This cumulative dissertation is a compendium of five peer-reviewed and published scientific papers on developing an advanced NMR Cryoporometry toolbox for pore architecture characterization. The dissertation contains five chapters. The first introduces porous materials, their types and applications. Chapter two describes the fundamentals of fluid phase equilibria in mesoporous solids and how modifications of the well-known Laplace equation describe various fluid phase equilibria. The basic principles of the Gas Sorption and NMR Cryoporometry techniques are discussed. In chapter three, different characterization techniques are amalgamated onto a common framework which can be used to compare fluid phase coexistence in porous materials of different pore sizes. Chapter four explains a completely new NMR Cryoporometry characterization methodology developed for cylindrical and spherical pore shapes. Chapter five concludes and crowns the present work by discussing the complementary benefits of the advanced technique in characterizing random porous materials and accounting for pore connectivity effects. All materials synthesized for the work in this dissertation have been obtained through collaborations with the groups of Profs. Dr. Michael Fröba and Simone Mascotto of the Hamburg University and Prof. Dr. Dirk Enke of the Leipzig University.:Table of Contents Thesis Summary ........................................................................................................1 List of publications ......................................................................................................2 Acknowledgements ...................................................................................................4 CHAPTER 1:.............................................................................................................10 Introduction ..............................................................................................................10 CHAPTER 2:.............................................................................................................12 Fluid Phase Equilibria in Mesoporous Solids ..........................................................12 2.1 Gas Sorption................................................................................................... 13 2.1.1 Adsorption Isotherms................................................................................ 15 2.1.2 Adsorption Hysteresis............................................................................... 18 2.1.3 Scanning Behavior.................................................................................... 23 2.2 NMR Cryoporometry ....................................................................................... 25 2.2.1 Pore Size Distribution (PSD)....................................................................... 28 2.3 Serially-Connected Pore Model (SCPM)......................................................... 29 2.4 Problem Statement ......................................................................................... 30 CHAPTER 3:..............................................................................................................32 Analogy between Characterization Techniques ......................................................32 • Publication 3. On the Comparative Analysis of Different Phase Coexistences in Mesoporous Materials CHAPTER 4:.............................................................................................................42 An Advanced NMR Cryoporometry Approach.........................................................42 • Publication 4.1. Nuclear Magnetic Resonance Cryoporometry Study of Solid−Liquid Equilibria in Interconnected Spherical Nanocages • Publication 4.2. A novel approach for advanced thermoporometry characterization of mesoporous solids: Transition kernels and the serially connected pore model CHAPTER 5:.............................................................................................................65 Characterizing Random Porous Materials................................................................65 • Publication 5.1. Comparative Gas Sorption and Cryoporometry Study of Mesoporous Glass Structure: Application of the Serially Connected Pore Model • Publication 5.2. Impact of Geometrical Disorder on Phase Equilibria of Fluids and Solids Confined in Mesoporous Materials Appendix A:.............................................................................................................100 Porous Solid Characterization Techniques............................................................100 A.1: Mercury Intrusion Porosimetry (MIP) ........................................................... 100 A.1.1. Experimental Set-up.............................................................................. 101 A.2: Gas Sorption................................................................................................ 103 A.2.1. Experimental Set-Up ............................................................................. 103 A.2: NMR Cryoporometry.................................................................................... 106 A.2.2. Experimental Set-Up ............................................................................. 106 Appendix B:..............................................................................................................109 Supporting information ............................................................................................109 Appendix C:.............................................................................................................115 Author contributions ................................................................................................115 Bibliography ............................................................................................................117

В работе рассматривается дискретная нейронная модель, введенная впервые Рульковым Н.Ф., которая хорошо отражает быстро-медленную динамику нейрона. В работе проводится исследование устойчивости точек покоя и предельных циклов модели Рулькова к случайным возмущениям. В первой части изучаются точки покоя и циклы детерминированной одномерной модели, исследуется их устойчивость и проведен бифуркационный анализ. Во второй части анализируется поведение аттракторов этой модели под влиянием случайных возмущений. В третьей части проведен анализ расширенной двумерной модели, построены бифуркационные диаграммы и фазовые портреты, проведен анализ устойчивости. / This paper considers a discrete neural model pioneered by Rulkov N.F. This model clearly reflects the fast-slow dynamics of the neuron. In this paper, we study the stability of equilibrium points and limit cycles of Rulkov model to random perturbations. In the first part, we study equilibria and cycles of deterministic one-dimensional model, investigate stability and carry out the bifurcation analysis. In the second part, we analyze the behavior of the attractors under the influence of random perturbations. In the third part, the bifurcations and phase portraits of extended two-dimensional model are studied, and stability analysis is carried out.

