<p>In this thesis some multivariate spectroscopic methods for the analysis of solutions are proposed. Spectroscopy and multivariate data analysis form a powerful combination for obtaining both quantitative and qualitative information and it is shown how spectroscopic techniques in combination with chemometric data evaluation can be used to obtain rapid, simple and efficient analytical methods. These spectroscopic methods consisting of spectroscopic analysis, a high level of automation and chemometric data evaluation can lead to analytical methods with a high analytical capacity, and for these methods, the term high-capacity analysis (HCA) is suggested. It is further shown how chemometric evaluation of the multivariate data in chromatographic analyses decreases the need for baseline separation. </p><p>The thesis is based on six papers and the chemometric tools used are experimental design, principal component analysis (PCA), soft independent modelling of class analogy (SIMCA), partial least squares regression (PLS) and parallel factor analysis (PARAFAC). The analytical techniques utilised are scanning ultraviolet-visible (UV-Vis) spectroscopy, diode array detection (DAD) used in non-column chromatographic diode array UV spectroscopy, high-performance liquid chromatography with diode array detection (HPLC-DAD) and fluorescence spectroscopy. The methods proposed are exemplified in the analysis of pharmaceutical solutions and serum proteins.</p><p>In Paper I a method is proposed for the determination of the content and identity of the active compound in pharmaceutical solutions by means of UV-Vis spectroscopy, orthogonal signal correction and multivariate calibration with PLS and SIMCA classification. Paper II proposes a new method for the rapid determination of pharmaceutical solutions by the use of non-column chromatographic diode array UV spectroscopy, i.e. a conventional HPLC-DAD system without any chromatographic column connected. In Paper III an investigation is made of the ability of a control sample, of known content and identity to diagnose and correct errors in multivariate predictions something that together with use of multivariate residuals can make it possible to use the same calibration model over time. In Paper IV a method is proposed for simultaneous determination of serum proteins with fluorescence spectroscopy and multivariate calibration. Paper V proposes a method for the determination of chromatographic peak purity by means of PCA of HPLC-DAD data. In Paper VI PARAFAC is applied for the decomposition of DAD data of some partially separated peaks into the pure chromatographic, spectral and concentration profiles. </p>

Submitted by Luanna Matias (lua_matias@yahoo.com.br) on 2015-02-06T11:55:41Z No. of bitstreams: 2 Dissertação - Guilherme Martins Teixeira Borges - 2014.pdf: 3642605 bytes, checksum: daab13868d7272e84e616f7f49ffec97 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-02-19T12:54:15Z (GMT) No. of bitstreams: 2 Dissertação - Guilherme Martins Teixeira Borges - 2014.pdf: 3642605 bytes, checksum: daab13868d7272e84e616f7f49ffec97 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-02-19T12:54:15Z (GMT). No. of bitstreams: 2 Dissertação - Guilherme Martins Teixeira Borges - 2014.pdf: 3642605 bytes, checksum: daab13868d7272e84e616f7f49ffec97 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-07-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This dissertation aims to analyze the relationship between the action of landless rural workers, especially the activities of members of the Landless Rural Workers Movement (MST), and the criminalization process of his conducts by Criminal Law. Therefore, this study aims to verify scientifically know as the criminal knowledge can be a legitimate instrument to promote the criminalization and stigmatization of these landless workers. Thus, the