4,968 research outputs found

    Symmetries of Riemann surfaces and magnetic monopoles

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    This thesis studies, broadly, the role of symmetry in elucidating structure. In particular, I investigate the role that automorphisms of algebraic curves play in three specific contexts; determining the orbits of theta characteristics, influencing the geometry of the highly-symmetric Bring’s curve, and in constructing magnetic monopole solutions. On theta characteristics, I show how to turn questions on the existence of invariant characteristics into questions of group cohomology, compute comprehensive tables of orbit decompositions for curves of genus 9 or less, and prove results on the existence of infinite families of curves with invariant characteristics. On Bring’s curve, I identify key points with geometric significance on the curve, completely determine the structure of the quotients by subgroups of automorphisms, finding new elliptic curves in the process, and identify the unique invariant theta characteristic on the curve. With respect to monopoles, I elucidate the role that the Hitchin conditions play in determining monopole spectral curves, the relation between these conditions and the automorphism group of the curve, and I develop the theory of computing Nahm data of symmetric monopoles. As such I classify all 3-monopoles whose Nahm data may be solved for in terms of elliptic functions

    Climate Change and Critical Agrarian Studies

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    Climate change is perhaps the greatest threat to humanity today and plays out as a cruel engine of myriad forms of injustice, violence and destruction. The effects of climate change from human-made emissions of greenhouse gases are devastating and accelerating; yet are uncertain and uneven both in terms of geography and socio-economic impacts. Emerging from the dynamics of capitalism since the industrial revolution — as well as industrialisation under state-led socialism — the consequences of climate change are especially profound for the countryside and its inhabitants. The book interrogates the narratives and strategies that frame climate change and examines the institutionalised responses in agrarian settings, highlighting what exclusions and inclusions result. It explores how different people — in relation to class and other co-constituted axes of social difference such as gender, race, ethnicity, age and occupation — are affected by climate change, as well as the climate adaptation and mitigation responses being implemented in rural areas. The book in turn explores how climate change – and the responses to it - affect processes of social differentiation, trajectories of accumulation and in turn agrarian politics. Finally, the book examines what strategies are required to confront climate change, and the underlying political-economic dynamics that cause it, reflecting on what this means for agrarian struggles across the world. The 26 chapters in this volume explore how the relationship between capitalism and climate change plays out in the rural world and, in particular, the way agrarian struggles connect with the huge challenge of climate change. Through a huge variety of case studies alongside more conceptual chapters, the book makes the often-missing connection between climate change and critical agrarian studies. The book argues that making the connection between climate and agrarian justice is crucial

    A Critical Review Of Post-Secondary Education Writing During A 21st Century Education Revolution

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    Educational materials are effective instruments which provide information and report new discoveries uncovered by researchers in specific areas of academia. Higher education, like other education institutions, rely on instructional materials to inform its practice of educating adult learners. In post-secondary education, developmental English programs are tasked with meeting the needs of dynamic populations, thus there is a continuous need for research in this area to support its changing landscape. However, the majority of scholarly thought in this area centers on K-12 reading and writing. This paucity presents a phenomenon to the post-secondary community. This research study uses a qualitative content analysis to examine peer-reviewed journals from 2003-2017, developmental online websites, and a government issued document directed toward reforming post-secondary developmental education programs. These highly relevant sources aid educators in discovering informational support to apply best practices for student success. Developmental education serves the purpose of addressing literacy gaps for students transitioning to college-level work. The findings here illuminate the dearth of material offered to developmental educators. This study suggests the field of literacy research is fragmented and highlights an apparent blind spot in scholarly literature with regard to English writing instruction. This poses a quandary for post-secondary literacy researchers in the 21st century and establishes the necessity for the literacy research community to commit future scholarship toward equipping college educators teaching writing instruction to underprepared adult learners

    Radiation-directed production of chemical reagents and petroleum additives from waste organic feedstocks

