VictorJuiz/thesis huggingface dataset:
Vector correlations in gas-phase inelastic collision dynamics
Keywords: molecular beam
non-adiabatic
quenching
inelastic scattering
quasi-classical trajectory

This thesis presents a joint experimental and theoretical study of vector correlations in the electronically, vibrationally, and rotationally inelastic collisions of simple molecules with rare-gas atoms.
In the first instance, empirical and calculated data are presented for rotationally inelastic scattering in the NO(X)+Ar and ND3(X(tilde))+Ar systems at collision energies in the range 405 − 2210 cm−1. These experiments – the first to be conducted on a newly commissioned crossed-molecular beam machine – measured the k − k′ correlation, i.e. that between the vectors describing the relative velocities before and after collision, respectively. The empirical data were subjected to rigorous comparison with both quantum-mechanical and quasi-classical trajectory (QCT) calculations. For both the NO(X)+Ar and ND3(X(tilde))+Ar systems, there is generally good agreement between experiment and theory at all four collision energies investigated.
Two chapters of this thesis focus on the development of trajectory surface-hopping (TSH) QCT models of the OH(A, v = 0)+Kr and OH(A, v = 0)+Xe systems. Experimental data relating to scalar quantities (rotational energy transfer (RET) and electronic quenching) and to the j − j′ correlation (which quantifies the depolarisation of the angular momentum of the OH(A) radical) are compared to variable-collision-energy TSH QCT calculations in which the length of the OH bond is fixed. The algorithms involve all three PESs of the OH(A/X)+Kr system, and the full range of electrostatic and roto-electronic mechanisms that couple them, for the first time. The most complete model succeeded in accounting for 93% of experimentally observed quenching. For the OH(A/X)+Xe system, coupling matrix elements were estimated from those of OH(A/X)+Kr, and the most complete model recovered 63% of experimentally observed quenching.
This thesis also presents a novel theoretical study of rotationally inelastic dynamics in the OH(A, v = 1)+Kr system. Provisional results from adiabatic calculations in which the OH bond length is allowed to vary over the course of a trajectory are presented alongside experimental data that were reported previously. To date, these calculations continue to underestimate the extent of empirical RET data. Reasons for the observed discrepancy, and suggestions to resolve it, are outlined in detail.
Separate and interactive effects of catechol-o-methyltransferase and tetrahydrocannabinol on frontostriatal dopamine function
Keywords: COMT
THC
dopamine
psychosis
gene-environment interaction
schizophrenia
cannabis

The frontostriatal dopamine system modulates brain function and is affected by both genetic and environmental factors. Dysfunction of this system is associated with many pathological states, including schizophrenia. The enzyme catechol-O- methyltransferase (COMT) metabolises dopamine and its gene contains a polymorphism (Val158Met) that affects enzyme activity. Delta-9- tetrahydrocannabinol (THC), the main psychoactive component of cannabis, has been suggested to interact with this polymorphism to increase the risk for psychosis and cognitive impairments. Dopaminergic mechanisms are a plausible candidate for mediating this interaction.
I used microdialysis coupled with high performance liquid chromatography (HPLC) to examine the effects of THC on extracellular dopamine and its metabolites in the nucleus accumbens, dorsal striatum and medial prefrontal cortex (mPFC) in freely moving mice. Following acute COMT inhibition with tolcapone, THC increased extracellular dopamine levels in the nucleus accumbens in tolcapone-, but not in vehicle-, treated mice. The introduction of the low activity Met allele into the COMT gene produced a highly specific, novel mouse model of the Val158Met polymorphism. In contrast to the effects of acute COMT inhibition, the Met allele protected against THC-induced changes in accumbal dopamine. No interactive neurochemical effects were observed in the dorsal striatum (pharmacological and genetic study) or in a preliminary study of the mPFC (genetic study only). On a progressive ratio task measuring motivational salience, the direction of the interactive effect between COMT genotype and THC differed between 2 independent cohorts and provided tentative leads that stress/arousal-dependent effects on COMT may have a confounding effect.
My data provide evidence that COMT activity modulates the effect of THC on accumbal dopamine function, and suggest the mechanism through which this interaction is mediated differs between acute and lifelong reduction in COMT activity. Through the interactive effect on the dopaminergic system, the data provide a potential mechanism for the reported interaction between COMT and cannabis/THC in determining psychosis risk and cognitive impairments.
Oxidative radical cyclisations for the synthesis of lactones
Keywords: Organic Chemistry
Oxidative Radical Cyclisation