Nuclear magnetic resonance (NMR) provides a variety of tools for the structural characterization of porous solids. In this paper, we discuss a relatively novel approach called NMR cryodiffusometry, which is based on a simultaneous assessment of both the phase state of intraporous liquids at low temperatures, using NMR cryoporometry, and their transport properties, using NMR diffusometry. Choosing two model porous materials with ordered and disordered pore structures as the host systems, we discuss the methodological and fundamental aspects of the method. Thus, with the use of an intentionally micro-structured mesoporous silicon, we demonstrate how its structural features give rise to specific patterns in the effective molecular diffusivities measured upon progressive melting of a frozen liquid in the mesopores. We then present the results of a detailed study of the transport properties of the same liquid during both melting and freezing processes in Vycor porous glass, a material with a random pore structure. 1

Die Frage nach der Möglichkeit von Leben auf anderen Planeten, vor allem auf dem Mars, steht in einem engen Zusammenhang mit der Verfügbarkeit von flüssigem Wasser. Dies ist bei den vorherrschenden klimatischen Bedingungen, vor allem der tiefen Temperatur, nur mittels einer Gefrierpunktserniedrigung durch Salze erklärbar. Die vorliegende Arbeit beschäftigt sich daher mit Phasengleichgewichten verschiedener Salz-Wasser-Systeme bei tiefen Temperaturen. Dabei wurden nach einer Sammlung von Literaturdaten und einer Ermittlung der Lücken innerhalb dieser verschiedene Systeme nach Mars-Relevanz, sowie chemischer Systematik ausgewählt und experimentell untersucht. Insgesamt wurden dabei 22 binäre Phasendiagramme von Salz-Wasser-Systemen betrachtet und 29 festen Phasen mittels Röntgen-Einkristallstrukturanalyse aufgeklärt. Aus diesen Strukturen wurde ein Modell zur Beschreibung einer zweiten Hydratationssphäre über eine Wechselwirkungsbilanz abgeleitet und an den verfügbaren Strukturen geprüft.

In this thesis examples of translationally invariant one-dimensional (1D) Vlasov-Maxwell (VM) equilibria are investigated. The 1D VM equilibrium equations are equivalent to the motion of a pseudoparticle in a conservative pseudopotential, with the pseudopotential being proportional to one of the diagonal components of the plasma pressure tensor. A necessary condition on the pseudopotential (plasma pressure) to allow for force-free 1D VM equilibria is formulated. It is shown that linear force-free 1D VM solutions correspond to the case where the pseudopotential is an attractive central potential. The pseudopotential for the force-free Harris sheet is found and a Fourier transform method is used to find the corresponding distribution function. The solution is extended to include a family of equilibria that describe the transition between the Harris sheet and the force-free Harris sheet. These equilibria are used in 2.5D particle-in-cell simulations of magnetic reconnection. The structure of the diffusion region is compared for simulations starting from anti-parallel magnetic field configurations with different strengths of guide field and self-consistent linear and non-linear force-free magnetic fields. It is shown that gradients of off-diagonal components of the electron pressure tensor are the dominant terms that give rise to the reconnection electric field. The typical scale length of the electron pressure tensor components in the weak guide field case is of the order of the electron bounce widths in a field reversal. In the strong guide field case the scale length reduces to the electron Larmor radius in the guide magnetic field.