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    Nuclear cogeneration is the collation of co-processes that aims to improve the sustainability, overall efficiency, and profitability of nuclear power by producing alternative products alongside electricity. A range of existing cogeneration processes explores the use of waste stream process heat for a variety of processes including district heating and desalination. However, the direct application of under-utilized ionization energy has yet to be fully realized. This thesis is a study on the potential application of ionizing radiation from nuclear facilities towards the radiolytic production of organic chemicals derived from waste renewable feedstocks. Here we show that glycerol, a notable waste feedstock from biodiesel production can be converted into acetol (hydroxyacetone) or solketal which are textile and biofuel additives, respectively using ionizing radiation from a 250-kW research fission reactor. The radical-initiated chain reaction for hydroxyl acetone (acetol) production is optimised to produce the highest G value (2.7 ± 0.4 ”mol J−1) and mass productivity (~1 %) to be reported in the available radiolysis literature. A previously unreported radiolytic product, solketal, which is a valuable biofuel additive is produced radiolytically using ternary glycerol, acetone, and water mixtures with G-values of 1.5 ± 0.2 ”mol J−1 at 50 kGy. Empirical data showed a preference for low LET, low dose rate, Îł-ray emissions such as those from spent fuel was found to be favourable for acetol and solketal production. Simulating three production scenarios with MCNP models for preferential solketal production found that a spent fuel facility consisting of ~1710 elements showed the largest production capacity at 57.4 ± 5.6 t year−1 due to the high volume available to be irradiated. Extrapolating to a theoretical European production network involving ~180 equivalent SFP facilities based on relative reactor power, a total of (1.3 ± 0.1) × 104 t year−1 of solketal could be produced, contributing to (2.5 ± 0.2) × 108 litres year−1 to a (95% petroleum, 5% solketal) fuel blend. While this represents only ~0.3 % of total transport fuels consumed within the EU, it presents a pioneering process that could be feasible if G-values and mass productivities were improved upon

    The Globalization of Artificial Intelligence: African Imaginaries of Technoscientific Futures

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    Imaginaries of artificial intelligence (AI) have transcended geographies of the Global North and become increasingly entangled with narratives of economic growth, progress, and modernity in Africa. This raises several issues such as the entanglement of AI with global technoscientific capitalism and its impact on the dissemination of AI in Africa. The lack of African perspectives on the development of AI exacerbates concerns of raciality and inclusion in the scientific research, circulation, and adoption of AI. My argument in this dissertation is that innovation in AI, in both its sociotechnical imaginaries and political economies, excludes marginalized countries, nations and communities in ways that not only bar their participation in the reception of AI, but also as being part and parcel of its creation. Underpinned by decolonial thinking, and perspectives from science and technology studies and African studies, this dissertation looks at how AI is reconfiguring the debate about development and modernization in Africa and the implications for local sociotechnical practices of AI innovation and governance. I examined AI in international development and industry across Kenya, Ghana, and Nigeria, by tracing Canada’s AI4D Africa program and following AI start-ups at AfriLabs. I used multi-sited case studies and discourse analysis to examine the data collected from interviews, participant observations, and documents. In the empirical chapters, I first examine how local actors understand the notion of decolonizing AI and show that it has become a sociotechnical imaginary. I then investigate the political economy of AI in Africa and argue that despite Western efforts to integrate the African AI ecosystem globally, the AI epistemic communities in the continent continue to be excluded from dominant AI innovation spaces. Finally, I examine the emergence of a Pan-African AI imaginary and argue that AI governance can be understood as a state-building experiment in post-colonial Africa. The main issue at stake is that the lack of African perspectives in AI leads to negative impacts on innovation and limits the fair distribution of the benefits of AI across nations, countries, and communities, while at the same time excludes globally marginalized epistemic communities from the imagination and creation of AI

    Rational development of stabilized cyclic disulfide redox probes and bioreductive prodrugs to target dithiol oxidoreductases

