<p>The realm of molecular physical chemistry ranges from the structure of matter and the fundamental atomic and molecular interactions to the macroscopic properties and processes arising from the average microscopic behaviour.</p><p>Herein, the conventional electrodic problem is recast into the simpler molecular problem of finding the electrochemical, real chemical, and chemical potentials of the species involved in redox half-reactions. This molecular approach is followed to define the three types of absolute chemical potentials of species in solution and to estimate their standard values. This is achieved by applying the scaling laws of statistical mechanics to the collective behaviour of atoms and molecules, whose motion, interactions, and properties are described by first principles quantum chemistry. For atomic and molecular species, calculation of these quantities is within the computational implementations of wave function, density functional, and self-consistent reaction field theories. Since electrons and nuclei are the elementary particles in the realm of chemistry, an internally consistent set of absolute standard values within chemical accuracy is supplied for all three chemical potentials of electrons and protons in aqueous solution. As a result, problems in referencing chemical data are circumvented, and a uniform thermochemical treatment of electron, proton, and proton-coupled electron transfer reactions in solution is enabled.</p><p>The formalism is applied to the primary and secondary radiation damage to DNA bases, e.g., absorption of UV light to yield electronically excited states, formation of radical ions, and transformation of nucleobases into mutagenic lesions as OH radical adducts and 8-oxoguanine. Based on serine phosphate as a model compound, some insight into the direct DNA strand break mechanism is given.</p><p>Psoralens, also called furocoumarins, are a family of sensitizers exhibiting cytostatic and photodynamic actions, and hence, they are used in photochemotherapy. Molecular design of more efficient photosensitizers can contribute to enhance the photophysical and photochemical properties of psoralens and to reduce the phototoxic reactions. The mechanisms of photosensitization of furocoumarins connected to their dark toxicity are examined quantum chemically.</p>

The realm of molecular physical chemistry ranges from the structure of matter and the fundamental atomic and molecular interactions to the macroscopic properties and processes arising from the average microscopic behaviour. Herein, the conventional electrodic problem is recast into the simpler molecular problem of finding the electrochemical, real chemical, and chemical potentials of the species involved in redox half-reactions. This molecular approach is followed to define the three types of absolute chemical potentials of species in solution and to estimate their standard values. This is achieved by applying the scaling laws of statistical mechanics to the collective behaviour of atoms and molecules, whose motion, interactions, and properties are described by first principles quantum chemistry. For atomic and molecular species, calculation of these quantities is within the computational implementations of wave function, density functional, and self-consistent reaction field theories. Since electrons and nuclei are the elementary particles in the realm of chemistry, an internally consistent set of absolute standard values within chemical accuracy is supplied for all three chemical potentials of electrons and protons in aqueous solution. As a result, problems in referencing chemical data are circumvented, and a uniform thermochemical treatment of electron, proton, and proton-coupled electron transfer reactions in solution is enabled. The formalism is applied to the primary and secondary radiation damage to DNA bases, e.g., absorption of UV light to yield electronically excited states, formation of radical ions, and transformation of nucleobases into mutagenic lesions as OH radical adducts and 8-oxoguanine. Based on serine phosphate as a model compound, some insight into the direct DNA strand break mechanism is given. Psoralens, also called furocoumarins, are a family of sensitizers exhibiting cytostatic and photodynamic actions, and hence, they are used in photochemotherapy. Molecular design of more efficient photosensitizers can contribute to enhance the photophysical and photochemical properties of psoralens and to reduce the phototoxic reactions. The mechanisms of photosensitization of furocoumarins connected to their dark toxicity are examined quantum chemically.

