Made available in DSpace on 2014-10-09T12:51:57Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:25Z (GMT). No. of bitstreams: 0 / Neste trabalho foram estudados os níveis excitados do 193Ir produzidos a partir do decaimento β do 193Os (T1/2 ~ 30h). Para a obtenção das amostras radioativas, ~ 5mg de Ósmio metálico (99% enriquecido em 192Os) foram irradiados no reator IEA-R1, sob um fluxo de nêutrons da ordem de 1012cm2 s1 e depois analisadas, empregando-se a técnica de espectroscopia γ simples (unidimensional) com espectrômetro γ de alta resolução, bem como as técnicas de espectroscopia de coincidência γγ e de correlação angular direcional γγ (θ) usando um sistema de aquisição multiparamétrica composto por 4 detectores HPGe. A partir destes dados, foi possível adicionar 28 transições a este esquema de decaimento, 11 das quais já eram conhecidas de outros estudos envolvendo reações nucleares, além de 17 observadas pela primeira vez. Também foram acrescentados 8 níveis excitados ao esquema de decaimento, sendo 3 conhecidos por outras reações e 5 completamente novos. Além disso, foi possível confirmar a suspeita encontrada na literatura de que os níveis a 848,93keV e 849,093keV são o mesmo, além de confirmar a existência de um nível excitado a 806,9keV. A análise de correlação angular direcional permitiu a definição do spin de do nível excitado a 874kev (5/2+), além de propor uma probabilidade de 79% do nível a 1078keV ter spin 5/2, e de restringir as possibilidades de spin para o nível novo a 960keV para duas (1/2 ou 3/2). Também foi possível determinar a razão de mistura multipolar (δLn+1/Ln) para 43 transições, sendo 19 pela primeira vez e praticamente todas as restantes com precisão melhor que a encontrada na literatura. Finalmente, foi feita uma tentativa de compreender o núcleo através de um modelo teórico, o qual reproduziu muito bem o estado fundamental e os dois primeiros estados excitados do 193Ir. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Foi investigada a correlação entre a energia transversa (ET) produzida e a energia de partículas neutras (En) emitidas em colisões de íons de 28Si (plab=14.6 GeV/c por nucleon) com alvos de Al, Cu e Pb, estudadas pelo Experimento 814 no acelerador AGS do Laboratório Nacional de Brookhaven. A correlação entre a energia transversa e a energia dianteira produzida em colisões com emissão dos fragmentos 2H, 3H, 3He, 4He, 6He, 5Li e 6Li também foi investigada. Foi observado que a energia En dianteira produzida pelas partículas neutras tem uma forte dependência com a energia transversa ET produzida na colisão. Uma parametrização eficiente dos dados é obtida utilizando um modelo estatístico que relaciona o numero de espectadores da colisão com o numero de nêutrons detectados na região dianteira. As distribuições de momento desses fragmentos foram investigadas através do modelo de Goldhaber e os seus respectivos parâmetros 0 foram calculados para os eventos referentes as colisões de 28Si com alvos de Al, Cu e Pb. / We carried out a study of the forward neutral energy (En) and its correlation with the produced transverse energy (ET ) in collisions of 28Si ions (plab=14.6 GeV/c per nucleon) with Al, Cu, and Pb targets, investigated by Experiment 814 at the Brookhaven AGS. The correlation of the produced transverse energy with forward neutral energy from fragments 2H, 3H, 3He, 4He, 6He, 5Li and 6Li was also investigated. We find that the forward neutral energy En has a strong dependence on transverse energy ET produced in the collision. An efficient parametrization of this data set is accomplished through the use of a statistical model which relates the number of spectators in the collision to the number of neutrons detected in the forward direction. Momentum distributions of the fragments were investigated through the use of the Goldhaber model and the 0 parameter was calculated to each of the fragments in reactions of 28Si with Al, Cu and Pb targets.