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    Countless biological processes allow cells to develop, survive, and proliferate. Among these, tightly balanced regulatory enzymatic pathways that can respond rapidly to external impacts maintain dynamic physiological homeostasis. More specifically, redox homeostasis broadly affects cellular metabolism and proliferation, with major contributions by thiol/disulfide oxidoreductase systems, in particular, the Thioredoxin Reductase Thioredoxin (TrxR/Trx) and the Glutathione Reductase-Glutathione-Glutaredoxin (GR/GSH/Grx) systems. These cascades drive vital cellular functions in many ways through signaling, regulating other proteins' activity by redox switches, and by stoichiometric reductant transfers in metabolism and antioxidant systems. Increasing evidence argues that there is a persistent alteration of the redox environment in certain pathological states, such as cancer, that heavily involve the Trx system: upregulation and/or overactivity of the Trx system may support or drive cancer progression, making both TrxR and Trx promising targets for anti-cancer drug development. Understanding the biochemical mechanisms and connections between certain redox cascades requires research tools that interact with them. The state-of-the-art genetic tools are mostly ratiometric reporters that measure reduced:oxidized ratios of selected redox pairs or the general thiol pool. However, the precise cellular roles of the central oxidoreductase systems, including TrxR and Trx, remain inaccessible due to the lack of probes to selectively measure turnover by either of these proteins. However, such probes would allow measuring their effective reductive activity apart from expression levels in native systems, including in cells, animals, or patient samples. They are also of high interest to identify chemical inhibitors for TrxR/Trx in cells and to validate their potential use as anti-cancer agents (to date, there is no selective cellular Trx inhibitor, and most known TrxR inhibitors were not comprehensively evaluated considering selectivity and potential off-targets). However, small molecule redox imaging tools are underdeveloped: their protein specificity, spectral properties, and applicability remain poorly precedented. This work aimed to address this opportunity gap and develop novel, small molecule diagnostic and therapeutic tools to selectively target the Trx system based on a modular trigger cargo design: artificial cyclic disulfide substrates (trigger) for oxidoreductases are tethered to molecular agents (cargo) such that the cargo’s activity is masked and is re-established only through reduction by a target protein. The rational design of these novel reduction sensors to target the cell's strongest disulfide-reducing enzymes was driven by the following principles: (i) cyclic disulfide triggers with stabilized ring systems were used to gain low reduction potentials that should resist reduction except by the strongest cellular reductases, such as Trx; and (ii) the cyclic topology also offers the potential for kinetic reversibility that should select for dithiol-type redox proteins over the cellular monothiol background. Creating imaging agents based on such two-component designs to selectively measure redox protein activity in native cells required to combine the correct trigger reducibility, probe activation kinetics, and imaging modalities and to consider the overall molecular architecture. The major prior art in this field has applied cyclic 5-membered disulfides (1,2 dithiolanes) as substrates for TrxR in a similar way to create such tools. However, this motif was described elsewhere as thermodynamically instable and was due to widely used for dynamic covalent cascade reactions. By comparing a novel 1,2 dithiolane-based probe to the state-of-the-art probes, including commercial TrxR sensors, by screening a conclusive assay panel of cellular TrxR modulations, I clarified that 1,2 dithiolanes are not selective substrates for TrxR in biological settings (Nat Commun 2022). Instead, aiming for more stable ring systems and thus more robust redox probes, during this work, I developed bicyclic 6 membered disulfides (piperidine fused 1,2 dithianes) with remarkably low reduction potentials. I showed that molecular probes using them as reduction sensors can be mostly processed by thioredoxins while being stable against reduction by GSH. The thermodynamically stabilized decalin like topology of the cis-annelated 1,2 dithianes requires particularly strong reductants to be cleaved. They also select for dithiol type redox proteins, like Trx, based on kinetic reversibility and offer fast cyclization due to the preorganization by annelation (JACS 2021). This work further expanded the system’s modularity with structural cores based on piperazine-fused 1,2 dithianes