VictorJuiz/thesis huggingface dataset:
An investigation of copper(I) active metal template synthesis of interlocked structures for anion binding

This thesis describes the synthesis and study of a series of novel macrocycles containing propyl-, 1,2-hydroxymethyl benzene-, and 1,3-benzene-linked bis(iodo)triazole motifs, as well as computational investigation of these and further bis(iodo)triazole marcrocycles
Chapter One introduces the field of supramolecular chemistry, highlighting areas of particular relevance to this thesis viz halogen bonding, anion coordination, recognition, and templa- tion routes to the synthesis of interlocked structural frameworks.
Chapter Two describes the synthesis of a series of macrocycles, containing propyl- and 1,2- hydroxymethyl benzene-linked bis(iodo)triazole motifs. Attempts to include them into [2]rotaxanes, pursuing understanding of how macrocycle flexibility impacts active metal templation outcomes are reported.
Chapter Three details computational methods used to determine if a simplified computational model has potential as a predictor for macrocycle viability in an active metal template re- action. Minimal conformations of known and novel macrocycles are generated complexed with CuI cations and the results presented for comparison with experimental outcomes.
Chapter Four focuses on the study of how macrocycle size variation impacts active metal template yield. A series of novel macrocycles containing the 1,3-bis(iodo)triazole ben- zene motif were prepared, then used in active metal template reactions to generate novel [2]rotaxanes for yield comparison.
Chapter Five provides a summary of the major conclusions of this thesis.
Chapter Six contains procedures pertaining to chemicals, instrumentation, data handling and analytical protocols, as well as detailing synthetic methods and characterisation of novel compounds.
Chapter Seven provides the references cited within Chapters One to Six.

Advisor: Beer, P
McGrady, J
Analysis of various estimators for multi-dimensional Zakai equations

We first consider a one-dimensional stochastic partial differential equation (SPDE) of Zakai type describing a large credit portfolio. Specifically, we construct estimators of linear functionals of the solution from an implicit Milstein scheme on a space-time mesh. We compare the complexity of a multi-index Monte Carlo (MIMC) approach with the multilevel Monte Carlo (MLMC) method of Giles and Reisinger (2012), and find, by means of Fourier analysis, that the MIMC method has slightly improved complexity O(ε-2|log ε|) for a root mean square error (RMSE) ε if a carefully adapted discretisation is used.
Then, we propose an implicit finite difference scheme for a two-dimensional parabolic SPDE of Zakai type, based on a Milstein approximation to the stochastic integral and an alternating direction implicit (ADI) discretisation of the elliptic term. We prove its mean-square stability and convergence in L2 of first order in time and second order in space, by Fourier analysis, in the presence of Dirac initial data.
Next, we analyse the accuracy and computational complexity of estimators for linear functionals of the solution to the 2-d SPDE, coupled with the sparse combination technique and MLMC. We find, by detailed Fourier analysis, that for a RMSE ε, MLMC with sparse combination has the optimal complexity O(ε-2), whereas MLMC on regular grids has O(ε-2(log ε)2), standard MC with sparse combination O(ε-7/2(|log ε|)5/2), and MC on regular grids O(ε-4). We give a discussion of the higher-dimensional setting without detailed proofs, which suggests that MLMC with sparse combination always leads to the optimal complexity.
Finally, we consider a particular two-dimensional SPDE with fast mean-reverting volatility on a timescale O(ε-1), and study the small ε asymptotics. We find an asymptotic expansion of the solution to the SPDE as ε → 0 and conclude from numerical experiments the convergence order 1=2 of the leading term and order 1 after inclusion of the first correction term.

Keywords: SPDE
Monte Carlo
Zakai equation
Finite difference
Advisor: Reisinger, C
Educational expansion, skills diffusion, and a new dimension of the OED triangle

Among wide-ranging functions of education, sociologists have paid close attention to its role in social stratification and mobility. While research has promoted our understanding of the association between origins, education, and destinations (OED triangle), the distinction between educational credentials and skills has been largely overlooked at both individual and societal levels. This paper thus empirically investigates the OED association in consideration of educational specifications (the combination of credentials and skills that individuals possess) and the degree of skills diffusion (the proportion of highly skilled people in a given society), which is a different societal condition from educational expansion that has been quantified by the share of highly educated people. Multilevel logistic regression analyses, using internationally comparable data for approximately 30,000 individuals in 26 OECD countries, reveal that educational credentials play more significant roles, as compared with skills, in forming the OED triangle. This supports the soundness of conventional approach focused on educational qualifications. Nevertheless, whereas credentials are likely to lose their economic returns in societies where the degree of educational expansion is relatively high, skills are not devalued even though their scarcity diminishes due to the higher extent of skills diffusion. Meanwhile, the impact of origins becomes smaller in association with the larger share of highly skilled people as well as that of highly educated people in a nuanced way. This suggests that what we have understood as the consequence of educational expansion is significantly shaped by skills diffusion. It is particularly important to note that, while educational expansion undermines the contribution of origins whilst penalising highly educated people, skills diffusion operates as an equaliser without diminishing rewards for high skills. This implies that skills diffusion is the key to realising meritocracy. I argue that these perspectives markedly contribute to elucidating the nuanced OED triangle and broader social mechanisms.