Neste trabalho apresentamos um estudo das reações nucleares de alta energia que são fundamentais na definição do termo fonte dos reatores nucleares subcríticos acionados por fonte externa. Estas reações nucleares, também conhecidas como \"spallation\", consistem na interação de hádrons de alta energia com os núcleons do núcleo atômico. A fenomenologia destas reações consiste em duas etapas, sendo que à primeira, o próton interage através de espalhamentos múltiplos, em um processo denominado cascata intra-nuclear seguido da etapa na qual o núcleo excitado oriundo da cascata intranuclear ou evapora partículas de forma a atingir estados energéticos moderados ou fissiona, em um processo conhecido como competição entre evaporação e fissão. Neste trabalho os principais modelos nucleares, os modelos de Bertini e Cugnon, são revistos, pois estes modelos são fundamentais para propósito de projeto devido à falta de dados nucleares avaliados para estas reações. A implementação e validação dos métodos de cálculo para o projeto destas fontes são realizadas. A implementação da metodologia é realizada utilizando o programa MCNPX ( \"Monte Carlo N-Particle eXtended\"), dedicado para cálculos de transporte destas partículas e a validação é realizada mediante uma cooperação internacional junto a um projeto coordenado de pesquisa da Agencia Internacional de Energia Atômica e trabalhos disponíveis. O objetivo é qualificar os cálculos relacionados às reações nucleares e os canais de desexcitação envolvidos. O CRISP, um código nacional para a descrição da fenomenologia das reações envolvidas, também foi estudado e os modelos implementados no código foram revistos e melhorados de forma a dar continuidade ao seu processo de qualificação. Devido às limitações dos principais modelos na descrição de produção de nuclídeos leves, a reação de multi-fragmentação foi estudada. As discrepâncias nos cálculos de produção destes nuclídeos são atribuídas à falta do canal de multi-fragmentação estatística do núcleo. A implementação deste canal foi realizada para a aplicação em reações de altas energias junto ao código CRISP de forma a reproduzir a produção de nuclídeos leves, bem como sua validação mediante a comparação com dados experimentais disponíveis para este fenômeno, obtendo com isso uma melhor reprodução de todo o espectro de produção de nuclídeos do processo. / This work presents a study of high energy nuclear reactions which are fundamental to dene the source term in accelerator driven systems. These nuclear reactions, also known as spallation, consist in the interaction of high energetic hadrons with nucleons in the atomic nucleus. The phenomenology of these reactions consist in two step. In the rst, the proton interacts through multiple scattering in a process called intra-nuclear cascade. It is followed by a step in which the excited nucleus, coming from the intranuclear cascade, could either, evaporates particles to achieve a moderate energy state or ssion. This process is known as competition between evaporation and ssion. In this work the main nuclear models, Bertini and Cugnon are reviewed, since these models are fundamental for design purposes of the source term in ADS, due to lack of evaluated nuclear data for these reactions. The implementation and validation of the calculation methods for the design v of the source is carried out to implement the methodology of source design using the program MCNPX (Monte Carlo N-Particle eXtended), devoted to calculation of transport of these particles and the validation performed by an international cooperation together with a Coordinated Research Project (CRP) of the International Atomic Energy Agency and available jobs, in order to qualify the calculations on nuclear reactions and the de-excitation channels involved, providing a state of the art of design and methodology for calculating external sources of spallation for source driven systems. The CRISP, is a brazilian code for the phenomenological description of the reactions involved and the models implemented in the code were reviewed and improved to continue the qualication process. Due to failure of the main models in describing the production of light nuclides, the multifragmentation reaction model was studied. Because the discrepancies in the calculations of production of these nuclides are attributes to the lack of reaction channel and the implementation of this channel was carried out for applications in high energy reactions with the CRISP code to reproduce the production of light nuclides, as well, as its validation by comparison with experimental data available for this phenomenon. Thus, obtaining a better reproduction of the whole spectrum of production of nuclides in the process.