with the two amines allowing independent derivatization. Diagnostic tools using them as reduction sensors proved equally robust but with highly improved activation kinetics and were thus cellularly activated. Cellular studies evolved that they are substrates for both Trxs and their protein cousins Grxs, so measuring the cellular dithiol protein pool rather than solely Trx activity (preprint 2023). Finally, a trigger based on a slightly adapted reduction sensor, a desymmetrized 1,2 thiaselenane, was designed for selective reduction by TrxR’s selenol/thiol active site, then combined with a precipitating large Stokes’ shift fluorophore and a solubilizing group, to evolve the first selective probe RX1 to measure cellular TrxR activity, which even allowed high throughput inhibitor screening (Chem 2022). The central principle of this work was further advanced to therapeutic prodrugs based on the duocarmycin cargo (CBI) with tunable potency (JACS Au 2022) that can be used to create off-to-on therapeutic prodrugs. Such CBI prodrugs employing stabilized 1,2 dichalcogenide triggers proved to be cytotoxins that depend on Trx system activity in cells. They could further be exploited for cell-line dependent reductase activity profiling by screening their redox activation indices, the reduction-dependent part of total prodrug activation, in 177 cell lines. Beyond that, these prodrugs were well-tolerated in animals and showed anti-cancer efficacy in vivo in two distinct mouse tumor models (preprint 2022). Taken together, I introduced unique monothiol-resistant reducible motifs to target the cellular Trx system with chemocompatible units for each for TrxR and Trx/Grx, where the cyclic nature of the dichalcogenides avoids activation by GSH. By using them with distinct molecular cargos, I developed novel selective fluorescent reporter probes; and introduced a new class of bioreductive therapeutic constructs based on a common modular design. These were either applied to selectively measure cellular reductase activity or to deliver cytotoxic anti cancer agents in vivo. Ongoing work aims to differentiate between the two major redox effector proteins Trx and Grx, requiring additional layers of selectivity that may be addressed by tuned molecular recognition. The flexible use of various molecular cargos allows harnessing the same cellular redox machinery by either probes or prodrugs. This allows predictive conclusions from diagnostics to be directly translated into therapy and offers great potential for future adaptation to other enzyme classes and therapeutic venues.Die zellulĂ€re Redox-Homöostase hĂ€ngt von Thiol/Disulfid-Oxidoreduktasen ab, die den Stoffwechsel, die Proliferation und die antioxidative Antwort von Zellen beeinflussen. Die wichtigsten Netzwerke sind die Thioredoxin Reduktase-Thioredoxin (TrxR/Trx) und Glutathion Reduktase-Glutathion-Glutaredoxin (GR/GSH/Grx) Systeme, die ĂŒber Redox-Schalter in Substratproteinen lebenswichtige zellulĂ€re Funktionen steuern und so an der Redox-Regulation und -SignalĂŒbertragung beteiligt sind. Persistente VerĂ€nderungen des Redoxmilieus in pathologischen ZustĂ€nden, wie z. B. bei Krebs, sind in hohem Maße mit dem Trx-System verbunden. Eine Hochregulierung und/oder ÜberaktivitĂ€t des Trx-Systems, die bei vielen Krebsarten auftreten, unterstĂŒtzt zudem das Fortschreiten des Krebswachstums, was TrxR/Trx zu vielversprechenden Zielproteinen fĂŒr die Entwicklung neuer Krebsmedikamente macht. Um die biochemischen Prozesse dahinter zu erforschen, sind spezielle Techniken zur Visualisierung und Messung enzymatischer AktivitĂ€t nötig. Die hierzu geeigneten, meist genetischen Sensoren messen ratiometrisch das VerhĂ€ltnis reduzierter/oxidierter Spezies in zellulĂ€rem Umfeld oder spezifisch ausgewĂ€hlte Redoxpaare. Die weitere Erforschung der exakten Funktion von TrxR/Trx und deren Substrate ist jedoch durch mangelnde Nachweismethoden limitiert. Diese sind außerdem zur Validierung chemischer Hemmstoffe fĂŒr TrxR/Trx in Zellen und deren potenziellen Verwendung als Krebsmittel von großem Interesse. Bislang gibt es keinen selektiven zellulĂ€ren Trx-Inhibitor und potenzielle Off-Target-Effekte der bekannten TrxR-Inhibitoren wurden nicht abschließend bewertet. Ziel dieser Arbeit ist die Entwicklung niedermolekularer, diagnostischer und therapeutischer Werkzeuge, die selektiv auf das Trx-System abzielen und auf einem modularen Trigger-Cargo Design basieren. Hierzu werden zyklische Disulfid-Substrate (Trigger) fĂŒr Oxidoreduktasen so mit molekularen Wirkstoffen (Cargo) verknĂŒpft, dass dabei die WirkstoffaktivitĂ€t maskiert, und erst nach Reduktion durch ein Zielprotein wiederhergestellt wird. Diese neuartigen, synthetischen Reduktionssensoren basieren auf den folgenden Grundprinzipien: (i) Zyklische Disulfide sind thermodynamisch stabilisiert und können nur durch die stĂ€rksten