The object of study of this thesis lies on the optimisation of the oxidative radical cyclisation methodology for the preferential formation of gamma-lactones from unsaturated alkyl malonate derivatives.
Chapter 1 introduces the concept of free-radical cyclisation; more extensive explanations are given for the intramolecular oxidative radical cyclisation using manganese(III) and copper(II) salts as oxidants. An overview of the contribution of the Burton group in the field is given, in which both the applicability and the limitations of the transformation are showcased.
Chapter 2 is concerned with the synthesis of the ethisolide family of natural products and one non-natural analogue, in which the oxidative radical cyclisation is key for the construction of the bis-gamme-lactone moiety present in such natural products. The initial limitations of the methodology allowed for the discovery of new conditions for the formation of chloro monocyclic systems and for the development of copper-free oxidative cyclisation conditions for gamma-lactone formation.
Chapter 3 reports the developments on the metal-free oxidative radical cyclisation. Bicyclic gamma-lactones were synthesised from all-carbon alkyl malonate derivatives through anodic oxidation via constant current electrolysis. The development of a novel ionic oxidative cyclisation is also discussed.
Chapter 4 describes our efforts towards the formation of both fused and spiro gamma-lactam-beta-lactone molecules, as potential analogues to proteasome inhibitors, from either gamma-lactam-gamma-lactones or exo-gamma-lactams precursors, previously synthesised through oxidative radical cyclisation.
Full experimental details, NMR spectra for the natural products and for the non-natural analogue, and a comparison between the obtained and the previously reported NMR data are also provided.
Development of a robust nanoscaffold as a modular vaccine platform
Keywords: Vaccines

Protein nanoparticles have been used as platforms to multimerize and present otherwise weakly immunogenic antigens to the immune system. Virus-like particles (VLPs) are self-assembling protein cages, forming the basis of safe and immunogenic vaccines that have been administered to millions of people. However, the creation of chimeric VLPs that display heterologous antigens through either genetic fusion or chemical coupling continues to be a challenge. To address this challenge, a modular vaccine platform has been previously developed that takes advantage of the spontaneous isopeptide bond between the protein domain SpyCatcher and its peptide partner SpyTag. Fusion of SpyCatcher to the surface-exposed N-terminus of the bacteriophage VLP AP205 afforded a particle that could be covalently coupled to a SpyTag-antigen simply by mixing. In the first part of this thesis I establish a methodology for the directed evolution of SpyCatcher-VLPs. I evolve the AP205 coat protein to attempt to address limitations in solubility and yield of the SpyCatcher-AP205 platform. I then extend the scope of SpyCatcher/SpyTag-mediated vaccines by characterizing a new modular platform based on the computationally designed I3-01 nanoparticle. I3-01 was rationally engineered to reduce aggregation by removing two surface-exposed cysteines. This mutated protein was given the name MI3. Genetic fusion of SpyCatcher to the N-terminus of MI3 yielded a platform that was purified in high yield from E. coli. I show that SpyCatcher-MI3 is robust and tolerates heating, freezing, and lyophilization. Immunization with SpyCatcher-MI3 particles conjugated with the SpyTagged malarial antigen CyRPA yielded high-avidity antibodies against CyRPA. The SpyCatcher-MI3 platform's stability, simple production method, and modular quantitative coupling should facilitate the development of new vaccines.
Kant &amp; Moral Character
Keywords: Moral Character
Virtue
Kant
Education
Moral Worth
Moral Psychology
Sympathy
Habit

This thesis argues that Kant has a viable, intellectualist account of moral character that is much richer and more interesting than has often been thought. This account is consistent with his broader practical philosophy, in particular, his account of moral worth. Chapter one establishes that Kant has a theory of education on which a child’s inclinations are to be trained in preparation for her to grasp the moral law and acquire full moral agency. It argues that his account of habit is complex, recognizing a kind of moral value that is broader than his definition of moral worth. Chapter two argues that sympathy is, for Kant, a primarily cognitive disposition of special importance; this is because it provides knowledge of how the moral law applies in particular circumstances, therefore enabling an agent to fulfill her duties toward others. This chapter also resolves a puzzle concerning Kant’s dual concept of character (as both intelligible and empirical) by drawing an analogy with one account of weakness of will. Chapter three develops an account of moral worth that incorporates these more palatable elements of Kant’s account of moral character with the seemingly more austere elements familiar from the Groundwork. This theory allows for positive, participating inclinations alongside ascriptions of moral worth. Further, it introduces a distinction between full and mitigated moral worth, to account for agents who, for example, act rightly but for confused reasons as in the case of Twain’s Huckleberry Finn. Chapter four responds to two objections to Kant on the basis of moral demandingness, one concerning psychological integration and personal relationships, the other concerning the value of non-moral goods more broadly. It then responds to some objections to his account of the highest good, or the idea of a world in which happiness is distributed in proportion to virtue.
Heat transfer for fusion power plant divertors
Keywords: high-heat flux
heat sink
cooling
divertor