work takes as its starting point the characterization of their research subject, namely, the landless rural workers in its meaning of agrarian social movement, why it held an approach to the construction of social inequality and its correlation with the emergence and structuring of social movements, for, in the end, weave important considerations about what is meant by social Movement and Agrarian MST. Following aimed to explain how the criminal know contemporary Brazilian still shows a strong influence of the positivist criminological thought inaugurated by the Italian school centuries ago. It is shown how positivist criminology was responsible for creating a conception of social dangerousness and embrace a segregationist and selective criminological project, such that those individuals who were "classified" as a threat, should be removed from social interaction. We report how this discourse entered " the back door " of the criminal laws homelands and enabled the creation of an ideology of social defense and the criminalization of minorities (poor, landless ruais, black and so on). Finally, aiming to demonstrate the hypothesis elected, held a review of the work conducted by the Joint Parliamentary Committee of Inquiry ( CPMI ) and Urban Land Reform, known as "CPMI of Land ", specially her Final Report , highlighting Project Senate n . 264/2006 ( PLS No. 264 /06 ) and Project of House of Representatives n . 7485/2006 ( PL No. 7485 / 06 ), whose proposals are, appropriately, intended to spearhead a process of criminalization of landless legitimized by criminal law. / A presente dissertação objetiva analisar a relação entre a atuação dos trabalhadores rurais sem terra, em especial a atuação dos integrantes do Movimento dos Trabalhadores Rurais Sem Terra (MST), e o processo de criminalização de suas condutas por parte dos operadores do direito. Para tanto, este estudo se propõe a verificar cientificamente como o saber penal pode ser um instrumento legítimo para promover a criminalização e estigmatização penal destes trabalhadores. Desta forma, o trabalho toma como ponto de partida a caracterização do seu sujeito de pesquisa, qual seja, os trabalhadores rurais sem terra em sua acepção de movimento social agrário, razão por que se realizou uma abordagem da construção das desigualdades sociais e a sua correlação com o surgimento e estruturação dos movimentos sociais, para, ao final, tecer importantes considerações sobre o que se entende por Movimento Social Agrário e MST. Na sequência, objetivou-se explanar como o saber penal brasileiro contemporâneo ainda ilustra uma forte influência do pensamento criminológico positivista inaugurado pela Escola Italiana séculos atrás. Demonstra-se como a criminologia positivista foi responsável por criar uma concepção de periculosidade social e abraçar um projeto criminológico segregacionista e seletivo, de tal forma que aqueles indivíduos os quais fossem “classificados” como uma ameaça, deviam ser afastados do convívio social. Relata-se como esse discurso adentrou “pelas portas dos fundos” das legislações penais pátrias e possibilitou a criação de uma ideologia da defesa social e da criminalização das minorias (pobres, trabalhadores ruais sem terra, negros e etc.). Ao final, objetivando demonstrar factivelmente a hipótese de trabalho eleita, realizou-se uma análise dos trabalhos realizados pela Comissão Parlamentar Mista de Inquérito (CPMI) da Reforma Agrária e Urbana, conhecida como “CPMI da Terra”, em especial os encaminhamentos por ela declarados em seu Relatório Final, com destaque para o Projeto de Lei do Senado n. 264, de 2006 (PLS N. 264/06) e o Projeto de Lei da Câmara dos Deputados n. 7485/2006 (PL N. 7485/06), cujas propostas revelam, com propriedade, a intenção de encabeçar um processo de criminalização dos trabalhadores rurais sem terra legitimado pelo próprio Direito Penal.