Funções de excitação para o espalhamento quase-elástico foram medidas com alta precisão e em passos de energia de 500 keV para os sistemas 16,18O + 56,60Ni. Dessas funções de excitação foram extraídas as distribuições de barreiras de fusão. Cálculos de canais acolplados foram realizados com o objetivo de evidenciar os canais responsáveis pelas estruturas observadas nas distribuições. Foram usados dois códigos computacionais, o CCFULL e o FRESCO, e os resultados foram similares. Comparamos Dfus com Dqe fornecidas pelo programa FRESCO para todos os sistemas e verificamos que são praticamente idênticas, confirmando que a aproximação Dfus = Dqe deve ser válida para esta região de massa. O que podemos concluir com o CCFULL é que o stripping de alfa para o sistema 16O + 58Ni é o canal de transferência mais importante em energias acima da barreira. Embora o cálculo com o FRESCO tenha mostrado que a importância desse canal é pequena. Para o sistema 16O + 60Ni, o canal de acoplamento mais forte é o pickup de alfa. Para os dois outros sistemas, 18O + 58,60Ni, foi verificado que o canal de transferência stripping de um nêutron tem forte influência sobre a forma das distribuições da barreira. Além dos canais de transferência, em todos os sistemas verificamos que a excitação do alvo é um canal de reação importante nos acoplamentos que originam as distribuições de barreiras obtidas experimentalmente. / Excitation functions for quasi-elastic scattering were measured with high precision with energy steps of 500 keV for the 16,18O + 56,60Ni systems. Fusion barrier distributions were extracted from the excitation functions. Coupled channel calculations were used in order to determine which channels are responsible for the structures observed in the experimental distributions. Two computation codes were used: CCFULL and FRESCO. Their results are similar. We compared Dfus with Dqe obtained with FRESCO and we have concluded that they are practically identical for all systems. This is a confirmation that the approximation Dfus = Dqe is reasonable in this mass region. The first conclusion with CCFULL code is that alpha stripping for the 16O + 58Ni system is the channel transfer most important at above barrier energies. However, the calculation with FRESCO showed that it has only minor importance. For the 16O + 60Ni system, the more expressive transfer channel is alpha pick-up. In the two other systems, 18O + 58,60Ni, we observed that one-neutron stripping has Strong influence on the barrier distributions. Beside the transfer channels, the target inelastic excitation is a very important reaction channel in all systems.

La formation des premières étoiles, quelques centaines de millions d'années après le Big Bang, marque la fin de l’âge sombre. Actuellement, nous n’avons aucune observation de la formation de ces étoiles, appelée popIII, mais d’après des simulations numériques de différents groupes, il semblerait que ces étoiles primordiales étaient très massives: plusieurs centaines de masses solaires. Ces premières étoiles, ont produits aussi des sursauts gamma (GRBs). Ainsi, l’étude des GRBs produits à partir des popIII, pourraient permette d’étudier directement le stade final des étoiles primordiales. Les télescopes d'aujourd'hui ne peuvent pas regarder assez loin dans le passé cosmique pour observer la formation des premières étoiles, mais la nouvelle génération de télescopes permettra de tester des idées théoriques sur la formation des premières étoiles.Les GRBs sont liés à la mort d’étoiles massives et qu'ils sont connectés avec des supernovae. En ce sens, les GRBs sont l'une des classes de processus explosifs en physique stellaire et devraient suivre les mêmes lois physiques que l'explosion des supernovae. Ce travail tente d'aborder le problème des GRBs comme un problème d'explosion stellaire et utilise les données d’observation sur les spectres et les courbes de lumières notamment.Dans le cadre de cette thèse, des outils spécifiques ont été développés pour étudier les explosions stellaires: un code numérique pour résoudre les réactions nucléaires a été incorporé dans le code hydrodynamique existant. Ces outils ont été utilisés dans les simulations de supernovae afin d’étudier les connections avec les sursauts gamma: analyse spectrale et étude statistique en fonction du redshift. / The formation of the first stars hundreds of millions of years after the Big-Bang marks the end of the Dark Ages. Currently, we have no direct observations on how the primordial stars formed, but according to modern theory of stellar evolution these stars should be very massive (about 100 Msun) Population III stars have a potential to produce probably most energetic flashes in the Universe - gamma-ray bursts. GRBs may provide one of the most promising methods to probe directly final stage of life of primordial stars. Today's telescopes cannot look far enough into the cosmic past to observe the formation of the first stars, but the new generation of telescopes will test theoretical ideas about the formation of the first stars.Thanks to many years of observations we have good GRB's data -statistics of occurrence, spectrum, lightcurves. But there are still a lot of questions in the theory of GRBs. We know that GRBs are related to the death of stars and that they are connected with supernovae. So gamma-ray bursts are one of the classes of explosive processes in stellar physics that should have a lot of common with supernovae explosions. In that case GRBs should follow the same physical laws of explosion as supernovae. This work tries to approach the problem of GRBs as a problem of stellar explosion.Necessary instruments of studying stellar explosion were developed as a part of doctoral research: code for solving systems of nuclear reaction equations was incorporated into hydrodynamical code. These tools were applied for supernovae simulations in order to find possible connection with GRBs. Basing on analysis of supernovae simulations spectral analysis of GRBs was performed.

