Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, 2016. / Submitted by Fernanda Percia França (fernandafranca@bce.unb.br) on 2016-05-04T13:42:07Z No. of bitstreams: 1 2016_CamilaSantosDourado_Parcial.pdf: 897868 bytes, checksum: 4c2fbabe28298cf0c58562430c485411 (MD5) / Approved for entry into archive by Patrícia Nunes da Silva(patricia@bce.unb.br) on 2016-05-15T13:29:54Z (GMT) No. of bitstreams: 1 2016_CamilaSantosDourado_Parcial.pdf: 897868 bytes, checksum: 4c2fbabe28298cf0c58562430c485411 (MD5) / Made available in DSpace on 2016-05-15T13:29:54Z (GMT). No. of bitstreams: 1 2016_CamilaSantosDourado_Parcial.pdf: 897868 bytes, checksum: 4c2fbabe28298cf0c58562430c485411 (MD5) / O N-nitrosoglifosato (NNG) é uma impureza altamente tóxica inerente aos produtos à base de glifosato, que é obtida durante a síntese deste herbicida. Órgãos reguladores nacionais e internacionais estabeleceram o limite máximo de 1,0 mg kg-1 de NNG nos produtos técnicos de glifosato. Apesar desta relevância existem poucos métodos para essa determinação e que ainda são baseados em técnicas e procedimentos de derivatização complexos e demorados. Este trabalho tem por objetivo o desenvolvimento de um método alternativo baseado na determinação indireta do NNG pela reação de Griess, com automação de duas etapas de preparo de amostra através de um sistema de análises por injeção sequencial – SIA, que proporciona ao procedimento analítico rapidez, simplicidade e maior sensibilidade. As etapas de preparo de amostra automatizadas consistiram na derivatização por fotólise e extração em fase sólida. A fotólise do NNG apresentou expressivas vantagens frente a derivatização química, através da utilização da radiação ultravioleta em 254 nm para a clivagem da ligação N-NO que forma espécies NO2-. Esses íons foram concentrados em uma fase sólida de troca aniônica e eluídos com o próprio reagente de Griess para posterior determinação em 540 nm. O método sequencial estabelecido com fotoderivatização e extração em linha apresentou resposta linear para uma ampla faixa de trabalho de 0,05 a 0,75 mg L-1 NNG. O limite de detecção foi estimado em 3,1 x 10-2mg L-1 , cerca de 32 vezes menor que o limite máximo estabelecido pela normativa e o coeficiente de variação para três injeções de 0,05 mg L-1 de NNG foi de 3,74%. O fator de pré–concentração da fase sólida igual a 12 vezes e reprodutibilidade da mesma foi de 48 extrações sucessivas sem mudanças significativas no sinal analítico. Ensaios de recuperação de NNG em diferentes proporções de amostras de produto técnico de glifosato (1:10, 1:100 e 1:1000) apontaram que pode ser possível a determinação de NNG em baixas concentrações de glifosato como, 10 mg L-1. / N-nitrosoglyphosate (NNG) is considered a highly toxic impurity originated during the glyphosate synthesis process. National and international regulatory agencies fixed the maximum limit of 1.0 mg kg-1 of NNG in technical glyphosate. In despite of this relevance, there are few methods for this determination based on complex procedures and time-consuming derivatization techniques. In this way, the aim of this work is to develop an alternative method based on indirect determination of NNG by Griess reaction, with automation of two sample treatment steps through of a sequential injection system - SIA that adds a fast and simple analytical procedure besides increase of sensitivity. Automated sample treatment steps consisted of derivatization by photolysis and solid phase extraction. The photolysis of NNG presented significant advantages over chemical derivatization, because of ultraviolet radiation at 254 nm that provides the cleavage of the N-NO, producing NO2- species. These ions were concentrated in an anion exchange solid phase and eluted with Griess reagent for subsequent determination at 540 nm. The sequential method with online extraction and photoderivatization provided a linear response in a concentration range of 0.05 to 0.75 mg L-1 NNG. A detection limit was estimated as 3.1 x 10-2 mg L-1, that is approximately 32 times higher than the maximum limit established by the regulatory agencies. The coefficient of variation to three injections of the 0.05 mg L-1 of NNG was estimated in 3,74%. The preconcentration factor of the solid phase resulted in 12 times and reproducibility was 48 successive extractions without significant changes in the analytical signal. Recovery tests of 1.0 mg L-1 NNG for different amounts of technical glyphosate solid samples (1:10, 1: 100 and 1: 1000) showed that can be possible to determine NNG at lower concentrations of glyphosate as, 10 mg L-1.

L’évolution du web, de ce qui était typiquement connu comme un moyen de communication à sens unique en mode conversationnel, a radicalement changé notre manière de traiter l’information. Des sites de médias sociaux tels que Flickr et Facebook, offrent des espaces d’échange et de diffusion de l’information. Une information de plus en plus riche, mais aussi personnelle, et qui s’organise, le plus souvent, autour d’événements de la vie réelle. Ainsi, un événement peut être perçu comme un ensemble de vues personnelles et locales, capturées par différents utilisateurs. Identifier ces différentes instances permettrait, dès lors, de reconstituer une vue globale de l’événement. Plus particulièrement, lier différentes instances d’un même événement profiterait à bon nombre d’applications tel que la recherche, la navigation ou encore le filtrage et la suggestion de contenus. L’objectif principal de cette thèse est l’identification du contenu multimédia, associé à un événement dans de grandes collections d’images. Une première contribution est une méthode de recherche d’événements basée sur le contenu visuel. La deuxième contribution est une approche scalable et distribuée pour la construction de graphes des K plus proches voisins. La troisième contribution est une méthode collaborative pour la sélection de contenu pertinent. Plus particulièrement, nous nous intéresserons aux problèmes de génération automatique de résumés d’événements et suggestion de contenus dans les médias sociaux. / The ease of publishing content on social media sites brings to the Web an ever increasing amount of user generated content captured during, and associated with, real life events. Social media documents shared by users often reflect their personal experience of the event. Hence, an event can be seen as a set of personal and local views, recorded by different users. These event records are likely to exhibit similar facets of the event but also specific aspects. By linking different records of the same event occurrence we can enable rich search and browsing of social media events content. Specifically, linking all the occurrences of the same event would provide a general overview of the event. In this dissertation we present a content-based approach for leveraging the wealth of social media documents available on the Web for event identification and characterization. To match event occurrences in social media, we develop a new visual-based method for retrieving events in huge photocollections, typically in the context of User Generated Content. The main contributions of the thesis are the following : (1) a new visual-based method for retrieving events in photo collections, (2) a scalable and distributed framework for Nearest Neighbors Graph construction for high dimensional data, (3) a collaborative content-based filtering technique for selecting relevant social media documents for a given event.