Os complexos [TR2(L)3⋅x(H2O)]y(H2O) (Eu3+, Gd3+ e Tb3+) com os ligantes dicarboxilatos alifáticos OXA, MAL, SUC, GLU, ADP, PIM, SUB, AZL, SEB, UND e DOD foram preparados pelo método de precipitação. Estes compostos de coordenação foram sintetizados em solução aquosa e com aquecimento (~ 80 ºC) e apresentaram-se na forma de pós brancos, cristalinos, não higroscópicos e insolúveis em solventes polares e apolares. A análise elementar (CHN) indicou a proporção molar M:L de 2:3 e o número de moléculas de H2O dos complexos, que foi confi rmado pelos dados de análise térmica (TG/DTG). A temperatura final de saída das moléculas de H2O dos complexos apresentou um padrão em ziguezague em função do tamanho da cadeia carbônica dos ligantes, levando ao chamado efeito odd-even. As análises de espectroscopia de absorção no infravermelho (FTIR) confirmaram a efetiva coordenação dos ligantes já desprotonados aos íons TR3+ via modo misto de coordenação ponte-quelato, exceto no caso dos complexos [TR2(OXA) 3⋅6(H2O)]4(H2O)4(H2O) que ocorre via ponte bidentada. Os difratogramas de raios-X pelo método do pó (XPD) indicam que os complexos apresentam elevada cristalinidade, pertencendo ao sistema cristalino monoclínico e que os complexos com o mesmo ligante e diferentes íons TR3+ são isomórficos. As imagens de microscopia eletrônica de varredura (MEV) mostram que os compostos apresentam diferentes morfologias tais como bastão, placas ou um misto de placas e cubos, como no caso dos complexos de Eu3+ com os ligantes OXA, SUC e DOD respectivamente. A investigação por espectroscopia de absorção dos sais sódicos dos ligantes (Na2L) e a reflectância difusa, bem como o estudo fotoluminescente (espectros de excitação e emissão) dos complexos de Eu3+, Gd3+ e Tb3+ foi realizada e discutida. O comportamento fotoluminescente dos complexos baseados nos tempos de vida (t) do nível emissor 5D0 do íon Eu3+, rendimento quântico intrínseco (QLnLn), taxas de decaimento radiativo (Arad) e não-radiativo (Anrad) foram determinadas. Ademais, foi realizado o estudo sistemático teórico e experimental para calcular os parâmetros de intensidade Ω2 e Ω4. Os espectros de fosforescência resolvidos no tempo dos complexos de Gd3+ apresentaram bandas largas oriundas dos níveis tripleto (T1) dos ligantes ~ 22950 cm-1, mais próximos do nível emissor 5D4 (Tb3+) do que do nível 5D0 (Eu3+), sugerindo que a alta intensidade luminescente exibida pelos complexos de Tb3+ comparados com os complexos análogos de Eu3+ é devida à transferência de energia intramolecular mais eficiente. Os espectros de reflectância difusa confirmam a presença de bandas 4f8→4f75d1 e LMCT nos complexos de Tb3+ e Eu3+, respectivamente. Os espectros de emissão dos íons Tb3+ e Eu3+ apresentaram bandas finas referentes a transições intraconfiguracionais 4f, sendo que as transições 5D4→7F5 (~ 545 nm) e 5D0→7F2 (~ 611 nm) foram as mais intensas, respectivamente. Os valores de rendimento quântico intrínseco QLnLn dos complexos variaram entre 13 e 28%, dentro dos quais o composto [Eu2 (SUC) 3⋅2(H2O)]H2O apresentou o maior valor. Este comportamento espectroscópico mostra que as moléculas de H2O atuam como um eficiente canal de supressão de luminescência. Os valores dos parâmetros de intensidade experimentais e teóricos (Ω2 e Ω4) apresentaram excelente concordância e mostraram o comportamento em ziguezague. Isto sugere que o íon Eu3+ atua como uma poderosa sonda espectroscópica para o efeito odd-even. Os complexos de Gd3+, Eu3+ e Tb3+ apresentaram cores de emissão azul, vermelha e verde, respectivamente, sugerindo que podem ser utilizados como dispositivos moleculares conversores de luz (DMCLs). / The [RE2(L)3⋅x(H2O)]y(H2O) complexes (RE3+: Eu3+, Gd3+ and Tb3+) with the aliphatic dicarboxylates ligands OXA, MAL, SUC, GLU, ADP, PIM, SUB, AZL, SEB, UND e DOD have been prepared by the precipitation method. These coordination compounds were synthesized in aqueous solution and heating (~ 80 °C) and presented as white crystalline powder, non-hygroscopic and insoluble in both polar and nonpolar solvents. The elemental analysis (CHN) indicated the M:L molar ratio of 2:3 and the number of water molecules of the complexes, which were confirmed by thermal analysis (TG/DTG) data. The final evaporating temperature of the H2O molecules of the complexes presented a zigzag pattern as a function of the carbon chain size of the ligands, leading to the so-called odd-even