Une bonne compréhension et une bonne capacité de prédiction de la section efficace de diffusion de neutron est essentielle à un grand nombre de technologies nucléaires, parmi lesquelles les réacteurs à fission. Pour les noyaux déformés, le calcul des observables de diffusion de nucléon pour la voie élastique et les premiers états excités de basse énergie requiert l'utilisation de calcul en voies couplées. Des potentiels optique et de transition phénoménologiques locaux sont le plus couramment utilisés dans les analyses par voies couplées, mais leur précision en dehors de leur domaine d'ajustement est imprévisible. Des approches microscopiques sont en cours de développement pour augmenter les capacités prédictives et résoudre les problèmes d'extrapolation. Un potentiel obtenu microscopiquement est non local, et de récentes études ont souligné l'importance de traiter explicitement cette non localité sans passer par une procédure de localisation. Notre but dans ce travail est d'étudier dans une approche microscopique, sans paramètre ajustable, l'impact de la non localité des potentiels sur les observables de diffusion de nucléon sur noyau cible. Pour ce faire, nous étudions la diffusion de neutron avec la matrice G de Melbourne qui représente l'interaction entre le projectile et un nucléon de la cible, et nous utilisons la RPA pour décrire la structure de la cible dans le cadre de nos premières applications sur le ⁹⁰Zr. Pour pouvoir étudier aussi des noyaux déformés, nous menons notre étude dans le cadre des voies couplées. La première partie de ce document contient la dérivation, faite dans un cadre unique et cohérent, des équations couplées pour la diffusion de nucléons et des potentiels microscopiques obtenues avec la matrice G de Melbourne et une description de la cible via la RPA. La deuxième partie est dédiée à la présentation des codes que nous avons développés durant ce projet de thèse : MINOLOP pour le calcul de potentiels microscopiques à partir de la matrice G de Melbourne et d'informations de structure données sous la forme d'une densité à 1 corps, et ECANOL pour la résolution des équations en voies couplées avec des potentiels non locaux en entrée. Enfin, nous présentons nos premières applications basées sur ces deux codes : l'étude d'émission de pré-équilibre due à des excitations à 2 phonons dans le ⁹⁰Zr. / A good understanding and prediction capacity of neutron scattering cross sections is crucial to many nuclear technologies, among which all kinds of reactors based on fission process. For deformed nuclei, the computation of scattering observables for the elastic channel and the first, low-lying excited states requires coupled channel calculations. Local, phenomenological optical and macroscopic transition potentials are the most commonly used in coupled channel analyses, but their accuracy outside of their fitting range remains unpredictable. Microscopic approaches are being developed in order to improve prediction power and solve the extrapolation issue. Potentials obtained microscopically are nonlocal, and recent studies have emphasized the importance of treating explicitly this nonlocality, without using a localization procedure. Our goal in the present work is to study in a quantum framework with no adjustable parameter, the impact of the nonlocality of potentials on scattering observables of nucleon-nucleus reactions. To achieve this we study neutron scattering with the Melbourne G matrix, which represents the interaction between the projectile and one nucleon of the target, and we describe the target’s structure using the RPA for our first applications to ⁹⁰Zr. In order to be able to study also deformed nuclei, we do our study in the coupled channel framework. The first part of this paper is dedicated to the derivation in a unique, consistent scope of coupled equations for nucleon-nucleus scattering and of the potentials obtained with the Melbourne G matrix and RPA structure input. Secondly, we describe the codes which we wrote during this Ph.D. project: MINOLOP for the computation of microscopic potentials using the Melbourne G matrix and structure inputs given in terms of a 1-body density, and ECANOL for the resolution of coupled channel equations using nonlocal potentials as input. Eventually, we present our first applications using these two codes to study pre-equilibrium emissions due to 2-phonon excitations in ⁹⁰Zr.