Reduktasen gespalten werden; und (ii) die zyklische Topologie ermöglicht die kinetische ReversibilitĂ€t der zwei Thiol-Disulfid-Austauschreaktionen, die eine erste Reaktion mit Monothiolen, wie z. B. GSH, sofort umkehrt und so eine vollstĂ€ndige Reduktion verhindert. Die meisten frĂŒheren Arbeiten auf diesem Gebiet verwendeten ein zyklisches, fĂŒnfgliedriges Disulfid (1,2 Dithiolan) als Substrat fĂŒr TrxR. Das gleiche Strukturmotiv wurde jedoch an anderer Stelle als thermodynamisch instabil beschrieben und aufgrund dieser Eigenschaft explizit fĂŒr dynamische Kaskadenreaktionen verwendet. Deshalb vergleicht diese Arbeit zu Beginn einen neuen 1,2 Dithiolan basierten fluorogenen Indikator mit bestehenden, z. T. kommerziellen, Redox Sonden fĂŒr TrxR in einer Reihe von Zellkultur-Experimenten unter Modulation der zellulĂ€ren TrxR AktivitĂ€t und stellt so einen Widerspruch in der Literatur klar: 1,2 Dithiolane eignen sich nicht als selektive Substrate fĂŒr TrxR, da sie labil sowohl gegen die Reduktion durch andere Redoxproteine, als auch gegen den Monothiol Hintergrund in Zellen sind (Nat. Commun. 2022). Als alternatives Strukturmotiv wird in dieser Arbeit ein bizyklisches sechsgliedriges Disulfid (anneliertes 1,2 Dithian) etabliert. Durch sein niedriges Reduktionspotenzial, also seine hohe Resistenz gegen Reduktion, werden molekulare Sonden basierend auf diesem 1,2 Dithian als Reduktionssensor fast ausschließlich von Trx aktiviert, nicht aber von TrxR oder GSH (JACS 2021). Dieses Kernmotiv bestimmt dabei die Reduzierbarkeit, und damit die EnzymspezifitĂ€t, durch seine zyklische Natur und die Annelierung, auch unter Verwendung unterschiedlicher Farb-/Wirkstoffe. Auf dieser Grundlage konnte die molekulare Struktur durch einen weiteren Modifikationspunkt fĂŒr die flexible Verwendung weiterer funktioneller Einheiten ergĂ€nzt werden. Obwohl zellulĂ€re Studien ergaben, dass diese neuartigen 1,2 Dithian Einheiten in Zellen sowohl Trx als auch das strukturell verwandte Grx adressieren, sind die daraus resultierenden diagnostischen MolekĂŒle wertvoll, um den katalytischen Umsatz zellulĂ€rer Dithiol-Reduktasen, der sogenannten Trx Superfamilie, selektiv anzuzeigen (Preprint 2023). BegĂŒnstigt durch das modulare MolekĂŒldesign stellt diese Arbeit zudem das erste Reportersystem RX1 zum selektiven Nachweis der TrxR-AktivitĂ€t in Zellen vor. Es basiert auf der Verwendung eines zyklischen, unsymmetrischen Selenenylsulfid-Sensors (1,2 Thiaselenan), der selektiv von dem einzigartigen Selenolat der TrxR angegriffen wird, und dadurch letztlich nur von TrxR reduziert werden kann. RX1 eignete sich zudem fĂŒr eine Hochdurchsatz-Validierung bestehender TrxR Inhibitoren und unterstreicht dadurch den kommerziellen Nutzen derartiger Diagnostika (Chem 2022). Das zentrale Trigger-Cargo Konzept dieser Arbeit wurde fĂŒr therapeutische Zwecke weiterentwickelt und nutzt dabei den einzigartigen Wirkmechanismus der Duocarmycin-Naturstoffklasse (CBI) (JACS Au 2022) zur Entwicklung reduktiv aktivierbarer Therapeutika. CBI Prodrugs basierend auf stabilisierten Redox-Schaltern (1,2 Dithiane fĂŒr Trx; 1,2 Thiaselenan fĂŒr TrxR) reagierten signifikant auf TrxR-Modulation in Zellen. Sie wurden darĂŒber hinaus durch das Referenzieren ihrer AktivitĂ€t gegenĂŒber nicht-reduzierbaren KontrollmolekĂŒle fĂŒr die Erstellung zelllinienabhĂ€ngiger Profile der ReduktaseaktivitĂ€t in 177 Zelllinien genutzt. Schließlich waren diese neuen Krebsmittel im Tiermodell gut vertrĂ€glich und zeigten in zwei verschiedenen Mausmodellen eine krebshemmende Wirkung (Preprint 2022b). Zusammenfassend prĂ€sentiert diese Dissertation monothiol-resistente reduzierbare Trigger-Einheiten fĂŒr das zellulĂ€re Trx-System zur Entwicklung neuartiger, selektiver Reporter-Sonden, sowie eine neue Klasse reduktiv aktivierbarer Krebsmittel auf Basis eines adaptierbaren Trigger-Cargo Designs. Diese fanden entweder zur selektiven Messung zellulĂ€rer ProteinaktivitĂ€t oder zum Einsatz als Antikrebsmittel Verwendung. Es wurden chemokompatible Motive sowohl fĂŒr TrxR als auch fĂŒr Trx/Grx identifiziert, wobei deren zyklische Natur eine Aktivierung durch GSH verhindert. Eine weitere Differenzierung zwischen den beiden Redox-Proteinen Trx und Grx und anderen Proteinen der Trx-Superfamilie erfordert eine zusĂ€tzliche Ebene der Selektierung, z. B. durch molekulare Erkennung, und ist Gegenstand laufender Arbeiten. Die flexible Verwendung verschiedener molekularer Wirkstoffe ermöglicht dabei die „Pipeline-Entwicklung“ von Diagnostika und Therapeutika, die von der zellulĂ€ren Redox-Maschinerie analog umgesetzt werden, und dadurch Schlussfolgerungen aus der Diagnostik direkt auf eine Therapie ĂŒbertragbar machen. Dies birgt großes Potenzial fĂŒr kĂŒnftige Entwicklungen bei einer potenziellen Übertragung des modularen Konzepts auf andere Enzymklassen und therapeutische Einsatzgebiete