Text in English / Developments in Internet technology and pervasive computing over the past two and half decades have resulted in a variety of Web-based applications (WBAs) that provide products and services to online users or customers. The Internet is used not only to transfer information via the web but is increasingly used to provide electronic services including business transactions, information-delivery and social networking, as well as e-government, e-health and e-learning. For such organisations, e-service quality, usability and user experience are considered to be critical determinants of their products’ or services’ success. Many studies to model these three concepts separately have been undertaken as part of broader studies of software quality or service quality modelling. However, to the current researcher’s knowledge, none of the studies have focussed on proposing an evaluation model that integrates and combines the three of them. This research is an effort to fill that gap. The primary purpose of this mixed-methods research was to develop a conceptual integrated model for evaluating e-service quality, usability and user experience (e-SQUUX) of WBAs and then contextualise it to evaluation of a University web portal (UWP). This was undertaken using an exploratory sequential research design. During a qualitative phase, an extensive extensive systematic literature review of 264 relevant sources relating to dimensions of e-service quality, usability and user experience, was undertaken to derive an integrated conceptual e-service quality, usability and user experience (e-SQUUX) Model for evaluating WBAs. The model was then empirically refined through a sequential series of validations, thus developing various versions of the e-SQUUX Model. First, it was content validated by a set of four expert reviewers. Second, during the quantitative phase, in the context of a University web portal, a questionnaire survey was conducted that included a comprehensive pilot study with 29 partipants, prior to the main survey. The main survey data from 174 particiapants was used to determine a validated model, using Exploratory factor analysis (EFA), followed by producing a structural model, using partial least square – structural equation modelling (PLS-SEM). This version consisted of the components of the final e-SQUUX Model. Consequently, the research enriches the body of knowledge on IS and HCI by providing the e-SQUUX Model as an evaluation tool. For designers, developers and managers of UWPs, the model serves as a customisable set of evaluation criteria and also provides specific recommendations for design. In line with the Exploratory sequential design of mixed methods research, the findings of the qualitative work in this research influenced the subsequent quantitative study, since the potential Likert-scale questionnaire items were derived from the definitions and meanings of the components that emanated from the qualitative phase of the study. Consequently, this research is an exemplar for developing an integrated evaluation model for specific facets or domains, and of its application in a particular context, in this case, a University web portal. Keywords: e-service quality, usability, user experience, evaluation model, integrated model, exploratory factor analysis, partial least square – structural equation modelling (PLS-SEM), mixed methods research, Exploratory sequential design, quantitative study, qualitative study, validation, Web-based applications, University web portal / Information System / Ph D. (Information Systems)

Le but de cette thèse est de développer des méthodes pratiques plus performantes pour la détection d'instances de classes d'objets de la vie quotidienne dans les images. Nous présentons une famille de détecteurs qui incorporent trois types d'indices visuelles performantes - histogrammes de gradients orientés (Histograms of Oriented Gradients, HOG), motifs locaux binaires (Local Binary Patterns, LBP) et motifs locaux ternaires (Local Ternary Patterns, LTP) - dans des méthodes de discrimination efficaces de type machine à vecteur de support latent (Latent SVM), sous deux régimes de réduction de dimension - moindres carrées partielles (Partial Least Squares, PLS) et sélection de variables par élagage de poids SVM (SVM Weight Truncation). Sur plusieurs jeux de données importantes, notamment ceux du PASCAL VOC2006 et VOC2007, INRIA Person et ETH Zurich, nous démontrons que nos méthodes améliorent l'état de l'art du domaine. Nos contributions principales sont : Nous étudions l'indice visuelle LTP pour la détection d'objets. Nous démontrons que sa performance est globalement mieux que celle des indices bien établies HOG et LBP parce qu'elle permet d'encoder à la fois la texture locale de l'objet et sa forme globale, tout en étant résistante aux variations d'éclairage. Grâce à ces atouts, LTP fonctionne aussi bien pour les classes qui sont caractérisées principalement par leurs structures que pour celles qui sont caractérisées par leurs textures. En plus, nous démontrons que les indices HOG, LBP et LTP sont bien complémentaires, de sorte qu'un jeux d'indices étendu qui intègre tous les trois améliore encore la performance. Les jeux d'indices visuelles performantes étant de dimension assez élevée, nous proposons deux méthodes de réduction de dimension afin d'améliorer leur vitesse et réduire leur utilisation de mémoire. La première, basée sur la projection moindres carrés partielles, diminue significativement le temps de formation des détecteurs linéaires, sans réduction de précision ni perte de vitesse d'exécution. La seconde, fondée sur la sélection de variables par l'élagage des poids du SVM, nous permet de réduire le nombre d'indices actives par un ordre de grandeur avec une réduction minime, voire même une petite augmentation, de la précision du détecteur. Malgré sa simplicité, cette méthode de sélection de variables surpasse toutes les autres approches que nous avons mis à l'essai.