Exhausting the thermal power from a fusion tokamak is a critical engineering challenge. The life of components designed for these conditions has a strong influence on the availability of the machine. For a fusion power plant this dependence becomes increasingly important, as it will influence the cost of electricity.
The most extreme thermal loading for a fusion power plant will occur in the divertor region, where components will be expected to survive heat fluxes in excess of 10 MW/m2 over a number of years. This research focussed on the development of a heat sink module for operation under such conditions, drawing on advanced cooling strategies from the aerospace industry.
A reference concept was developed using conjugate Computational Fluid Dynamics. The results were experimentally validated by matching Reynolds numbers on a scaled model. Heat transfer data was captured using a transient thermochromic liquid crystal technique. The results showed excellent agreement with the corresponding numerical simulations.
To facilitate comparison against other divertor heat sink proposals, a nondimensional figure of merit for cooling performance was developed. When plotted against a non-dimensional mass flow rate, the reference heat sink was shown to have superior cooling performance to all other divertor proposals to date.
Results from Finite Element Analysis were used in conjunction with the ITER structural design criteria to life the heat sink. The sensitivity of life to both boundary conditions, and local geometric features, were explored. The reference design was shown to be capable of exceeding the life requirements for heat fluxes in excess of 15 MW/m2.
A number of heat sinks, based on the reference design, were fabricated. These underwent non-destructive testing, before experimentation in a high-heat flux facility developed by the author. The heat transfer performance of the tested modules was found to exceed that predicted by numerical modelling, which was concluded to be caused by the fabrication processes used.
A socio-legal analysis of the divergent approaches of the EU Data Protection Directive and individuals’ attitudes towards novel uses of administrative data in social science research
Keywords: Individuals' attitudes
Data protection
Administrative data
Data Re-use
Privacy
Research

Governments around the world are encouraging social science research using administrative data to support policy development. These initiatives depend on wide-scale public acceptance to succeed and are often supported by a legal basis. The care.data initiative in the UK, which sought to open up routinely collected health data to researchers, is an example where societal expectations of privacy diverged from legally permissible data processing practices. This discord led to the closing down of the project. The factors influencing societal expectations and causing these divergences are currently under-theorised, and little understood, particularly in the field of administrative data.
The thesis argues that data processing utilising innovative technologies challenge current constructions of privacy and the notion of the public interest in data processing. As a result, the approaches of the EU Data Protection Directive and individuals’ attitudes towards these practices diverge. In developing this argument, the contested nature of the interests of privacy and the public interest in data processing, which are interests present in the objectives of the Directive are explored. The thesis suggests that different values underpin the construction of these interests and further proposes that these different values are a potential source of the divergences between the Directive and individuals’ attitudes.
This claim is tested by examining the Directive and the empirical findings from two focus groups to identify potential divergences. The analysis suggests the Directive constructs privacy by reference to its value to society and perceives research as a data processing activity in the public interest. The qualitative findings, however, suggest individuals ascribe less value to research as an activity in the public interest. Due to individuals’ uncertainty as to the risks generated by novel practices, they adopted a more individualistic construction of privacy, enabling greater control over their data. Considering these divergences, possible legal responses are explored, including the suitability of the law aligning with individuals’ expectations, the ability of the law to guide societal expectations, and the possibility of the law fostering deliberative dialogues between the actors involved in data processing.
Children’s use of personal knowledge and adult testimony in fantasy/reality distinctions
Keywords: conceptual development
testimony
fantasy/reality distinction