Ein Ziel der Arbeit war die Entwicklung eines Verfahrens zur 3D-Positionierung auf Basis elektrooptischer Pseudostreckenmessung. Ein zweites Ziel war die Entwicklung eines Reflexgoniometers zur zweiachsigen Winkelmessung. Im Rahmen der Arbeit wurden die Grundlagen zur instrumentellen Umsetzung beider Verfahren erarbeitet, die Genauigkeitspotentiale ermittelt und mögliche Anwendungen für die einzelnen Schlüsseltechnologien und deren Kombination abgeleitet. In einer Prototyp-Entwicklung wurden Vorschläge für die wesentlichen Funktionselemente des räumlichen Weg- bzw. Winkelmesssystems gemacht. Hierzu gehören das kardanisch aufgehängte Etalon, die temperaturstabilisierte Laseroptik und die temperaturkalibrierte CCD der Winkelmesseinheit (Reflexgoniometer), die Systeme zur Erzeugung und Detektion ultrakurzer Laserpulse, eine elastische Optik, Möglichkeiten zur Formung des transversalen Strahlprofils, das TCSPC-System und die zur Auswertung und Kalibrierung notwendigen Algorithmen, wie z.B. die Autokollimation eines Lasers. (&amp;quot;Veröffentlicht von der Deutschen Geodätischen Kommission Reihe C (Dissertationen) unter der Nummer C 614 (München 2008; ISBN 3 7696 5053 0; 2; 144 S.&amp;quot;) / One goal of the thesis was the development of a method for three-dimensional positioning based on electro-optical measurement of pseudo ranges. Another goal was the development of a reflex goniometer for biaxial angle measurement. Within the scope of this thesis the basics for the instrumental realisation of both methods were developed, the accuracy potentials were determined and possible applications for the separate key technologies and their combination were deduced. In a prototype development proposals were made for the main functional elements of the spatial distance and angle measurement systems. These include the gimbal mounted etalon, the temperature stabilised laser optics and the temperature calibrated CCD of the angle measurement device (reflex goniometer), the systems for creation and detection of ultrashort laser pulses, an elastic optical device, possibilities of transversal beam shaping, the TCSPC system and the algorithms which are necessary for analysis and calibration, e.g. the autocollimation of a laser.

Heavy oil production depends on the understanding of mechanical and flow properties of unconsolidated or weakly consolidated sands under different loading paths and boundary conditions. Reconstituted bitumen-free Athabasca oil-sands samples were used to investigate the geomechanics of a steam injection process such as the Steam Assisted Gravity Drainage (SAGD). Four stress paths have been studied in this work: triaxial compression, radial extension, pore pressure increase and isotropic compression. Absolute permeability, end-point relative permeability to oil & water (kro and krw), initial water saturation and residual oil saturation were measured while the samples deformed. Triaxial compression is a stress path of increasing mean stress while radial extension and pore pressure increase lead to decreasing mean stress. Pore pressure increase experiments were carried out for three initial states: equal axial and confining stresses, axial stress greater than confining stress and confining stress greater than axial stress. Pore pressure was increased under four boundary conditions: 1) constant axial and confining stress; 2) constant axial stress and zero radial strain; 3) zero axial strain and constant confining stress; and 4) zero axial and radial strain. These experiments were designed to mimic geologic conditions where vertical stress was either S1 or S3, the lateral boundary conditions were either zero strain or constant stress, and the vertical boundary conditions were either zero strain or constant stress. Triaxial compression caused a decrease in permeability as the sample compacted, followed by appreciable permeability enhancement during sample dilation. Radial extension led to sample dilation, shear failure and permeability increase from the beginning. The krw and kro increased by 40% and 15% post-compaction respectively for the samples corresponding to lower depths during triaxial compression. For these samples, residual oil saturation decreased by as much as 40%. For radial extension, the permeability enhancement decreased with depth and ranged from 20% to 50% while the residual oil saturation decreased by up to 55%. For both stress paths, more shear-enhanced permeability was observed for samples tested at lower pressures, implying that permeability enhancement is higher for shallower sands. The pore pressure increase experiments showed an increase of only 0-10% in absolute permeability except when the effective stress became close to zero. This could possibly have occurred due to steady state flow not being reached during absolute permeability measurement. The krw curves generally increased as the pore pressure was increased from 0 psi. The increase ranged from 5% to 44% for the different boundary conditions and differential stresses. The kro curves also showed an increasing trend for most of the cases. The residual oil saturation decreased by 40-60% for samples corresponding to shallow depths while it increased by 0-10% for samples corresponding to greater depths. The reservoirs with high differential stress are more conducive to favorable changes in permeability and residual oil saturation. These results suggested that a decreasing mean stress path is more beneficial for production increase than an increasing mean stress path. The unconsolidated sands are over-consolidated because of previous ice loading which makes the sand matrix stiffer. In this work, it was found that over-consolidation, as expected, decreased the porosity and permeability (40-50%) and increased the Young’s and bulk moduli of the sand. The result is sand which failed at higher than expected stress during triaxial compression. Overall, results show that lab experiments support increased permeability due to steam injection operations in heavy oil, and more importantly, the observed reduction in residual oil saturation implies SAGD induced deformation should improve recovery factors. / text

