and reagent use and toxic solvents, particularly if compared to the established methodologies.

Desenvolvimento de métodos para quantificação de benzilpenicilina em medicamentos veterinários e seus resíduos em leite bovino e caprino por UFLC-DAD

The Benzylpenicillin (PENG) have been as the active ingredient in veterinary medicinal products, to increase productivity, due to its therapeutic properties. However, one of unfortunate quality and used indiscriminately, resulting in residues in foods exposed to human consumption, especially in milk that is essential to the diet of children and the ageing. Thus, it is indispensable to develop new methods able to detect this waste food, at levels that are toxic to human health, in order to contribute to the food security of consumers and collaborate with regulatory agencies in an efficient inspection. In this work, were developed methods for the quality control of veterinary drugs based on Benzylpenicillin (PENG) that are used in livestock production. Additionally, were validated methodologies for identifying and quantifying the antibiotic residues in milk bovine and caprine. For this, the analytical control was performed two steps. At first, the groups of samples of medicinal products I, II, III, IV and V, individually, were characterized by medium infrared spectroscopy (4000 – 600 cm-1). Besides, 37 samples, distributed in these groups, were analyzed by spectroscopy in the ultraviolet and near infrared region (UV VIS NIR) and Ultra Fast Liquid Chromatograph coupled to linear arrangement photodiodes (UFLC-DAD). The results of the characterization indicated similarities, between PENG and reference standard samples, primarily in regions of 1818 to 1724 cm-1 of ν C=O that shows primary amides features of PENG. The method by UFLC-DAD presented R on 0.9991. LOD of 7.384 × 10-4 μg mL-1. LOQ of 2.049 × 10-3 μg mL-1. The analysis shows that 62.16% the samples presented purity ≥ 81.21%. The method by spectroscopy in the UV VIS NIR presented medium error ≤ 8 – 12% between the reference and experimental criteria, indicating is a secure choice for rapid determination of PENG. In the second stage, was acquiring a method for the extraction and isolation of PENG by the addition of buffer McIlvaine, used for precipitation of proteins total, at pH 4.0. The results showed excellent recovery values PENG, being close to 92.05% of samples of bovine milk (method 1). While samples of milk goats (method 2) the recovery of PENG were 95.83%. The methods for UFLC-DAD have been validated in accordance with the maximum residue limit (LMR) of 4 μg Kg-1 standardized by CAC/GL16. Validation of the method 1 indicated R by 0.9975. LOD of 7.246 × 10-4 μg mL-1. LOQ de 2.196 × 10-3 μg mL-1. The application of the method 1 showed that 12% the samples presented concentration of residues of PENG > LMR. The method 2 indicated R by 0.9995. LOD 8.251 × 10-4 μg mL-1. LOQ de 2.5270 × 10-3 μg mL-1. The application of the method showed that 15% of the samples were above the tolerable. The comparative analysis between the methods pointed better validation for LCP samples, because the reduction of the matrix effect, on this account the tcalculs < ttable, caused by the increase of recovery of the PENG. In this mode, all the operations developed to deliver simplicity, speed, selectivity, reduced analysis time and reagent use and toxic solvents, particularly if compared to the established methodologies.

Estudo e desenvolvimento de algoritmos criptográficos para redes de sensores sem fio, utilizando técnicas de programação genética

Cryptography is the main form to obtain security in any network. Even in networks with great energy consumption restrictions, processing and memory limitations, as the Wireless Sensors Networks (WSN), this is no different. Aiming to improve the cryptography performance, security and the lifetime of these networks, we propose a new cryptographic algorithm developed through the Genetic Programming (GP) techniques. For the development of the cryptographic algorithm’s fitness criteria, established by the genetic GP, nine new cryptographic algorithms were tested: AES, Blowfish, DES, RC6, Skipjack, Twofish, T-DES, XTEA and XXTEA. Starting from these tests, fitness functions was build taking into account the execution time, occupied memory space, maximum deviation, irregular deviation and correlation coefficient. After obtaining the genetic GP, the CRYSEED and CRYSEED2 was created, algorithms for the 8-bits devices, optimized for WSNs, i.e., with low complexity, few memory consumption and good security for sensing and instrumentation applications.