In this thesis some multivariate spectroscopic methods for the analysis of solutions are proposed. Spectroscopy and multivariate data analysis form a powerful combination for obtaining both quantitative and qualitative information and it is shown how spectroscopic techniques in combination with chemometric data evaluation can be used to obtain rapid, simple and efficient analytical methods. These spectroscopic methods consisting of spectroscopic analysis, a high level of automation and chemometric data evaluation can lead to analytical methods with a high analytical capacity, and for these methods, the term high-capacity analysis (HCA) is suggested. It is further shown how chemometric evaluation of the multivariate data in chromatographic analyses decreases the need for baseline separation. The thesis is based on six papers and the chemometric tools used are experimental design, principal component analysis (PCA), soft independent modelling of class analogy (SIMCA), partial least squares regression (PLS) and parallel factor analysis (PARAFAC). The analytical techniques utilised are scanning ultraviolet-visible (UV-Vis) spectroscopy, diode array detection (DAD) used in non-column chromatographic diode array UV spectroscopy, high-performance liquid chromatography with diode array detection (HPLC-DAD) and fluorescence spectroscopy. The methods proposed are exemplified in the analysis of pharmaceutical solutions and serum proteins. In Paper I a method is proposed for the determination of the content and identity of the active compound in pharmaceutical solutions by means of UV-Vis spectroscopy, orthogonal signal correction and multivariate calibration with PLS and SIMCA classification. Paper II proposes a new method for the rapid determination of pharmaceutical solutions by the use of non-column chromatographic diode array UV spectroscopy, i.e. a conventional HPLC-DAD system without any chromatographic column connected. In Paper III an investigation is made of the ability of a control sample, of known content and identity to diagnose and correct errors in multivariate predictions something that together with use of multivariate residuals can make it possible to use the same calibration model over time. In Paper IV a method is proposed for simultaneous determination of serum proteins with fluorescence spectroscopy and multivariate calibration. Paper V proposes a method for the determination of chromatographic peak purity by means of PCA of HPLC-DAD data. In Paper VI PARAFAC is applied for the decomposition of DAD data of some partially separated peaks into the pure chromatographic, spectral and concentration profiles.

L'objectif de cette thèse était d'appliquer des méthodes d'analyse multivariées au traitement des données provenant de la spectroscopie de plasma induit par laser (LIBS) et de la spectroscopie térahertz (THz) dans le but d'accroître les performances analytiques de ces techniques.Les spectres LIBS provenaient de campagnes de mesures directes sur différents sites géologiques. Une approche univariée n'a pas été envisageable à cause d'importants effets de matrices et c'est pour cela qu'on a analysé les données provenant des spectres LIBS par réseaux de neurones artificiels (ANN). Cela a permis de quantifier plusieurs éléments mineurs et majeurs dans les échantillons de sol avec un écart relatif de prédiction inférieur à 20% par rapport aux valeurs de référence, jugé acceptable pour des analyses sur site. Dans certains cas, il a cependant été nécessaire de prendre en compte plusieurs modèles ANN, d'une part pour classer les échantillons de sol en fonction d'un seuil de concentration et de la nature de leur matrice, et d'autre part pour prédire la concentration d'un analyte. Cette approche globale a été démontrée avec succès dans le cas particulier de l'analyse du plomb pour un échantillon de sol inconnu. Enfin, le développement d'un outil de traitement par ANN a fait l'objet d'un transfert industriel.Dans un second temps, nous avons traité des spectres d'absorbance terahertz. Ce spectres provenaient de mesures d'absorbance sur des mélanges ternaires de Fructose-Lactose-acide citrique liés par du polyéthylène et préparés sous forme de pastilles. Une analyse semi-quantitative a été réalisée avec succès par analyse en composantes principales (ACP). Puis les méthodes quantitatives de régression par moindres carrés partiels (PLS) et de réseaux de neurons artificiels (ANN) ont permis de prédire les concentrations de chaque constituant de l'échantillon avec une valeur d'erreur quadratique moyenne inférieure à 0.95 %. Pour chaque méthode de traitement, le choix des données d'entrée et la validation de la méthode ont été discutés en détail.