We report the first total synthesis of oxydimurrayafoline via nucleophilic substitution at the benzylic position at C-3 of the carbazole framework. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

O presente trabalho visa apresentar um panorama geral a respeito da terceira espécie de inadimplemento no Direito brasileiro, considerando os esforços da doutrina e da jurisprudência em nosso sistema jurídico no trato deste tema, bem como considerando aspectos relevantes colhidos na experiência estrangeira. Na tentativa de contribuir para debate, será apresentada uma proposição para a identificação dessa terceira espécie de inadimplemento no Direito brasileiro. / The present work aims to present an overview regarding the third kind of default in Brazilian law, considering the efforts of the doctrine and of the jurisprudence in our legal system in dealing with this issue, as well as considering relevant aspects gathered from the experience of foreign law. In an attempt to contribute to debate, a proposition will be presented for the identification of this third kind of default in Brazilian law.

This thesis deals with the objective and subjective cognition of beauty by a scholastic philosopher Thomas Aquinas. The initial chapters provide historical sources and a source of St. Thomas´s beauty, because beauty was not the main topic of theology and philosophy in the Middle Ages. From the definition of beauty, we know that beauty belongs to the cognitive power, thus next chapters present the activity of the senses and reason, by which we recognize beauty. (Pulchrum autem respicit vim cognoscitivam). This cognitive power results in the objective characteristics of beauty, ie.: a) integrity; b) proportion; c) clarity.) The penultimate chapter justifies the importance of knowledge of objective and subjective beauty, from which it follows in us enjoyment (delectatio et amor). If there is a reason to evaluate the knowledge and principles relating to the beauty, there is a necessary overlap present knowledge such as science. The final chapter addresses the interesting question of modern science - aesthetics: "Whether beauty, as written by Thomas Aquinas, is a specific distinct transcendental or only implicit transcendental initiated by the philosophers of the 20th century?" The thesis tries to show the importance of studying medieval philosophy in shaping topics such as beauty and art.

Alors que nous faisons face à une crise biologique majeure, acteurs institutionnel et ONGs exhortent les entreprises à s’engager pour enrayer cette érosion écologique. L’objectif de la thèse est d’analyser, évaluer et faire évoluer la contribution potentielle des entreprises à la conservation de la biodiversité dans le cadre de leur responsabilité sociétale (RSE).Un cadre d’analyse est développé pour évaluer la prise en charge par une entreprise de ses responsabilités écologiques en termes de moyens – les initiatives RSE a priori favorables à la biodiversité mises en œuvre – et de résultats – la compatibilité des activités de l’entreprise avec la conservation de la biodiversité. Après avoir caractérisé les initiatives RSE à partir de l’étude d’engagements d’entreprises endossés comme contributions à la Stratégie nationale pour la biodiversité, une méthode est proposée pour détecter si les activités d’une entreprise sont écologiquement non-durables. Le postulat est que le respect des capacités de charge des écosystèmes est un prérequis à la conservation effective de la biodiversité. Cette méthode, adaptée de l’évaluation environnementale absolue de la durabilité, est appliquée, dans le cadre de deux projets de recherche-intervention, au portfolio alimentaire du Groupe Casino et au cycle de vie de deux installations de stockage de déchets dangereux de SARP Industries. Des orientations stratégiques visant à éviter-réduire-compenser les pressions non durables sont proposées. Soulignant l’importance de renforcer la prise en charge des pressions étendues, cette thèse ouvre plus largement des perspectives pour les secteurs d’activité et les politiques publiques. / As we are experiencing a major biological crisis, institutional actors and NGOs are calling on businesses to engage efforts aiming at halting biodiversity loss. The objective of the thesis is to analyze and evaluate the potential contribution of corporate social responsibility (CSR) to biodiversity conservation.A framework is developed to analyze to which extent a company takes in charge its ecological responsibilities. After characterizing CSR initiatives based on the case study of business commitments to contribute to the French National Biodiversity Strategy, a method is proposed to test whether business activities exert unsustainable pressures on ecosystems. It is assumed that compatibility with ecosystems’ carrying capacities is a prerequisite for effective biodiversity conservation. This method, adapted from the “absolute environmental sustainability assessment” (AESA) approach, is applied in the context of research-intervention projects to the food portfolio of the mass-market retailer Groupe Casino and to the life cycle of two facilities of SARP Industrie specialized in the disposal and storage of hazardous waste. The comparison of the company’s environmental footprints with the ecological constraints is used to draw a comprehensive strategy based on the mitigation hierarchy. As our results highlight the opportunity to strengthen the management of extended pressures through CSR, possible implications for sectors and public policies are discussed.