This study aimed to investigate children’s conceptual understanding of particular human attributes and their relation to children’s judgements that a person was ‘real’ or ‘not real’. The study explored the extent to which children relied on their own knowledge versus the testimony of others when making reality-status judgements about unfamiliar people with characteristics that were possible, improbable or impossible of human beings. Testimony came from a child or an adult in order to make comparisons of children’s trust in two different informants with varying amounts of knowledge. The sample consisted of 61 children between the ages of 3 and 6 recruited from a primary school in Essex.
The study employed a within-subject experimental design, in which both the attributes of the stimuli and the testimony of informants were manipulated in order to observe the effect on children’s reality-status judgements. In order to investigate the possibility of developmental trends, the sample was divided into two age groups made up of 3-4 and 5-6 year olds. A novel categorisation task and interview schedule were developed for this study, which measured children’s initial reality-status judgements and compared these with their judgements after hearing testimony from an adult or a child.
Analysis of children’s judgements showed that children across the sample distinguished between possible and impossible attributes, both in their initial judgements and in their use of testimony, but that only the older age group distinguished between improbable and impossible attributes. There were no significant differences in children’s trust in the two different informants, but children did rely on testimony differentially according to both age and the type of attribute.
The findings suggest that young children are able to reflect upon the extent of their own knowledge, and the potential reliability of other people, in order to make decisions about an unfamiliar entity’s reality status. This study extends the findings from previous research by addressing children’s understanding of the kinds of attributes that render human beings real or unreal. Future research could build on this study by employing a longitudinal within-subject design, which would suggest possible causal influences, and would also offer insights into the developmental trajectory of children’s conceptual understanding within this field.
The Greater Bundahisn
Keywords: Zoroastrian
Bundahisn
Bundahishn
Cosmology
Greater

The task which I set myself when I undertook to study the text of the Greater Bundahisn was at that time by no means clear either in its difficulty or its extent. Nor could I then know to what degree the increased knowledge of Iranian, in particular, of Middle Iranian, the period from about 300 B.C. to 900 A.D., had made understanding of this text possible.
Iranian studies attained to a new birth when in 1904 the results of archaeological expeditions to central Asia were first made known. By these discoveries of MSS the difficulties of reading Pahlavi were at once lightened. It was certain that if the vocabulary of Western Persia of Sasanian times were fully known, the Zoroastrian Pahlavi texts could no longer hide their secrets under the cursive alphabet which had hindered the progress of earlier scholars. Not only the Western dialects but also the recently discovered Sogdian and Saka have naturally enriched our understanding of the Middle Iranian vocabulary. But the lack of complete indexes of the words of theses two dialects still renders their use difficult. For Saka, besides the published indexes (of which the most important has only just appeared in Sten Konow's Saka Studies) I made my own index of all the unindexed Saka so far published. For Sogdian there has been the grammar of Buddhist Sogdian by R. Gauthiot, besides which I have had some indexed material of my own. Reichelt's promised glossary of Buddhist Sogdian has not yet appeared. The few Manichean Sogdian texts so far published (by F.W.K. Miller and Waldschmidt-Lentz) have yielded interesting words. For the Christian Sogdian there is the index in F.W.K. Muller's Soghdische Texte.
From Introduction; continued in thesis ... .
Ricci solitons and geometric analysis
Keywords: Differential Geometry
Poincare inequality
Ricci soliton
Einstein metric

This thesis studies Ricci solitons of cohomogeneity one and uniform Poincaré inequalities for differentials on Riemann surfaces.
In the two summands case, which assumes that the isotropy representation of the principal orbit consists of two inequivalent Ad-invariant irreducible summands, complete steady and expanding Ricci solitons have been detected numerically by Buzano-Dancer-Gallaugher-Wang. This work provides a rigorous construction thereof.
A Lyapunov function is introduced to prove that the Ricci soliton metrics lie in a bounded region of an associated phase space. This also gives an alternative construction of non-compact Einstein metrics of non-positive scalar curvature due to Böhm. It is explained how the asymptotics of the Ricci flat trajectories induce Böhm's Einstein metrics on spheres and other low dimensional spaces. A numerical study suggests that all other Einstein metrics of positive scalar curvature which are induced by the generalised Hopf fibrations occur in an entirely non-linear regime of the Einstein equations.
Extending the theory of cohomogeneity one steady and expanding Ricci solitons, an estimate which allows to prescribe the growth rate of the soliton potential at any given time is shown. As an application, continuous families of Ricci solitons on complex line bundles over products of Fano Kähler Einstein manifolds are constructed. This generalises work of Appleton and Stolarski. The method also applies to the Lü-Page-Pope set-up and allows to cover an optimal parameter range in the two summands case.
The Ricci soliton equation on manifolds foliated by torus bundles over products of Fano Kähler Einstein manifolds is discussed. A rigidity theorem is obtained and a preserved curvature condition is discovered.
The cohomogeneity one initial value problem is solved for m-quasi-Einstein metrics and complete metrics are described.
Lp-Poincaré inequalities for k-differentials on closed Riemann surfaces are shown. The estimates are uniform in the sense that the Poincaré constant only depends on p &GE;1, k ≥ 2 and the genus γ ≥ 2 of the surface but not on its complex structure. Examples show that the analogous estimate for 1-differentials cannot be uniform. This part is based on joint work with Melanie Rupflin.