    Hiérarchie de fusion et systÚmes T et Y pour le modÚle de boucles diluées A2(2)A_2^{(2)} sur le ruban

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    Le modĂšle de boucles diluĂ©es A2(2)A_2^{(2)} est Ă©tudiĂ© pour la gĂ©omĂ©trie d'un ruban de taille NN. Deux familles de conditions frontiĂšres sont connues pour satisfaire l’équation de Yang-Baxter Ă  la frontiĂšre. Fixer ces conditions aux deux bouts du ruban donne un total de quatre modĂšles. Pour chaque modĂšle, les matrices de transfert, qui commutent entre elles, sont connues. Dans ce mĂ©moire, la hiĂ©rarchie de fusion des matrices de transfert et les systĂšmes T et Y sont construits pour chaque modĂšle et pour un paramĂštre de croisement λ\lambda gĂ©nĂ©rique. Pour λ/π\lambda/\pi rationnel, il est prouvĂ© qu'il existe une relation linĂ©aire entre les matrices fusionnĂ©es qui ferme la hiĂ©rarchie de fusion en un systĂšme fini. Les relations de fusion et de fermeture permettent de calculer les premiers termes d'une expansion de l'Ă©nergie libre lorsque NN est grand. Ces premiers termes correspondent Ă  l'Ă©nergie libre de bulk et de bord. Les rĂ©sultats analytiques sont en accord avec des rĂ©sultats numĂ©riques obtenus pour de petits NN. Ce mĂ©moire complĂšte une Ă©tude des modĂšles A2(2)A_2^{(2)} avec des conditions frontiĂšres pĂ©riodiques (A. Morin-Duchesne, P.A. Pearce, J. Stat. Mech. (2019)).We study the dilute A2(2)A_2^{(2)} loop models on the geometry of a strip of width NN. Two families of boundary conditions are known to satisfy the boundary Yang-Baxter equation. Fixing the boundary condition on the two ends of the strip leads to four models. We construct the fusion hierarchy of commuting transfer matrices for the model as well as its T- and Y-systems, for these four boundary conditions and with a generic crossing parameter λ\lambda. For λ/π\lambda/\pi rational we prove a linear relation satisfied by the fused transfer matrices that closes the fusion hierarchy into a finite system. The fusion relations allow us to compute the two leading terms in the large-NN expansion of the free energy, namely the bulk and boundary free energies. These are found to be in agreement with numerical data obtained for small NN. The present work complements a previous study (A. Morin-Duchesne, P.A. Pearce, J. Stat. Mech. (2019)) that investigated the dilute A2(2)A_2^{(2)} loop models with periodic boundary conditions