Keywords: educational credentials
social closure
skills
human capital
labour market outcomes
meritocracy
parental education
signalling
Advisor: Kariya, T
Hadronic jet physics and the quest for new matter in multi-jet final states with the ATLAS detector at the Large Hadron Collider

The Standard Model of particle physics is one of the triumphs of contemporary science, but it is well-established that this theory must be incomplete. This thesis focuses on searching for the production of new matter, motivated by beyond-Standard Model framework of supersymmetry, with data recorded by the ATLAS experiment during Run 2 of the Large Hadron Collider. One of the crucial physics objects in the search for new matter described in this thesis is the hadronic jet. Before describing in detail the `multi-jets' search for new matter, which uses 36 fb−1 of ATLAS data in signal regions where at least 7 hadronic jets are required in the final state, the latest developments in hadronic jet physics at ATLAS shall be motivated and studied. Particular detail will be paid to new approaches in jet reconstruction, jet mass calculations and the corresponding jet mass resolution, and jet calibration at the energy and mass scales. Furthermore the issue of pileup contributions to hadronic jets shall be described, together with recent studies outlining how new developments in inputs to jet reconstruction and jet grooming can be used to improve the performance of hadronic jets in ATLAS and mitigate the effects of pileup therein. The full power of jet reconstruction at ATLAS will then be utilised in the multi-jets analysis. With the 36 fb−1 ATLAS data-set, no statistically significant evidence for new matter is reported, and new constraints on the mass of gluinos and stops are pushed up to 1.8 TeV and 1.4 TeV, at the 95 % confidence level, respectively (within the context of particular sets of new physics models). The multi-jets search is sensitive to final states with moderate ETmiss, and consequently is used to assess the LHC sensitivity to both R-parity-conserving (RPC) and R-parity-violating (RPV) supersymmetric scenarios. World-leading constraints across this `RPC-meets-RPV' spectrum will be assessed at the 95 % confidence level. Finally the ultimate plans for the full Run 2 iteration of the multi-jets analysis, amounting to 140 fb−1 of data, will be described.

Advisor: Gwenlan, C
Crime and equality, or crime and punishment?

Despite its significance as a social, economic and—as I argue below—fundamentally political phenomenon, crime remains a largely overlooked topic in political economy. This dissertation argues that this represents an unfortunate omission. Over the pages that follow, I analyse the political implications of crime and fear of crime for the politics of inequality and redistribution. Modelling fear of crime as a negative externality of inequality, I argue that its consequences depend on who the criminals are: building on work in social psychology, I find that the identity of those who are perceived as likely perpetrators of crime significantly affects how criminal behaviour is interpreted. This comes with important implications for views about how crime as a social problem can (and should) be solved. Using a combination of observational data from Western Europe and the US, together with the results from a laboratory experiment conducted in Oxford, I first demonstrate that there exists a robust and systematic positive relationship between the local level of income inequality and fear of crime. In a second step, I show that shared group membership—manifested empirically as low population heterogeneity—facilitates situational explanations of crime, including poverty, while divergent identities promote dispositional attributions unrelated to inequality. As a result, while fear of crime in homogenous contexts is associated with a significant increase in demand for redistribution, particularly among high-income voters, I find no parallel effect in settings that are more diverse. The opposite relationship holds true for support for harsher punishment and law enforcement spending: whereas fear of crime increases support for such policies in settings that are sufficiently heterogenous, the same does not hold true when the level of population heterogeneity is lower. This finding both challenges previous accounts of the relationship between inequality, fear of crime and support for redistribution, and helps to explain cross-national differences in criminal justice policy.