Algorithmically designed reward functions can influence groups of learning agents toward measurable desired sequential joint behaviours. Influencing learning agents toward desirable behaviours is non-trivial due to the difficulties of assigning credit for global success to the deserving agents and of inducing coordination. Quantifying joint behaviours lets us identify global success by ranking some behaviours as more desirable than others. We propose a real-valued metric for turn-taking, demonstrating how to measure one sequential joint behaviour. We describe how to identify the presence of turn-taking in simulation results and we calculate the quantity of turn-taking that could be observed between independent random agents. We demonstrate our turn-taking metric by reinterpreting previous work on turn-taking in emergent communication and by analysing a recorded human conversation. Given a metric, we can explore the space of reward functions and identify those reward functions that result in global success in groups of learning agents. We describe 'medium access games' as a model for human and machine communication and we present simulation results for an extensive range of reward functions for pairs of Q-learning agents. We use the Nash equilibria of medium access games to develop predictors for determining which reward functions result in turn-taking. Having demonstrated the predictive power of Nash equilibria for turn-taking in medium access games, we focus on synthesis of reward functions for stochastic games that result in arbitrary desirable Nash equilibria. Our method constructs a reward function such that a particular joint behaviour is the unique Nash equilibrium of a stochastic game, provided that such a reward function exists. This method builds on techniques for designing rewards for Markov decision processes and for normal form games. We explain our reward design methods in detail and formally prove that they are correct.

Ce travail est consacré à l’étude du procédé de synthèse, d’extraction et de purification d’une hydrazine exocyclique à applications cosmétiques, la N-aminopyrrolidine (NAPY). Dans un premier temps, l’optimisation des conditions de synthèse par la voie Raschig e été conduite en étudiant l’influence de deux paramètres, rapport molaire des réactifs (NH2Cl, pyrrolidine) et la température, sur le rendement de la réaction. Les solutions brutes de synthèse étant très diluées (≈5%g en NAPY), l’extraction et la purification du produit utile sont souvent liées à des opérations successives de démixtion et de distillation. La détermination de ces conditions de séparation requière alors la connaissance des propriétés thermodynamiques des équilibres entre phases impliqués dans ces opérations unitaires. L’optimisation de la démixtion nécessite alors l’étude du système ternaire solide-liquide-liquide NaOH/Pyrrolidine/Eau. Trois coupes isothermes isobares ont été complètement déterminées, par ATI (Analyse Thermique Isopléthique) combinée à des dosages chimiques. La méthode du diamètre et des modules a été mise au point pour la détermination du point critique de la courbe de démixtion. Les opérations de distillation mettent en jeu le système ternaire NAPY/Pyrrolidine/Eau. Le binaire limite liquide-vapeur Eau/Pyrrolidine a été déterminé par ébulliométrie à la pression atmosphérique. Pour essayer de mieux comprendre les interactions hétéromoléculaires ayant lieu en phase liquide, deux autres binaire liquide-vapeur eau/amine ont été obtenus. L’étude su système ternaire liquide-vapeur nous a permis de déduire deux schémas de distillation possibles. Une fois les conditions de synthèse et d’extraction définies et un schéma de procédé a été proposé, la NAPY est obtenue conforme aux spécifications cosmétiques / This global work is related to the synthesis, extraction and purification of a new exocyclic hydrazine with cosmetic applications, the N-aminopyrrolidine (NAPY). Firstable, the optimization of the synthesis conditions by the Raschig way are carried out by studying the influence of two parameters, the reagents’ molar ratio and the temperature, on the yield of the reaction. Due to the very low hydrazine content in the reaction liquors (≈5%w of NAPY), the extraction and purification of the useful product are often linked to successive demixing and distillation operations. The determination of these separation conditions requires then the knowledge of thermodynamics’ properties of the phase equilibria in these unitary steps. The optimization of the demixing needs then the study of the solid-liquid-liquid ternary solution NaOH/Pyrrolidine/Water. In this aim, three isothermal isobaric sections were studied, by combination of ATI (Isoplethic Thermal Analysis) and chemical analysis. The diameter and modulus method was developed in order to determine the composition of the critical point of the demixing curve. The distillation steps involve the liquid-vapor ternary system NAPY/Pyrrolidine/Water. The limit binary system Water/Pyrrolidine was determined by ebulliometry under atmospheric pressure. For a better understanding of the heteromolecular interactions in the liquid phase, two others liquid-vapor binary systems Water/Amine were obtained. The study of the ternary liquid-vapor system lad us to deduce two various distillation schemes. Once the synthesis and extraction conditions defined, a global process scheme was proposed, and NAPY was obtained in conformity with the cosmetical specifications