Many neutron rich nuclei are involved in the astrophysical r-process (rapid neutron capture process). The r-process forms an important path for heavy element nucleosynthesis and runs along the neutron drip line. Astrophysicists suggested core-collapse supernovae within a neutrino-driven wind scenario where the neutrino wind dissociates all previously formed elements into protons, neutrons and α particles, to be a possible astrophysical scenario for the r-process. Furthermore, reaction network calculations reported a high impact of light neutron rich nuclei to the r-process abundance. Reactions on these exotic nuclei can only be studied with radioactive ion beams as their half lifes, in the order of a few hundred milliseconds (T1/2,19N=330ms), are too low to fabricate target material out of them. Two examples of reactions along the path of the r-process are the 19N(n,γ)20N and the 20N(n, γ)21N reactions. Using 20N (resp. 21N) as a beam, these reactions were studied at the GSI Fragment Separator (FRS) in time-reversed conditions via Coulomb dissociation in the S393 experiment exploiting the virtual gamma field of a lead target. The experiment was performed at the LAND/R3B setup (Large Area Neutron Detector, Reactions with Relativistic Radioactive Beams) in a kinematically complete measurement, i.e., detecting all particles leaving the nuclear reaction. The neutrons flying at relativistic velocity were observed by the LAND detector, the calibration of which plays a crucial role for the present reaction. The Smiley effect, meaning that the measured energy of impinging particles in long scintillators is not independent of the hit position of the particle, has been investigated. It will be shown that reflections of the light traveling through the scintillator and the resulting longer path length of the light when not emitted directly towards the ends of the bar were identified to cause the Smiley effect. Gamma spectra in coincidence with outgoing 19N (resp. 20N) were generated. These fit well to recent publications and were utilized to separate transitions of the projectile nucleus into the ground state or first excited state of the ejectile nucleus. The Coulomb dissociation cross section was calculated for the total reaction, transitions into the ground state and the first excited state of the ejectile nucleus. Furthermore, excitation energy spectra were derived for both reactions separately for ground state transitions and for the dominating transitions into the first excited state. In order to facilitate future experiments on exotic nuclei, two detector solutions for the NeuLAND detector (the successor of LAND) were investigated. Utilizing minimum ionizing electrons of 30MeV at the ELBE facility, time resolutions and detection efficiencies were studied for an MRPC (Multi-gap Resistive Plate Chamber) based neutron detector with passive iron converters, on the one hand, and a pure scintillator based neutron ToF detector on the other hand. The ELBE data show good time resolutions (σt,electron < 120 ps) and detection efficiencies (ǫelectron > 90%) for both systems. Small MRPC prototypes were irradiated with 175MeV quasi-monochromatic neutrons at The Svedberg Laboratory (TSL) in Uppsala measuring efficiencies of ǫMRPC,neutron = 1.0%. It will be shown that MRPCs with passive steel converters may be included as neutron detectors in experiments where a lower multi-neutron capability than the one needed for NeuLAND is sufficient. / Viele neutronenreiche Kerne sind im schnellen Neutroneneinfangprozess (r-Prozess, engl. für rapid) involviert. Der r-Prozess bildet einen wichtigen Pfad für die Nukleosynthese schwerer Elemente und verläuft entlang der Neutronen-Dripline. Astrophysiker schlugen Kernkollaps-Supernovae innerhalb eines neutrinogetriebenen Windes als mögliches astrophysikalisches Szenario für den r-Prozess vor. Dabei werden alle zuvor gebildeten Elemente in Protonen, Neutronen und Alphapartikel dissoziiert. Außerdem ist von Berechnungen mit Reaktionsnetzwerken bekannt, dass leichte neutronenreiche Kerne einen hohen Einfluss auf die Elementverteilung des r-Prozesses haben. Reaktionen dieser exotischen Kerne können nur mit radioaktiven Ionenstrahlen studiert werden, da ihre Halbwertszeiten im Bereich von wenigen hundert Millisekunden (T1/2,19N=330ms) zu gering sind, um Probenmaterial daraus herzustellen. Zwei Beispiele solcher Reaktionen, die auf dem Pfad des r-Prozesses liegen, sind die 19N(n,γ)20N und die 20N(n,γ)21N Reaktionen. Unter Verwendung von 20N (bzw. 21N) als Strahl wurden diese Reaktionen am Fragment Separator (FRS) der GSI unter zeitumgekehrten Bedingungen mittels Coulomb-Aufbruch gemessen, indem das virtuelle Photonenfeld einer Bleiprobe ausgenutzt wurde. Das Experiment wurde am LAND/R3B Aufbau (Large Area Neutron Detector, Reactions with Relativistic Radioactive Beams) in einer kinematisch