Keywords: Inequality
Redistribution
Political science
Political economy
Crime
Advisor: Rueda, D
Reliable automatic model reduction combining a posteriori error analysis and a posteriori model reduction

Mathematical models are used for simulations and predictions of various phenomena and processes that can be translated into mathematical language. Nowadays, with easy access to powerful computers and specialised software, even complicated models can be handled. Model output can be generated even by users that may not have specialised mathematical training. A consequence of the increase in complexity of the models on the one hand, and the relative ease of numerical output generation on the other hand, can be a loss of insight into the mathematical model. One way to regain this is to reduce the original model to a simpler form that will nevertheless capture the key features of the model and elucidate the processes that are modelled, especially those that are of interest to the user.
In this thesis I develop a model reduction algorithm that is based on a technique borrowed from finite element methods. An a posteriori error estimate, where the error is defined as the difference between the unknown solution and a FE approximation thereof, is used to ensure that the mesh on the computational domain is fine enough such that the discretised scheme approximates the differential operator sufficiently accurately. Model reduction on the other hand uses an a posteriori error estimate, where the error is defined as the difference between the solutions to the original model and a reduced model, to generate a differential operator that is a close enough approximation of the original operator.
The main research chapter focuses on the mathematical analysis that this automated method entails. The model reduction technique is then applied to model problems to validate the numerical methods that are employed. An enzyme kinetic reaction model is discussed in detail as the application of the developed model reduction method satisfies the aim of this thesis to a great extent. In particular, I can show with that example that the reduced models which were automatically generated correspond to those obtained by asymptotic analysis. The same elucidation of the processes that are modelled could therefore be achieved with the automatic model reduction technique as with methods that usually need considerable mathematical expertise.

Keywords: a posteriori error analysis
Psycho-social dynamics of shame in poverty: a South Korean case study

Poverty studies worldwide have continuously demonstrated that poverty entails not only material hardships but also other non-material hardships, such as shame. Yet, a substantive empirical investigation of why and how shame is experienced in poverty and its relevance for social policy interventions has been significantly lacking in the literature. Accordingly, this thesis documents an in-depth empirical investigation of an increasingly significant, yet under-researched, psycho-social dimension of shame in poverty. Acknowledging the limitations of focusing either on the individual or the social level processes alone in poverty and shame research, it employs a psycho-social approach that takes a comprehensive account of the dual dimensions of shame. Empirical investigations are conducted with three different qualitative research methods (in-depth interviews with people living in poverty, sociological discourse analysis of popular films, and social policy analysis of the social assistance programme in South Korea), together with a historical contextualization of the empirical findings with secondary historical sources. Taking South Korea as a case study, it offers an empirically-based theoretical framework that explains the root causes, working mechanisms and impacts of shame in poverty, and the fundamental nature of the association between poverty and shame. It demonstrates that the current psycho-social dynamics of shame in poverty is a contemporary phenomenon underpinned by the socio-relational conditions that emerged from the major socio-historical shift to modern capitalism. The social level dynamics are shown to equally manifest in the personal level working mechanisms and subsequent impacts of shame in poverty. The findings show that in order for the anti-poverty social assistance in South Korea to continue promoting the improvement of people’s lives via their own self-agency, its design and implementation should equally be geared toward improving people’s self-agency rather than undermining it as it currently stands.

Keywords: psycho-social dimension
social policy
poverty
shame
cultural discourse
modern capitalism
Advisor: Walker, R
The illusion of solution? The politics of Jakarta’s quest to achieve water security

The increasing number of large water infrastructures built or planned worldwide denotes the (re)turn to a hydraulic mission in water management. Infrastructures are pursued mainly for water supply augmentation and flood control, that is, delivering water security for the people especially in packed urban areas. Jakarta, the capital city of Indonesia, has pressing water issue as the city is experiencing land subsidence. Combined with sea level rise and perennial flooding problem, the city’s risk of sinking is extremely high. Following a major flood in 2013, the Government of Indonesia launched the NCICD (National Capital Integrated Coastal Development) plan to close Jakarta Bay with a 32-km length offshore sea wall for flood control defence. The plan also includes 5,100 hectares of land reclamation (located between the coastal line and the seawall), which was said, to fund the seawall construction. Such a megaproject whose total costs is estimated at USD 40 billion will significantly alter the biophysical as well as the social landscape of Jakarta. This thesis investigates the socio-political dynamics behind this megastructure from historical institutionalism and political ecology lenses, in which both anchored on power relations. Framing the overall discussion using ‘water security’ approach, it asks: How do relations of power drive large infrastructure investments in Jakarta, and how does this contribute and respond to the problem of water security?
Data collection primarily included 48 key informant interviews, around 400 newspaper articles and secondary data (archives and policy documents). In order to analyse these diverse data sources, I employed three types of data analyses accordingly: historical analysis for historical data, thematic analysis for interviews and policy documents, and discourse analysis for newspaper articles. This research reveals that NCICD has advanced the infrastructural pathway in Jakarta’s flood policy which has been established since the colonial times. NCICD as a contemporary project is, thus, a product of the past. Furthermore, rather than dealing with complex institutional challenges associated with multiple water sectors, the government instead focuses on the seawall, which only deals with the flooding issue as a symptom of sinking, rendering the highly political issue apolitical. Reflecting on the power asymmetries manifested in NCICD and situating them on broader literature on water security, I conclude that the politics of water security, in the context of water hazards, is the politics of fear and in consequently meeting demand for security through the prescription of infrastructure. Fear is built from memories of past floods and ultimately from the construction of future uncertainties, where our knowledge is limited.