effect. The infrared absorption spectroscopy (FTIR) confirmed the effective coordination of the already deprotonated ligands to the RE3+ ions via the mixed mode of bridge-chelate coordination, except for the [RE2 (OXA)3⋅6(H2O)]4(H2O) complexes that occur via bidentate bridge mode. The X-ray powder diffraction (XPD) patterns indicate that the complexes present high crystallinity and the compounds with the same ligand and different RE3+ ions present isomorphic character. Scanning electron microscopy (SEM) images showed that the Eu3+ complexes with OXA, SUC and DOD ligands exhibited different morphologies such as rods, sheets or a mixture of sheets and cubes, respectively. The absorption spectroscopy investigation of the ligand sodium salts (Na2L) and the diffuse reflectance as well as the luminescence study (excitation and emission spectra) for the Eu3+, Gd3+ and Tb3+ complexes have been performed and discussed. The photoluminescent behavior of the complexes based on the lifetime (t) of the 5D0 emitting level of the Eu3+ ion, intrinsic quantum yield (QLnLn), radiative (Arad) and nonradiative (Anrad) were determined. In addition, the theoretical and experimental systematic study was carried out to calculate the intensity parameters Ω2 and Ω4. The time resolved phosphorescence spectra of the Gd3+ complexes showed broad emission bands assigned to the triplet (T1) states of the ligands at ~ 22950 cm-1, closer to the 5D4 emitting level (Tb3+) than to the 5D0 level (Eu3+), suggesting that the higher luminescent intensity exhibited by the Tb3+ complexes compared to the Eu3+ analog complexes are due to a more efficient L—RE3+ intramolecular energy transfer. The diffuse reflectance data confirmed the presence of 4f8→4f75d1 and LMCT absorption bands in the Tb3+ and Eu3+ complexes, respectively. The emission spectra of the Tb3+ and Eu3+ ions showed narrow bands due to the intraconfigurational 4f transitions, among them the 5D4→7F5 (~ 545 nm) and 5D0→7F2 (~ 611 nm) transitions were the most intense, respectively. The values of intrinsic quantum yield QLnLn of the complexes ranged from 13 to 28%, in which the [Eu2 (SUC)3⋅2(H2O)]H2O complex presented the highest value due to its lower number of H2O molecules. This optical behavior shows that the H2O molecules act as an efficient luminescence quenching channel. The values of experimental and theoretical intensity parameters (Ω2 and Ω4) presented excellent agreement which showed the zigzag behavior. These indicate that the Eu3+ ion acts as a powerful spectroscopic probe for the odd-even effect. The Gd3+, Eu3+ and Tb3+ complexes showed blue, red and green emission colors, respectively, suggesting that can be applied as light-converting molecular devices.

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Made available in DSpace on 2016-03-15T19:37:56Z (GMT). No. of bitstreams: 1 CARLOS EDUARDO PROFETA DE CARVALHO.pdf: 1714302 bytes, checksum: 9f543bb164424f04ade23ddc5bedeb07 (MD5) Previous issue date: 2015-03-04 / Cellular automata are discrete complex systems and also fully distributed computational systems, with arbitrarily simple local processing. One of computations that can be made with cellular automata is sorting of numerical sequences. Sorting is a quite relevant topic and widely used in computing, as one of its fundamental processes. This research aimed at the development of sorting algorithms based on one-dimensional cellular automata. Two new versions with range 1 and 3 have been proposed, inspired by the characteristics of existing studies in the literature. In the analysis carried out, the proposed cellular automata have advantages over the approaches that originated them. / Autômatos celulares são sistemas complexos discretos e também sistemas computacionais totalmente distribuídos, com processamento local arbitrariamente simples. Uma das computações que se pode realizar com autômatos celulares é a ordenação de sequências numéricas. A ordenação é um tema bastante relevante e utilizado amplamente na computação, como um de seus processos fundamentais. A presente pesquisa visou o desenvolvimento de algoritmos de ordenação baseados em autômatos celulares unidimensionais. Foram propostas duas novas versões, de raios 1 e 3, inspirados por características de trabalhos existentes na literatura. Em análise realizada, os autômatos celulares propostos apresentam vantagens com relação às abordagens que lhes deram origem.