vollständigen Messung durchgeführt, d.h. alle ausgehenden Reaktionsprodukte wurden detektiert. Die relativistischen Neutronen wurden mit dem LAND-Detektor untersucht. Dessen Kalibration spielt eine wichtige Rolle für die hier analysierten Reaktionen. Dabei wurde der Smiley-Effekt studiert, welcher beinhaltet, dass die gemessene Energie von einfallenden Teilchen mittels langen Szintillatorstreifen nicht unabhängig von der Position ist, an der die Teilchen auf den Detektor treffen. Es wird gezeigt, dass Reflexionen des Lichtes beim Durchgang durch den Szintillator und die größere Weglänge, die das Licht zurücklegen muss, wenn es nicht direkt in Richtung der Enden des Szintillators emittiert wird, den Smiley-Effekt verursachen. Gamma-Spektren in Koinzidenz mit ausgehenden 19N (bzw. 20N) wurden gewonnen und stimmen gut mit früheren Veröffentlichungen überein. Diese Spektren wurden dazu verwendet, die Übergänge des Projektilkerns in den Grundzustand und den ersten angeregten Zustand des Ejektilkerns zu identifizieren. Die Wirkungsquerschnitte des Coulombaufbruchs der Projektilkerne und die Anregungsenergiespektren beider Reaktionen wurden berechnet und separiert in Übergänge in den Grundzustand und die dominierenden Übergänge in den ersten angeregten Zustand. Um künftige Experimente an exotischen Kernen zu ermöglichen, wurden zusätzlich zwei Detektorkonzepte für NeuLAND (Nachfolger von LAND) untersucht. Mit minimal ionisierenden Elektronen mit Energien von 30MeV aus dem Elektronenbeschleuniger ELBE wurden die Zeitauflösungen und Detektionseffizienzen zum einen für einen MRPC (Multi-gap Resistive Plate Chamber) basierenden Neutronendetektor mit passiven Stahlkonverter und zum anderen für einen reinen szintillatorbasierenden Neutronendetektor studiert. Die ELBE-Daten zeigen gute Zeitauflösungen (σt,electron < 120ps) und Detektionseffizienzen (ǫelectron > 90%) für beide Systeme. Kleine MRPC-Prototypen wurden mit quasi-monochromatischen Neutronen mit einer Energie von 175MeV am TSL (The Svedberg Laboratory) in Uppsala bestrahlt. Dabei wurden Effizienzen von ǫMRPC,neutron = 1.0% gemessen. Es wird gezeigt, dass MRPCs mit passiven Stahlkonvertern als Neutronendetektoren bei Experimenten, bei denen eine geringere Multineutronenfähigkeit als für NeuLAND ausreichend ist, eingesetzt werden können.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20897号 / 理博第4349号 / 新制||理||1624(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)准教授 川畑 貴裕, 教授 永江 知文, 教授 鶴 剛 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

<p dir="ltr">Partial methane oxidation (PMO) to methanol is a desirable route for upgrading natural and shale gas resources to liquid chemical intermediates and has been extensively studied on Cu-zeolites. Prior work has studied the stoichiometric PMO reaction on O₂-activated Cu-zeolites, leading to several proposals for candidate O_x-bridged Cu active site structures. More recent studies have investigated the catalytic PMO reaction and have reported that Cu-chabazite (CHA) zeolites tend to exhibit the highest methane oxidation rate (per Cu) among other Cu-zeolite topologies. Multiple studies have reported that decreasing the Cu site density and increasing the framework Al density increase the selectivity towards methanol, but have proposed different mechanistic explanations. Here, we study the influence of Cu active site distribution, which was altered by varying the extraframework Cu site density and the arrangement of framework Al atoms, on the kinetic parameters governing continuous PMO. The number of redox active Cu species was quantified through linear combination fitting of XANES spectra collected under <i>in situ</i> and transient conditions after reactant (O₂) cut-off, and the Cu speciation was investigated with XAS. Total methane oxidation rates and individual product formation rates (CH₃OH, CO, CO₂), normalized per total Cu, increased with Cu density because this influenced the speciation of Cu formed during the reaction. All Cu-CHA samples showed PMO rates that were nearly first-order in CH₄ pressure, consistent with prior reports that C-H activation in CH₄ is the rate limiting step. Samples with differing framework Al arrangement, but fixed extraframework Cu density, showed formation rates of over-oxidation products (e.g., CO₂) that had different apparent reaction orders in O₂, implying differences in the Cu active sites formed during reaction. Changes to Cu oxidation states were monitored with <i>in situ</i> XAS. Samples were first subjected to an oxidative pretreatment (723 K, 5 kPa O₂) and then to catalytic PMO conditions to reach steady-state. Steady-state XANES spectra collected after O₂ was removed from the reactant stream showed the expected reduction from Cu(II) to Cu(I), and the fraction of CH₄-reducible Cu(II) sites decreased with increasing Cu content; increasing the CH₄ pressure ten-fold increased the number of CH₄-reducible sites by a factor of ~1.5. These spectroscopic and kinetic observations suggest there are a mixture of Cu site types that are present during catalysis, each with different intrinsic reactivity toward CH₄ and selectivity to CH₃OH. To rationalize these observations, a reaction mechanism is proposed for a two-site model and used to derive rate expressions that describe apparent reaction orders for the total CH₄ oxidation rate and product formation rates on Cu-CHA zeolites of varying Cu content.