La proximité constitue l'une des préoccupations stratégiques actuelles majeures de la distribution alimentaire. Cette recherche porte sur les raisons de la réhabilitation des formats de proximité et s'intéresse aux représentations de la proximité d'un magasin par les distributeurs et par les consommateurs. Il ressort des analyses qualitatives et quantitatives menées auprès des distributeurs et des consommateurs que cette distance spatiale, temporelle, fonctionnelle et social qui unit un magasin et ses clients est multidimensionnelle. Sept dimensions ont été identifiées : la proximité d'accès, la proximité fonctionnelle, la proximité de processus, la proximité relationnelle, la proximité identitaire, la proximité d'intégration et la proximité d'assortiment. Certains points de convergence et divergence apparaissent dans les représentations de la proximité d'un magasin par les distributeurs et les consommateurs. Plus généralement, tous deux perçoivent les aspects symboliques et fonctionnels du magasin de proximité. Les représentations de la proximité d'un magasin du point de vue des distributeurs sont plus complètes et positives ; les consommateurs se concentrent davantage sur les aspects fonctionnels et utilitaires du magasin de proximité. Le test des hypothèses du modèle théorique (PLS) nous amènent finalement à identifier les antécédents de la proximité perçue d'un magasin (positionnement perçu et localisation géographique) et ses conséquences (intentions d'achat futures, évaluation positive et attachement). Nos résultats démontrent que la localisation géographique ne suffit pas à créer une relation entre client et le magasin. Le distributeur ne doit pas se contenter d'être géographiquement près de son client pour être proche de lui ; il doit dépasser la vision géographique de la proximité pour valoriser d'autres aspects fonctionnels et symboliques

90年代的後期，敏捷式系統發展方法開始被倡導。相對於傳統的系統發展方法，敏捷式系統發展方法著重於回饋機制而非事前的計畫、以人為中心而非以流程為中心。這樣的方法希望能助於提高組織對回應市場、客戶的效率，進而提高效益。目前在商場中使用此方法做為開發工具的企業仍是少數，本研究希望透過探討敏捷式系統發展方法論的使用時機來進行教學，進而得知系統開發人員對於接受敏捷式系統發展方法的關鍵因素，並藉此了解該如何在企業中導入此方法。本研究發現除了使用此方法的能力會影響影響使用意圖之外，在內在因素方面也包含了公司結構與團隊因素，外部因素則包含了顧客與成功案例因素，這些都是接受敏捷式系統發展方法的關鍵因素。本研究希望根據以上的分析結果，提出敏捷式系統發展方法導入之建議，提供組織做為參考用。 / Awareness of agile system development methodologies (SDM) has grown among information systems development community in recent years. Many of their advocates consider the agile and the plan-driven SDMs polar opposites. Indeed there are circumstances where agile SDMs are more suitable than plan-driven SDMs. Yet, there have been few studies on understanding developers’ adoption intention. This paper takes an initial attempt to gauge new generation of software developers’ intention to select agile SDMs. To many of these developers, agile SDMs are relatively new if not unheard of, in order to assess their intention to choose such category of methodologies, this research first introduced the methodologies to a group of 21 IS-major graduate students and discussed how and when to use agile SDMs. Then a survey was conducted, which was comprised of two parts of questions: agile SDM self-efficacy and intention to use. PLS analysis results showed that agile SDM self-efficacy influence the intention to use through performance outcome expectation, personal outcome expectation, and affect. Although the relationship between self-efficacy and anxiety was not confirmed, anxiety does affect intention to use. The fact that direct relationships between all four emotive variables and the intention to use are established implies that in order to encourage the use of agile SDMs, the focus should be emotive variables, and that self efficacy may be just one of various ways to promote the favorable emotional states. In addition, these participates were invited to a three-round Delphi test and analytic hierarchy process to retrieved their concerns about accepting or rejecting agile SDMs. Ten key factors were extracted and categorized. Adding up the pros and cons, team dimension is the most important dimension, which explains individual first concerns about how the collaboration when using agile SDMs. Other than team dimension, customer, corporate structure, project, success cases and methodology dimensions were consistent with the literatures. Thus our study provides a critical understanding of the factors that affect new generation of software developers’ intention to select agile SDM.