Immer mehr Verlage etablieren glatte Preise bei ihren Erzeugnissen, um der Forderung des Buchhandels nach glatten Preisen zu entsprechen. Die vorliegende Arbeit untersucht inwieweit diese Fragestellung aus preispsychologsicher Sicht für die Warengruppen Belletristik und Sachbuch berechtigt ist und welche Produkteigenschaften einen Einfluss auf die Zahlungsbereitschaft haben. Hierfür sind 14 branchenfremde Studien nach dem PICO(C)-Schema auf Adaptionspotenzial überprüft worden. Ergänzend sind aktuelle theoretische Forschungserkenntnisse nach WENGER dargestellt worden. Die aktuellen Preisstrategien für die Warengruppen Belletristik und Sachbuch in den Ausgabeformen: Hardcover, Taschenbuch, E-Book und Hörbuch, werden in einer IST-Analyse dargestellt. Da bis heute keine repräsentativen Daten bzgl. des Preisendung im Buchhandel vorliegen, wurde ein Datenerhebungskonzept erarbeitet. Zunächst wurde eine Choice-Based-Conjoint-Analyse mit einer Stichprobe von N=176 Teilnehmern durchgeführt. Ebenfalls wurde mit einer qualitativen Stichprobe von N=11 eine van-Westerndorp-Befragung durchgeführt. Zentrale Ergebnisse der Arbeit sind, dass überwiegend glatte Preise gegenüber gebrochenen präferiert werden. Die Aussage, dass es zentrale Preisschwellen für die genannten Warengruppen gibt, konnte in dieser Arbeit nicht bestätigt werden. Alle Ergebnisse dieser Arbeit sind stark von individuellen Produkteigenschaften abhängig. Für den Transfer in die Praxis wurden, neben der Definition eines SOLL-Zustands, für beide Warengruppen, Preissimulatoren programmiert. Auf dieser Basis kann künftig ein ganzheitliches Preismanagement in Verlagen und dem Buchhandel etabliert werden.:1. Einleitung und Problemstellung 1.1. Motivation 1.2. Ziele der Arbeit 1.3. Aufbau der Arbeit und Methodik 2. Stand der Forschung zu Preisendungen 2.1. Klassische und verhaltensorientierte Studien zu Preisendungen 2.2. Zusammenfassung und Beurteilung 3. Theoretischer Bezugsrahmen 3.1. Preis- und Konsumentenverhalten 3.2. Preiswürdigkeitsurteil 3.3. Phasen eines Kaufprozesses am Beispiel des SOR-Modells 3.4. Verhaltenspsychologische Theorien der Preisforschung 3.6. Zusammenfassung und Beurteilung 4. Analyse deutscher Buchmarkt 4.1. Abgrenzung und Darstellung Buchhandel und Buchmarkt 4.2. Preispolitik im deutschen Buchhandel 4.3. Vorstellung und Analyse ausgewählter Warengruppen im Buchhandel 4.4. Zusammenfassung und Beurteilung 5. Methodisches Vorgehen 5.1. Vorstellung Preisforschungsmethoden 5.2. Datenerhebungskonzept und Vorüberlegungen 5.3. Zusammenfassung und Beurteilung 6. Erstellung und Durchführung der Studien 6.1. Toolauswahl 6.2. Umfrageerstellung 6.3. Durchführung und Verteilung 6.4. Zusammenfassung und Beurteilung 7. Analyse und Auswertung der Ergebnisse 7.1. Demographische Daten und Rating-Teil 7.2. Auswertung CBC I 7.3. Auswertung CBC II 7.4. Auswertung van-Westerndorp PSM 7.5. Zusammenfassung und Beurteilung 8. Implikationen für die Preis- und Produktpolitik 8.1. Entscheidungsmatrix und Definition SOLL-Zustand 8.2. Zusammenfassung und Beurteilung 9. Fazit und Ausblick

Les algorithmes cryptographiques actuels se répartissent en deux grandes familles : les algorithmes symétriques et les algorithmes asymétriques. En 1991, S. Even et Y. Mansour ont proposé une construction simple d'un algorithme de chiffrement par blocs en utilisant une permutation aléatoire. Récemment, surtout pour répondre aux nouveaux enjeux de la cryptographie à bas coût, plusieurs algorithmes ont été proposés dont la construction est basée sur le schéma Even-Mansour. Les travaux réalisés dans cette thèse ont pour objet l'analyse de ce type d'algorithmes. À cette fin, nous proposons une nouvelle attaque générique sur le schéma Even-Mansour. Ensuite, afin de montrer l'importance particulière du modèle multi-utilisateurs, nous appliquons cette attaque générique dans ce modèle. Ces deux attaques sur Even-Mansour introduisent deux nouvelles idées algorithmiques : les chaînes parallèles et la construction