Dans les applications industrielles et lors des opérations de transport du gaz naturel, la présence d'eau sous forme liquide ou en phase vapeur peut entraîner la formation d'hydrates provoquant le colmatage des unités industrielles et des lignes de conduites et il est indispensable de définir précisément les seuils de déshydratation à réaliser, afin d'éviter la formation d'hydrates. Cela est réalisé à l'aide d'un modèle thermodynamique qui prédit la stabilité des hydrates, en fonction de la température, de la pression et de la composition du gaz.Les modèles thermodynamiques classiques, développés uniquement sur la base de données expérimentales de formation d'hydrates en présence d'eau liquide, surestiment fortement la température de dissociation des hydrates en l'absence d'une phase aqueuse.Dans le but de définir un modèle thermodynamique capable de représenter convenablement les équilibres de phases vapeur-hydrate et prédire ainsi la température de dissociation des hydrates que l'on soit en présence ou en l'absence d'eau liquide, nous avons mis au point une méthodologie originale pour la détermination de la température de dissociation des hydrates de corps purs et de mélanges en l'absence d'eau liquide. Cette méthodologie, basée sur le suivi de la teneur en eau de phase vapeur, en fonction de la température par coulométrie Karl Fischer, a permis la détermination de la température de dissociation de plusieurs hydrates simples et mixtes à des teneurs en eau et pressions différentes ainsi que les quantités d'hydrates formées dans ces conditions.Sur la base de ces nouvelles données, nous avons défini un modèle thermodynamique basé sur l'utilisation de l'approche de Dharmawardhana pour le calcul de la fugacité de l'eau dans l'hydrate vide,le potentiel de Kihara pour le calcul de la constante de Langmuir et l'équation d'état CPA (Cubic Plus Association) pour la modélisation des phases fluides. Nous avons montré que l'utilisation de l'équation d'état CPA, capable de prendre en compte l'auto association de l'eau apporte une amélioration très significative.Le développement d'un flash biphasique hydrate-fluide nous a permis de calculer les quantités d'hydrates mixtes formées et de les comparer à nos données expérimentales. / In industrial applications and during natural gas transport, the presence of water under liquid form or within a vapour phase can lead to gas hydrate formation causing the blockage of industrial units and transport lines. Hence, in order to avoid such situation, it is very important to well determine its formation conditions. It is occurred by using a rigorous thermodynamic model. Due to the lack of data in the literature concerning gas hydrates formation in the absence of an aqueous phase,usual thermodynamic models predict correctly gas hydrate dissociation temperature only in the presence of aqueous water. Our purpose is to propose a thermodynamic model with hydrate phase that can predict gas hydrate dissociation temperature in both cases: with and without water liquid phase.At first, using an existing apparatus, we have developed a new experimental protocol in order tomeasure gas hydrate dissociation temperature in the absence of liquid water. It consists in measuring the water content in the vapour phase as a function of the temperature by using a Karl Fischer coulometer. We have measured the dissociation temperature of many simple and mixture hydrates.We have also developed a thermodynamic model that is able to predict correctly gas hydrate dissociation temperature, in the absence and in the presence of liquid water. This model is based onthe use of Dharmawardhana's approach for the calculation of hydrate fugacity in the empty hypothetical hydrate, Kihara potential for the calculation of the Langmuir constant and CPA EoS forfluid phases modelling. We have shown that the use of CPA EoS improves the prediction of gas hydrate dissociation temperature. We have also developed a biphasic flash (hydrate-fluid) allowing the calculation of the formed mixture hydrate amounts. The calculated amounts are in agreement with the experimental ones.