Estudo e desenvolvimento de algoritmos criptográficos para redes de sensores sem fio, utilizando técnicas de programação genética

Cryptography is the main form to obtain security in any network. Even in networks with great energy consumption restrictions, processing and memory limitations, as the Wireless Sensors Networks (WSN), this is no different. Aiming to improve the cryptography performance, security and the lifetime of these networks, we propose a new cryptographic algorithm developed through the Genetic Programming (GP) techniques. For the development of the cryptographic algorithm’s fitness criteria, established by the genetic GP, nine new cryptographic algorithms were tested: AES, Blowfish, DES, RC6, Skipjack, Twofish, T-DES, XTEA and XXTEA. Starting from these tests, fitness functions was build taking into account the execution time, occupied memory space, maximum deviation, irregular deviation and correlation coefficient. After obtaining the genetic GP, the CRYSEED and CRYSEED2 was created, algorithms for the 8-bits devices, optimized for WSNs, i.e., with low complexity, few memory consumption and good security for sensing and instrumentation applications.

Photographs of the Mount Meager, southwestern British Columbia

On August 6, 2010, a large (~50 Mm**3) debris avalanche occurred on the flank of Mount Meager in the southern Coast Mountains of British Columbia, Canada. We studied the deposits to infer the morphodynamics of the landslide from initiation to emplacement. Structure from motion (SfM) photogrammetry, based on oblique photos taken with a standard SLR camera during a low helicopter traverse, was used to create high-resolution orthophotos and base maps. Interpretation of the images and maps allowed us to recognize two main rheological phases in the debris avalanche. Just below the source area, in the valley of Capricorn Creek, the landslide separated into two phases, one water-rich and more mobile, and the other water-poor and less mobile. The water-rich phase spread quickly, achieved high superelevation on the valley sides, and left distal scattered deposits. The main water-poor phase moved more slowly, did not superelevate, and formed a thick continuous deposit (up to ~30 m) on the valley floor. The water-poor flow deposit has structural features such as hummocks, brittle-ductile faults, and shear zones. Our study, based on a freshly emplaced deposit, advances understanding of large mass movements by showing that a single landslide can develop multiple rheology phases with different behaviours. Rheological evolution and separation of phases should always be taken into account to provide better risk assessment scenarios.

Undersampled Critical Branching Processes on Small-World and Random Networks Fail to Reproduce the Statistics of Spike Avalanches

The power-law size distributions obtained experimentally for neuronal avalanches are an important evidence of criticality in the brain. This evidence is supported by the fact that a critical branching process exhibits the same exponent t~3=2. Models at criticality have been employed to mimic avalanche propagation and explain the statistics observed experimentally. However, a crucial aspect of neuronal recordings has been almost completely neglected in the models: undersampling. While in a typical multielectrode array hundreds of neurons are recorded, in the same area of neuronal tissue tens of thousands of neurons can be found. Here we investigate the consequences of undersampling in models with three different topologies (two-dimensional, small-world and random network) and three different dynamical regimes (subcritical, critical and supercritical). We found that undersampling modifies avalanche size distributions, extinguishing the power laws observed in critical systems. Distributions from subcritical systems are also modified, but the shape of the undersampled distributions is more similar to that of a fully sampled system. Undersampled supercritical systems can recover the general characteristics of the fully sampled version, provided that enough neurons are measured. Undersampling in two-dimensional and small-world networks leads to similar effects, while the random network is insensitive to sampling density due to the lack of a well-defined neighborhood. We conjecture that neuronal avalanches recorded from local field potentials avoid undersampling effects due to the nature of this signal, but the same does not hold for spike avalanches. We conclude that undersampled branching-process-like models in these topologies fail to reproduce the statistics of spike avalanches.

Évaluation de la modélisation de la taille de grain de neige du modèle multi-couches thermodynamique SNOWPACK: implication dans l'évaluation des risques d'avalanches