Made available in DSpace on 2016-06-02T19:53:32Z (GMT). No. of bitstreams: 1 MARTINEZ_Jonathan_2014.pdf: 11989383 bytes, checksum: 96fb53d9544014ea55b1e53ee779c134 (MD5) Previous issue date: 2014-03-14 / Financiadora de Estudos e Projetos / This study presents a pump scheduling problem for the capture, transfer and storage of water supply systems in urban networks, whose objective is to minimize the electricity cost associated to the pumping operations. To deal with the dynamic and random nature of the water-demand, we propose two-stage stochastic programming with recourse models, where the random variables are represented by a finite and discrete set of realizations or scenarios. The developed mathematical models are extensions of previous deterministic models of the literature and they reflect the basic assumption that a fixed cost could be incurred by the turn on/ turn off activities of the hydraulic pumps. In order to control violations of the water-demand constraints in the presence of multiple different scenarios, we also consider a robustness technique in an attempt to obtain almost feasible solutions. Last, but not least, we adopt a risk-aversion criteria so-called mean absolute deviation to obtain second-stage costs less dependent on the realizations of the scenarios. The scenarios were generated according to a Monte-Carlo simulation procedure that may use any probability distributions to produce the empirical probabilities of the random variables. As the proposed pump scheduling problem with fixed cost is a two-stage stochastic mixed 0 &#8722; 1 program, we develop a efficient hybrid heuristic to obtain good-quality solutions of practical instances in a plausible running time. Overall results evidence the stability of the scenario generation method, the sensitivity of the solution according to the key parameters of the mathematical model, and the efficiency of the heuristic in solving large instances. Finally, we show that is possible to save resources by solving the stochastic programming model instead of adopting simpler approaches based on the expected value. / Esse estudo apresenta um problema de programação de bombas para a captação, armazenamento e transferência de água em sistemas de abastecimentos de água em redes urbanas, cujo objetivo é minimizar o custo de energia elétrica associado às operações de bombeamento. Para lidar com a natureza dinâmica e aleatória da demanda por água, foram propostos modelos de programação estocástica de dois estágios com recurso, em que a variável aleatória é representada por um conjunto finito de realizações ou cenários. Os modelos matemáticos desenvolvidos são extensões de modelos determinísticos da literatura e refletem a suposição básica de que é possível se incorrer em um custo fixo pelas atividades de liga/desliga das bombas hidráulicas. Para controlar as violações das restrições de demanda por água na presença de múltiplos cenários diferentes, considerou-se também uma técnica de robustez na tentativa de gerar soluções quase factíveis. Por último, mas não menos importante, adotou-se um critério de aversão ao risco denominado desvio médio absoluto para obter custos de segundo estágio menos dependentes das realizações dos cenários. Os cenários foram gerados de acordo com um procedimento baseado em simulação Monte-Carlo que pode utilizar qualquer distribuição de probabilidade para produzir as probabilidades empíricas das variáveis aleatórias. Como o problema de programação de bombas com custo fixo proposto é um programa inteiro misto 0&#8722;1 estocástico, desenvolve-se uma heurística híbrida eficiente para obter soluções de boa qualidade de instâncias práticas em um tempo computacional plausível. Os resultados evidenciam a estabilidade do método de geração de cenários, a sensibilidade da solução de acordo com parâmetros-chave do modelo matemático, e a eficiência da heurística na resolução de instâncias de grande porte. Finalmente, foi demonstrado que é possível poupar recursos pela resolução do modelo de programação estocástica, em vez de adotar abordagens mais simples baseadas no valor esperado.

This work discourses about the teaching of bulgarian {--} french philosopher, pedagogue and spiritual teacher Omraam Mikhaël Aivanhov. It is divided in several thematic chapters discoursing always a certain philosofical {--} spiritual theme from the point of view how is it treated in the teaching of Aivanhov. Among those themes are for example: Creation, Good and evil, About God, Jesus and Christ, Reincarnation, Soul, Ressurection, Holy Trinity. Aivanhov has fresh and undogmatic approach to these themes and he accents that his teaching can serve to a man for the practical work on him or herself. He does not stick to any particular tradition neither he arteficially syncretizes. He rather sees the various levels of the creation and its Creator as a reality which has universal laws and principles. And a mission of man is according to Aivanhov to discover those laws and principles and to live in harmony with them.