A fim de possibilitar o emprego industrial dos óleos essenciais como agentes aromatizantes, é interessante que estes sejam submetidos à desterpenação, obtendo-se uma fração mais enriquecida em oxiterpenos, que é mais solúvel em água, estável, além de manter o aroma característico do óleo bruto. Este fracionamento pode ser realizado por extração líquida utilizando etanol como solvente. Neste contexto, o processo de desterpenação de óleo essencial de bergamota em coluna de discos rotativos perfurados (PRDC), utilizando como solventes soluções etanólicas com diferentes teores de água foi estudado por meio da obtenção de dados experimentais e de simulação computacional do processo. Em adição, o equilíbrio de fases, a 25 °C, de sistemas modelo de óleo de eucalipto, cravo e pimenta da Jamaica e de sistemas contendo óleos essenciais brutos de bergamota e lavandim também foram estudados nesta tese. Observou-se que, no estudo do equilíbrio de fases, dentre os sistemas monitorados, o composto oxigenado eugenol e o hidrocarboneto sesquiterpênico cariofileno, presentes nos óleos de cravo e pimenta da Jamaica apresentaram, respectivamente, o maior e menor valores de coeficiente de distribuição. Para os sistemas contendo óleos brutos de bergamota e lavandim verificou-se que os parâmetros binários dos modelos NRTL e UNIQUAC, ajustados previamente para o sistema modelo de óleo de bergamota, são capazes de descrever o equilíbrio de fases dos sistemas mais complexos. Ademais, com relação ao estudo do processo de desterpenação de óleo essencial em PRDC, pode-se inferir que a obtenção de frações enriquecidas nos compostos oxigenados é viável e factível para óleos que apresentem baixos teores de linalol em sua composição. / In order to enable the industrial use of essential oils as flavoring agents, they should be fractionated by means of deterpenation, yielding a fraction enriched in oxiterpenes, which is more soluble in water and more stable, besides keeping the characteristic aroma of the crude oil. This fractionation can be performed by liquid extraction using ethanol as solvent. In this context, the deterpenation process of bergamot essential oil was investigated in a perforated rotating disc column (PRDC) using ethanol solutions with different percentages of water as the solvent. The separation process was studied here by experimental data and computer simulations. Additionally, the phase equilibrium at 25 oC of systems containing eucalyptus, clove, and allspice, and systems containing crude essential oils of bergamot and lavandin were also analyzed. In the phase equilibrium analysis, it was observed that, among the evaluated components, the oxygenated compound eugenol and the terpenic hydrocarbon caryophyllene, found in the clove and allspice oil, showed, respectively, the highest and lowest values of distribution coefficient. For systems containing bergamot and lavandin crude essential oils, it was observed that the NRTL and UNIQUAC binary parameters, previously adjusted to the bergamot essential oil model system, were able to describe the phase equilibrium of more complex systems. Besides, in relation to the study of the deterpenation process of crude essential oils in PRDC, it could be inferred that enriched fractions in oxygenated compounds are viable and feasible to be obtained in oils that show low levels of linalol in their composition.

La spectroscopie RMN alliée à l’utilisation de solvants cristal-liquide fortement et faiblement orientants est une stratégie efficace pour élucider les structures et distributions conformationnelles de petites molécules organiques rigides et flexibles en solution, et déterminer les ordres orientationnel et positionnel des solutés comme des solvants orientés. Dans une première partie, afin d’explorer les différentes contributions aux couplages dipolaires d’un soluté donné, la très faible amplitude de l’ordre orientationnel d’une molécule quasi-sphérique, le tetramethylallène, dissoute dans un nématique thermotrope est exploitée. Dans cette situation limite, le caractère prédominant des mécanismes de réorientation et de vibration moléculaire est mis en évidence, et estimé. Dans une seconde partie, les données RMN obtenues à partir de solutés de petites tailles dissous dans des solvants smectiques sont combinées aux résultats de calculs reposant sur des concepts de thermodynamique statistique et de la théorie de la fonctionnelle de densité. L’efficacité de cette méthode dans la détermination des paramètres d’ordres positionnel du solvant et orientationnel des molécules-sondes est démontrée aussi bien dans le cas de phases conventionnelles smectiques A que celui plus délicat de smectiques interdigitées Ad. La stratégie d’analyse