</p><p dir="ltr">Additional routes for CH₄ activation include partial CH₄ oxidation over Fe zeolites that convert CH₄ at ambient temperature following an activation in nitrous oxide (N₂O), or through CH₄ dehydroaromatization (DHA) to benzene over Mo zeolites under non-oxidative conditions. Prior work on PMO over Fe-zeolites has identified candidate active site structures, but the influence of zeolite structural properties on ion-exchanged Fe speciation remains unclear. This work sought to understand the interaction of Fe with the zeolite framework during solvent-assisted deposition procedures and subsequent thermal treatments. In pursuit of this objective, Fe uptake isotherms were measured, and Fe speciation was characterized with UV-Vis spectroscopy and H₂ temperature programmed reduction (H₂ TPR). Increased framework Al site pairing increased the uptake of Fe in CHA zeolites, and high temperature treatments (723 K) resulted in the formation of oligomeric Fe structures as indicated by UV-vis. In CH₄ DHA over Mo-MFI, a principal challenge is the irreversible loss of catalytic reactivity with repeated reaction-regeneration cycles, attributed to dealumination of the zeolite structure during high-temperature oxidative regeneration treatments that produce steam. CHA zeolites are known to be more resistant to dealumination than MFI, but its smaller pore structure prevents diffusion of benzene and other aromatic products leading to rapid coking. This work attempted to address the diffusion limitations for benzene in Mo-CHA by synthesizing crystals with nanoscale dimensions by incorporating a surfactant into the crystallization procedure, generating solids with a flake-like morphology.</p><p dir="ltr">The overarching strategy in this work was to influence the speciation of metal sites and complexes in zeolites by controlling the density and arrangement of anionic Al anchoring sites within the framework and the density of extraframework metal species. In the case of Cu-zeolites, the amount of Cu present on the material influences the structures that form during catalysis that influences both the rate and selectivity of catalytic PMO.</p>

<p dir="ltr">Regulation of complex biological processes aims to achieve goals essential for an organism's survival or to exhibit specific phenotypes in response to stimuli. This regulation can occur at several levels, such as cellular metabolism, signaling pathways, gene transcription, mRNA translation into proteins, and post-translational modifications. Systems biology approaches can facilitate integrating mechanistic knowledge and high-throughput omics data to develop quantitative models that can help improve our understanding of regulations at various levels. However, computational modeling of biological processes is challenging due to the vast details of the control processes with unknown details. The cybernetic modeling approach accounts for unknown control mechanisms by defining a biological goal that the system aims to optimize, and subsequently mathematically formulates the cybernetic goal.</p><p dir="ltr">This thesis aims to develop a mathematical framework that integrates a cybernetic model with novel information-theoretic methods to study the inflammatory response in mammalian macrophage cells. The inflammatory response of the body is a protective mechanism that fights off infecting pathogens by inducing the production of immune signaling proteins called cytokines and chemokines, as well as specific lipids known as eicosanoids. However, excessive levels of cytokines and eicosanoids may result in chronic inflammatory diseases such as hyper-inflammation syndrome, COVID-19, and asthma. Only a few studies have focused on modeling AA metabolism, and the developed models utilize Michaelis-Menten kinetics or assume the linear form and can, at best, include control at the gene expression level only. The distinguishing feature of a cybernetic model is that by defining a cybernetic objective, it can account for control at multiple levels, including transcriptional, translational, and post-translational modifications.</p><p dir="ltr">The following paragraphs address a specific research problem, outline the approaches to investigate it, and summarize the key findings.