Gleichzeitig mit der weit verbreiteten Verwendung von traditionellen einkommens- oder konsumbasierten Maßnahmen zur Messung menschlicher Armut und Entwicklung gibt es seit den späten 70er Jahren zunehmendes Interesse an der Ökonomie des Glücks. Ebenso gibt es einen breiten Literaturbereich, der Indizes definiert und diskutiert hat, die „functionings" auf der Grundlage des „Capabilities Approach“ von Sen (1985) auf sich vereinen, welche auf einer Vielzahl von ideologischen Urteilen und Zielen zur Bestimmung des objektiven Wohlbefindens (1984), S. 187) beruhen. Beide Ansätze sind ähnlich in ihrer Prämisse, dass Einkommen oft eine unzureichende Determinante des Wohlbefindens ist – ein latenter Begriff, dass besser mit anderen, breiteren Definitionen- subjektiv oder objektiviert- erfasst wird. Beide Konzepte des Wohlbefindens wurden im Hinblick auf ihr Verhältnis zum Einkommen untersucht, und es wurde ein klarer Unterschied zwischen Einkommen und diesen beiden Maßnahmen festgestellt. Angesichts der relativen Neuheit und Komplexität beider Ansätze sind sie jedoch bislang selten in wissenschaftlichen Arbeiten zusammengebracht worden. Den dritten Aufsatz in dieser Arbeit ist ein Versuch, diese beiden Ansätze zu kombinieren und damit diese Lücke in der Literatur zu erfüllen. Subjektives Wohlbefinden wird mit verfügbaren Daten, die Zufriedenheit messen, festelegt, während das objektive Wohlbefinden durch einen Multidimensional Poverty Index (MPI) operationalisiert wird (Alkire & Santos, 2010). Der MPI ist einer der neuesten Versuche zur Messung des menschlichen Wohlbefindens im Rahmen des Capabilities Approach. Die Entwicklungspolitik erkennt ebenfalls graduell diese Maße als eine genauere Beschreibung des Wohlbefindens an, oder betrachtet diese zumindest als eine sinnvolle Ergänzung zu metrisch-monetären Maßen. Angesichts der vielen nationalen und internationalen Programme, die eine umfassende Verbesserung des menschlichen Wohlbefindens zum Ziel haben, gibt es erstaunlich wenige Arbeiten, die dazu beitragen können, die Auswirkungen eines bestimmten Programms auf das allgemeine Wohlbefinden und nicht nur auf eine bestimmte Dimension zu quantifizieren und zu bewerten. Der zweite Aufsatz in dieser Arbeit beschäftigt sich kritisch mit diesem Ansatz und betrachtet dabei den besonderen Fall Südafrikas. Aufgrund der steigenden Beliebtheit der mehrdimensionalen Armutsmaße besteht ein zunehmender Bedarf an einer Überprüfung ihrer grundlegenden Eigenschaft, ebendies zu erreichen. Eine wachsende Zahl von Forschern hat sich mit den Problemen beschäftigt, die ein zusammengesetztes Maß wie der MPI mit sich bringen kann und dessen Fähigkeit zur Messung multidimensionalen Wohlbefindens beeinträchtigen kann. Ein bestimmter Aspekt ist hierbei die Gewichtung der einzelnen Dimensionen und Indikatoren, um Armut über verschiedene Regionen hinweg zu definieren. Diese Dissertation schafft in Aufsatz eins eine Brücke zwischen den statistischen Methoden und den optimalen Gewichtungsschemata, die speziell zur Messung des multidimensionalen Wohlbefindens in verschiedenen Ländern genutzt werden können.

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