Résumé: L’Institut pour l'étude de la neige et des avalanches en Suisse (SLF) a développé SNOWPACK, un modèle thermodynamique multi-couches de neige permettant de simuler les propriétés géophysiques du manteau neigeux (densité, température, taille de grain, teneur en eau, etc.) à partir desquelles un indice de stabilité est calculé. Il a été démontré qu’un ajustement de la microstructure serait nécessaire pour une implantation au Canada. L'objectif principal de la présente étude est de permettre au modèle SNOWPACK de modéliser de manière plus réaliste la taille de grain de neige et ainsi obtenir une prédiction plus précise de la stabilité du manteau neigeux à l’aide de l’indice basé sur la taille de grain, le Structural Stability Index (SSI). Pour ce faire, l’erreur modélisée (biais) par le modèle a été analysée à l’aide de données précises sur le terrain de la taille de grain à l’aide de l’instrument IRIS (InfraRed Integrated Sphere). Les données ont été recueillies durant l’hiver 2014 à deux sites différents au Canada : parc National des Glaciers, en Colombie-Britannique ainsi qu’au parc National de Jasper. Le site de Fidelity était généralement soumis à un métamorphisme à l'équilibre tandis que celui de Jasper à un métamorphisme cinétique plus prononcé. Sur chacun des sites, la stratigraphie des profils de densités ainsi des profils de taille de grain (IRIS) ont été complétés. Les profils de Fidelity ont été complétés avec des mesures de micropénétromètre (SMP). L’analyse des profils de densité a démontré une bonne concordance avec les densités modélisées (R[indice supérieur 2]=0.76) et donc la résistance simulée pour le SSI a été jugée adéquate. Les couches d’instabilités prédites par SNOWPACK ont été identifiées à l’aide de la variation de la résistance dans les mesures de SMP. L’analyse de la taille de grain optique a révélé une surestimation systématique du modèle ce qui est en accord avec la littérature. L’erreur de taille de grain optique dans un environnement à l’équilibre était assez constante tandis que l’erreur en milieux cinétique était plus variable. Finalement, une approche orientée sur le type de climat représenterait le meilleur moyen pour effectuer une correction de la taille de grain pour une évaluation de la stabilité au Canada.

The Southern Ischia canyon system: examples of deep sea depositional systems on the continental slope off Campania (Italy)

The Southern Ischia canyon system has been investigated in detail through Multibeam bathymetry and Sparker seismic data and has been put in the geological framework of the deep sea depositional systems off the Campania region. The geological and geomorphological characteristics of the canyon system have been also compared with the characters of the Mediterranean submarine canyons and with the deep sea depositional systems of the Tyrrhenian sea. The Southern Ischia canyon system engraves a narrow continental shelf from Punta Imperatore to Punta San Pancrazio, being limited southwestwards from the relict volcanic edifice of the Ischia Bank. It consists of twenty-two drainage axes, whose planimetric trending has been reconstructed in a sketch morphological map realized through the geological interpretation of Multibeam bathymetry. While the eastern boundary of the canyon system is controlled by extensional tectonics, being limited by a NE-SW trending (anti-Apenninic) normal fault, its western boundary is controlled by volcanism, due to the growth of the Ischia volcanic bank. Submarine gravitational instabilities also acted in relationships to the canyon system, allowing for the individuation of large-scale creeping at the sea bottom and hummocky deposits already interpreted as debris avalanche deposits. Quaternary marine seismic sequences have been reconstructed through a densely spaced seismic grid recorded through a Sparker multitip seismic source, allowing for a detailed observation of steep erosional slopes occurring on the southern flank of the island and related deep sea depositional systems. Important implications of this study will regard the coastal monitoring and beach nourishment of the southern flank of the island, being involved by a strong erosion of marine and coastal systems.

Stratigraphic Architecture of Deep Sea Depositional Systems in the Southern Tyrrhenian Sea: Some Examples in the Ischia and Stromboli Volcanic Islands (Southern Italy)

The stratigraphic architecture of deep sea depositional systems has been discussed in detail. Some examples in Ischia and Stromboli volcanic islands (Southern Tyrrhenian sea, Italy) are here shown and discussed. The submarine slope and base of slope depositional systems represent a major component of marine and lacustrine basin fills, constituting primary targets for hydrocarbon exploration and development. The slope systems are characterized by seven seismic facies building blocks, including the turbiditic channel fills, the turbidite lobes, the sheet turbidites, the slide, slump and debris flow sheets, lobes and tongues, the fine-grained turbidite fills and sheets, the contourite drifts and finally, the hemipelagic drapes and fills. Sparker profiles offshore Ischia are presented. New seismo-stratigraphic evidence on buried volcanic structures and overlying Quaternary deposits of the eastern offshore of the Ischia Island are here discussed to highlight the implications on marine geophysics and volcanology. Regional seismic sections in the Ischia offshore across buried volcanic structures and debris avalanche and debris flow deposits are here presented and discussed. Deep sea depositional systems in the Ischia Island are well developed in correspondence to the Southern Ischia canyon system. The canyon system engraves a narrow continental shelf from Punta Imperatore to Punta San Pancrazio, being limited southwestwards from the relict volcanic edifice of the Ischia bank. While the eastern boundary of the canyon system is controlled by extensional tectonics, being limited from a NE-SW trending (counter-Apenninic) normal fault, its western boundary is controlled by volcanism, due to the growth of the Ischia volcanic bank. Submarine gravitational instabilities also acted in relationships to the canyon system, allowing for the individuation of large scale creeping at the sea bottom and hummocky deposits already interpreted as debris avalanche deposits. High resolution seismic data (Subbottom Chirp) coupled to high resolution Multibeam bathymetry collected in the frame of the Stromboli geophysical experiment aimed at recording seismic active data and tomography of the Stromboli Island are here presented. A new detailed swath bathymetry of Stromboli Island is here shown and discussed to reconstruct an up-to-date morpho-bathymetry and marine geology of the area, compared to volcanologic setting of the Aeolian volcanic complex. The Stromboli DEM gives information about the submerged structure of the volcano, particularly about the volcano-tectonic and gravitational processes involving the submarine flanks of the edifice. Several seismic units have been identified around the volcanic edifice and interpreted as volcanic acoustic basement pertaining to the volcano and overlying slide chaotic bodies emplaced during its complex volcano-tectonic evolution. They are related to the eruptive activity of Stromboli, mainly poliphasic and to regional geological processes involving the geology of the Aeolian Arc.