</p><p dir="ltr">First, we studied the cellular response to inflammatory stimuli that produce eicosanoids—prostanoids (PRs) and leukotrienes (LTs)—and signaling molecules—cytokines and chemokines—by macrophages. A few studies suggest that targeting eicosanoid metabolism could be a promising new approach to regulating cytokine storm in COVID-19 infection. We developed a cybernetic model combined with novel information-theoretic approaches to study the integrated system of eicosanoids and cytokines. Our cybernetic model formulates a cybernetic goal, which requires the causal relationship between the eicosanoid and cytokine secretion processes; however, this causal relationship is unknown due to insufficient mechanistic information. We developed novel information-theoretic approaches (discussed later in detail) to understand the causality between eicosanoids and cytokines. The causality result from information theory suggests that Arachidonic acid (AA) may be the cause for initiating the secretion of cytokine TNF. The model captured the data for all experimental conditions, including control, treatment with Adenosine triphosphate (ATP), (3-deoxy-d-manno-octulosonic acid)2-lipid A<i> </i>(KLA), and a combined treatment of ATP and KLA in mouse bone marrow-derived macrophages (BMDM). The model explains the dynamics of metabolite for all experimental conditions, validating the hypothesis. It also enhanced our understanding of enzyme dynamics by predicting their profiles. The results indicated that the dominant metabolites are PGD₂ (a PR) and LTB₄ (an LT), aligning with their corresponding known prominent biological roles during inflammation. Based on the causality and cybernetic model result and using heuristic arguments, we also infer that AA overproduction can lead to increased secretion of cytokines/chemokines. Consequently, a potential clinical implication of this study is that modulating eicosanoid levels could lower TNFα expression, suggesting eicosanoids could be a viable strategy for managing hyperinflammation.</p><p dir="ltr">Second, we studied the dynamics of the anti-inflammatory lipid mediators from eicosapentaenoic acid (EPA) metabolism, which can be beneficial in reducing the severity of diseases such as cancer, cardiovascular effects, and promoting visual and neurological development. This study employed a cybernetic model to study the enzyme competition between AA and EPA metabolism in murine macrophages. The cybernetic model adequately captured the experimental data for control and EPA-supplemented conditions in RAW 264.7 macrophages. The cybernetic variables provide insights into the competition between AA and EPA for the COX enzyme. Predictions from our model suggest that the system undergoes a switch from a predominantly pro-inflammatory state in control to an anti-inflammatory state with EPA supplementation. A potential application of this study is utilizing the model estimation of the ratio of and concentrations required for the switch to occur as 2.2, which aligns with the experimental observations and falls within the recommended range of 1-5 needed to promote anti-inflammatory response.</p><p dir="ltr">Third, we focused on predicting novel causal connections between AA and cytokines using time series analysis as mechanistic information connecting AA and cytokines is unknown. In this work, we developed Time delay Renyi Symbolic Transfer Entropy (TDRSTE), a novel model-free information-theoretic metric. We computed it from high-throughput omics datasets for bivariate non-stationary time series to quantify causal time delays. The TDRSTE method adequately estimated time delay for the synthetic dataset, captured causality for the real-world biological dataset of the AA metabolic network with a prediction accuracy of 80.6%, where it correctly identified 25 out of 31 connections, and detected novel connections between non-stationary lipidomics and transcriptomics profiles for eicosanoids and cytokines, respectively. The results indicate that AA may initiate the secretion of cytokines like TNFα, IL1α, IL18, and IL10. Conversely, cytokines such as IL6 and IL1β may have an early causal impact on AA. These findings suggest a potential causal link between AA and cytokines, paving the way for further exploration with more extensive experimental data in future investigations.</p><p dir="ltr">This thesis develops a theoretical framework that integrates cybernetic modeling technique with novel information-theoretic approaches to study inflammatory response in mouse macrophages. As described in previous paragraphs, the success of cybernetic framework in capturing the dynamic behavior of multiple processes serves to validate the idea that regulation is driven towards achieving cellular goals. The cybernetic framework can be applied to better understand the mechanisms underlying the normal and diseased states, and to predict the behavior of the inflammatory system given a perturbation.</p>