d'un graphe qui illustre les liens entre les clés des utilisateurs du modèle multi-utilisateurs. Finalement, basés sur ces idées, nous proposons des attaques sur les algorithmes de chiffrement par blocs DESX et PRINCE et sur le code d'authentification de message Chaskey. / Current cryptographic algorithms are divided into two families: secret-key algorithms (or symmetric algorithms) and public-key algorithms. Secret-key cryptography is characterized by the sharing of the same key K used by both legitimate users of the cryptosystem. Bloc ciphers are one of the main primitives of symmetric cryptography. In 1991, S. Even and Y. Mansour proposed a minimal construction of a bloc cipher which uses a random permutation. Recently, in the context of lightweight cryptography, many algorithms based on the Even-Mansour scheme have been proposed. In this thesis, we focus on the analysis of this type of algorithms. To this purpose, we propose a generic attack on the Even-Mansour scheme. To show the particular importance of the multi-user model, we adapt our attack to this context. With these attacks, we introduce two new algorithmic ideas: the parallel chains and the construction of graph which represents the relations between the keys of the users of the multi-user model. Finally, we use these ideas and we present attacks on the bloc ciphers DESX and PRINCE and on the message authentication code (MAC) Chaskey.

Master of Agribusiness / Department of Agricultural Economics / Jason Bergtold / Efficiency and technology are increasingly important selling points for combine harvesters. Diesel-electric hybrid drives have taken hold in the construction equipment industry, and are providing marketable efficiency benefits for some heavy equipment customers. This thesis explores the technical and economic feasibility of utilizing diesel-electric hybrid drives on AGCO combine harvesters. To determine the technical feasibility of utilizing diesel-electric hybrid drives on AGCO combine harvesters, a search was conducted for prior literature relating to the use of electric drives on other heavy, off-highway equipment. This information, coupled with data provided by experts in the field, was used to determine if electric drives could fulfill the unique requirements of combine harvesters, and be practically utilized for this application. To determine the economic feasibility of utilizing diesel-electric hybrid drives on AGCO combine harvesters, an optimization model was constructed to seek out the most economically viable configuration of electric drives for this application. The model takes in to consideration the different use-cases in which this equipment is expected to perform, as well as the component costs and operating efficiencies of both the drives in place currently and the proposed electric drives. The outcome of the model was then utilized to compare the best-case configuration to the minimum requirement for economic feasibility. The technical feasibility assessment conducted for this thesis led to the conclusion that it would be technically feasible to utilize electric drives on a combine harvester. There are commercially available electric drive components which are suitable for use in the environment that this equipment is expected to operate in, and a prototype combine harvester having electric drives has previously been constructed. The economic feasibility assessment conducted for this thesis revealed that it is not economically feasible to utilize electric drives on AGCO combine harvesters at this time. Under the current circumstances, the most economically viable configuration would take nearly twice the machine’s usable operating life to provide a benefit to a customer from fuel savings. Sensitivity analysis revealed that significant changes in the price of fuel or electric drive components would be necessary to change the outcome of this study.

published_or_final_version / Business Administration / Master / Master of Business Administration