proposée est ensuite étendue à l’investigation des structures tridimensionnelles et équilibres conformationnels de molécules flexibles bioactives ou biomimétiques. Dans une perspective méthodologique, à l’aide d’études expérimentale et théorique portant sur le biphényle, molécule symétrique constituée d’un unique rotor, il est tout d’abord démontré l’intérêt des méthodes de simulations par dynamique moléculaire pour évaluer l’ensemble des couplages dipolaires d’un soluté donné dans une phase thermotrope, ultérieurement utilisés comme paramètres initiaux dans une analyse spectrale itérative, et in fine déterminées précisément. L’analyse spectrale chronophage et dont l’aboutissement est incertain si les paramètres initiaux sont difficiles à estimer, en est ainsi facilitée. Puis, les distributions conformationnelles d’anti-inflammatoires non stéroïdiens de dérivés salicylés et profènes, fluorés ou non, constitués d’un ou deux rotors indépendants sont présentées. Via l’utilisation inédite du modèle AP-DPD dans les solvants nématiques (chiraux) lyotropes faiblement orientants, et à partir des couplages dipolaires homo- et hétéronucléaires notamment obtenus grâce à l’expérience RMN GET-SERF, créée à propos pour permettre l’extraction simple et rapide des couplages 1H-19F, les surfaces d’énergie potentielle de ces biomolécules sont décrites de façon satisfaisante. Enfin, les équilibres conformationnels de deux stilbénoïdes constitués de deux rotors coopératifs sont déterminés dans deux solvants cristal-liquide, l’un fortement, l’autre faiblement orientant. Ces études comparatives permettent de discuter la fiabilité, la précision et l’accessibilité des observables RMN extraites dans les phases, et d’établir la complémentarité des analyses RMN réalisées dans ces solvants. / NMR spectroscopy in weakly and highly orienting media is used as a route for dealing with orientational, positional, structural and conformational problems of a variety of small rigid and flexible organic molecules in solution. First, the very weak orientational order of a quasi-spherical molecule dissolved in a nematic phase is exploited for exploring the role of the different contributions to the observed dipolar coupling. In such a limit condition, a predominant effect of the non-rigid reorientation-vibration coupling term emerges. Then, NMR data obtained from small rigid probes dissolved in smectic solvents are combined with a statistical thermodynamic density functional theory, in order to measure the positional order parameters of both solutes and solvent. The methodology gives good results when applied to a conventional smectic A liquid crystal and to the more delicate case of an interdigitated smectic Ad phase. The strategy is subsequently extended to the investigation of structure, order and conformational equilibrium of flexible bioactive or biomimetic molecules dissolved in various partially ordered NMR solvents. A first experimental and theoretical study is presented on the symmetric single-rotor molecule of biphenyl dissolved in a thermotropic liquid crystal. This test-case indicates molecular dynamics simulations are a promising tool for estimating a set of dipolar couplings of a solute in a thermotropic solvent, to be used as starting set of parameters in a standard operator-mediated NMR spectral analysis. Then, we report the conformational study of some single- and two-rotor nonsteroidal anti-inflammatory drugs, belonging to the families of salicylates and profens, dissolved in weakly orienting chiral nematic PBLG phases. A new pulse sequence, the Gradient Encoded heTeronuclear 1H-19F SElective ReFocusing NMR experiment (GET-SERF), is proposed here for the trivial edition of all 1H-19F couplings in one single NMR experiment, for a given fluorine atom. Starting from homo- and heteronuclear dipolar couplings, difficult to extract in thermotropic solvents because of a too complex spectral analysis, the torsional distributions of such molecules can be satisfactory described by the Additive Potential model combined with the Direct Probability Description of the torsional distribution in terms of Gaussian functions (AP-DPD approach). Finally, the conformational and orientational study of two stilbenoids displaying cooperative torsions is discussed in both a highly and weakly ordering liquid crystal phase. This comparative study allows to draw some conclusions on reliability, accuracy and accessibility of desired data in the two phases. Overall, this work proves NMR in liquid crystals is a flexible and meaningful tool for studying order, structure and conformation and it can greatly benefit from the availability of several aligning media inducing a different degree of order.