    A numerical study of the shape mode oscillation of microbubbles in a viscous compressible liquid

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    Recent experiments (Vyas et al. [2020]) have revealed the interesting cleaning effects that take place due to the shape mode oscillation of bubbles over a rigid boundary. Whilst a microbubble was undertaking shape oscillation moving over a bacterial biofilm, it removed the contaminants from the boundary and created a clean path through the biofilm. This demonstrated much higher cleaning efficiency than that associated with the volume oscillation of cavitation bubbles. Hence, the shape mode oscillation of bubbles near to a rigid boundary proves to be an important topic of research and the main topic of this thesis. The viscous, weakly compressible boundary integral method (VCBIM) is initially described and validated against analytical, numerical, and experimental results, achieving excellent agreement. The characteristics of a microbubble in shape oscillation are then studied, finding that the rigid boundary decreases the natural frequency of the modes. It is found that shape oscillation of a nearby bubble generates a significantly larger amount of shear stress on a rigid boundary, agreeing with experimental observations. This exemplifies the applicability of shape oscillation to ultrasonic cleaning. Additionally, the effects of a surfactant on bubble oscillation are examined. The presence of a surfactant is found to have a significant effect on the shape oscillation of bubbles, as well as greatly increasing the shear stress generated on a rigid boundary. Thus, it is found that the presence of a surfactant enhances the cleaning of a surface by the shape oscillation of a nearby bubble

    From a better use of instrumentation to new detection methods in NMR and EPR spectroscopy

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    NMR and EPR spectroscopy are two of the most important techniques to get quantitative, structural or dynamical information on molecular systems. After covering the fundamentals of these magnetic resonance techniques, this thesis explores ways to improve the usage of current spectrometers and to create new instruments altogether using different detection methods with quantum sensing. First, to deal with bandwidth and oscillating magnetic field limitations typically present for 19F nuclei in NMR or unpaired electrons in EPR, improved methods based on frequency-swept pulses are presented. The implementation of the CHORUS sequence in EPR spectroscopy is detailed. New pulse sequences, namely CHORUSCPMG, PROCHORUS and superposed frequency-swept pulses, are presented in the context of solution-state NMR spectroscopy. Then, on-the-fly optimisation is proposed as a tool to automate EPR experiments and even develop new ones. A software package, ESR-POISE, was released to allow EPR users with commercial spectrometers to access such methods. Finally, the construction of a spectrometer which can conduct magnetic resonance at unconventionally small scales thanks to quantum sensors (NV centres) is detailed. After describing design choices for the different elements of the instrument, a focus is made on the static magnetic field with Finite Element Analysis
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