Localização em espaços interiores por luz visível para robôs móveis

Esta dissertação investiga a localização em espaços interiores através da comunicação por luz visível para robôs móveis, com base nos LEDs fixos nos edifícios, dando particular atenção à simulação e desenho do sensor, com vista ao desenvolvimento de um sensor de localização. Explica-se o crescimento da tecnologia LED e da constante necessidade de localização do homem em espaços interiores. Apresentado algumas características do LED e dos foto-detetores existentes. Com uma breve referencia a algumas das comunicações por luz visível de baixo débito possíveis de implementar. O desenvolvimento do protótipo do sensor inicia-se, principalmente, pela simulação de alguns dispositivos essenciais e das suas caraterísticas, como o emissor LED no controlo do ^angulo de meia potência (HPA) e a altura a que se encontra, e no recetor foto-díodo e a sua restrição de campo de visão (FOV). Simula-se o sensor pretendido com o número de foto-díodos necessários otimizando o espaço físico disponível e fazendo não só um refinamento no FOV mas também na distribuição espacial dos foto-díodos com funções predefinidas para a redução de incertezas de decisão de localização do robô. Estes resultados permitiram a construção física do sensor, desde o suporte para os foto-díodos, tendo em conta todas as medidas durante as simulações, e terminando com o desenvolvimento dos sensores e a sua integração completa. O tratamento de dados da leitura dos sinais recebidos do sensor são tratados por um microcontrolador, permitindo calcular parâmetros fundamentais no cálculo da posição. No final, os resultados teóricos bem como os práticos obtidos ao longo do desenvolvimento e possíveis propostas para trabalhos futuros que beneficiam desta investigação

The experimental determination of impact ionization coefficients in gallium arsenide and indium phosphide

U of I Only

Undersampled Critical Branching Processes on Small-World and Random Networks Fail to Reproduce the Statistics of Spike Avalanches

The power-law size distributions obtained experimentally for neuronal avalanches are an important evidence of criticality in the brain. This evidence is supported by the fact that a critical branching process exhibits the same exponent t~3=2. Models at criticality have been employed to mimic avalanche propagation and explain the statistics observed experimentally. However, a crucial aspect of neuronal recordings has been almost completely neglected in the models: undersampling. While in a typical multielectrode array hundreds of neurons are recorded, in the same area of neuronal tissue tens of thousands of neurons can be found. Here we investigate the consequences of undersampling in models with three different topologies (two-dimensional, small-world and random network) and three different dynamical regimes (subcritical, critical and supercritical). We found that undersampling modifies avalanche size distributions, extinguishing the power laws observed in critical systems. Distributions from subcritical systems are also modified, but the shape of the undersampled distributions is more similar to that of a fully sampled system. Undersampled supercritical systems can recover the general characteristics of the fully sampled version, provided that enough neurons are measured. Undersampling in two-dimensional and small-world networks leads to similar effects, while the random network is insensitive to sampling density due to the lack of a well-defined neighborhood. We conjecture that neuronal avalanches recorded from local field potentials avoid undersampling effects due to the nature of this signal, but the same does not hold for spike avalanches. We conclude that undersampled branching-process-like models in these topologies fail to reproduce the statistics of spike avalanches.

Desenvolvimento de sistema automatizado para o monitoramento da degradação de resíduos de brometo de etídio

Tese (doutorado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.