Keywords: Jakarta
Seawall
Historical institutionalism
Infrastructure
Political ecology
Water security
Urban water
Advisor: Charles, K
Heterodinuclear cooperativity in oxygenated polymer catalysis

The following thesis describes the synthesis and characterisation of a series of heterodinuclear complexes derived from either a diphenolate macrocycle, or an ovanillin derived dinucleating ligand. Their application as catalysts for the ringopening copolymerisation of CO2/epoxide, or anhydride/epoxide are investigated.
Chapter 2: Explores the role of ionic Lewis acids, where a series of Group 1 and 2 metals with zinc (II) complexes are synthesised. All heterocomplexes are less active in the ROCOP of CO2/CHO compared to the di-zinc analogue, with the exception of Mg(II)Zn(II). The chain-shuttling mechanistic hypothesis is advanced with the assignment of Mg(II) as the epoxide binder and Zn(II) as the carbonate donor.
Chapter 3: Explores the role of covalent Lewis acids, where a series of Group 13 metals with zinc (II) complexes are synthesised. Activity and CO2 uptake increases down the Group 13 homologues. All complexes are less active than the dizinc counterpart
Chapter 4: A Mg(II)Co(II) catalyst is synthesised and shows excellent activity, better than either di-Mg or di-Co analogues. Mg(II)Co(II) has a lower transition state Gibbs free energy vs. the homodinuclear analogues. Its superior performance arises from a combination of favourable entropy, provided by Mg(II) and reduced enthalpy, provided by Co(II). The experimental data supports a chain-shuttling mechanism, with epoxide coordination at Mg(II) and Co(II) accelerating carbonate attack.
Chapter 5: A series of Zn(II) and Mg(II) dinucleating o-vanillin complexes with Na(I), Ca(II) and Cd(II) are reported. All zinc heterodinuclear catalysts are less active compared to the homodinuclear complex, where the converse is true for the magnesium complexes.

Advisor: Williams, C
Robustness and entropy for dynamics on networks

Robustness and entropy are widely used concepts in the study of networks in various disciplines. There exist various notions of network robustness and network entropy, because there are many network properties that can be robust to perturbations and there are many network-associated distributions for which one can calculate a notion of entropy. In this dissertation, we explore several notions of robustness and entropy --- and connections between them --- on networks. We investigate the robustness of structural properties of protein-interaction networks to the targeted removal of nodes and propose a test for identifying structural properties that are plausible proxies for measures of performance or viability of a protein-interaction network. Several researchers have suggested that structural redundancy and functional redundancy are important mechanisms by which a biological system can achieve robustness. A connection between redundancy and the mean subsystem entropy of a network with Ornstein--Uhlenbeck dynamics motivates our study of the relationship between the entropy of a multivariate Ornstein--Uhlenbeck process and the structure of an underlying network. We introduce walk graphs as a type of network motif that can help one understand the relationship between network structure and the covariance and entropy of a multivariate Ornstein--Uhlenbeck process. Because of the large number of subsystems in systems with as few as 20 nodes, studying the mean entropy of subsystems computationally is a difficult task. To address this issue, we derive sampling guarantees that indicate that one can calculate a very accurate sample mean of subsystem entropy by sampling very few subsystems.
The results in this dissertation offer new approaches to studying performance, viability, and robustness of systems on the basis of network structure and dynamics on networks. They demonstrate the importance of the choice of an appropriate performance measure for the study of network robustness and provide a framework for identifying plausible performance measures or plausible proxies of performance measures. The analysis of walk graphs and their contribution to covariance and entropy demonstrates that it can be useful to consider dynamics on a network (instead of just a network's structure) as a composite entity that one can decompose into many small parts. This decomposition of dynamics on networks provides a framework for studying the mechanisms by which dynamics and network structure contribute to covariance, entropy, redundancy, and other properties of dynamics on networks.

Advisor: Porter, M
Wray, J
Maini, P