VictorJuiz/thesis huggingface dataset:
Essays in climate policy and exhaustible resource economics
Keywords: exhaustible resource
climate policy

Owners of exhaustible resources will respond to climate policies, and these policies have to take such responses into account. This thesis considers three separate instances in which market power and exhaustible resources interact with climate policy.
Chapter 2 considers research and development (R&D;) into green substitutes to oil as a climate policy instrument. Oil exporters will respond to such R&D; efforts in ways which reduce the effectiveness of the policy. Making substitute technologies competitive against current oil prices is not sufficient. R&D; efforts will only force higher oil supplies, aggravating short-term pollution. Eventually, the oil age will end as the substitutes become competitive against the marginal cost of producing oil. This motive encourages an R&D; push to leave more oil underground. Strategic gaming between the importers and exporters may reduce both oil supply and R&D; efforts.
Chapter 3 considers fixed costs into opening a deposit of an exhaustible resource. Counterintuitively, a monopolist may invest too early, into too much capacity. I then apply this model to an unconventional exhaustible resource: empty space underground, in which to store captured carbon emissions. I focus on the case of storing European emissions under the North Sea. Monopolistic storage is only a concern if storage space is sufficiently abundant. In this case, the monopolist will not invest enough, to cut back the cumulative storage capacity. Duopolistic storage may involve tacit collusion.
Chapter 4 considers an unconventional climate policy instrument: capital income taxes imposed on oil exporters. Such taxes can motivate conservation of polluting resources and allow oil importers to appropriate some oil wealth. These benefits come at the cost of inducing productive distortions, which diminish overall economic output.
Coarse-grained modelling of DNA and DNA self-assembly
Keywords: nanotechnology
simulation
DNA

In this thesis I present a novel coarse-grained model of deoxyribonucleic acid (DNA). The model represents single-stranded DNA as a chain of rigid nucleotides, and includes potentials to represent chain connectivity, excluded volume, hydrogen-bonding and base stacking interactions. The parameterization of these interactions is justified by comparing the model's representation of a range of physical phenomena to experimental data. In particular, the geometrical structure and elastic moduli of duplex DNA, and the flexibility of single-stranded DNA, are shown to be physically reasonable. Additionally, the thermodynamics of single-stranded stacking, duplex hybridization, hairpin formation and more complex motifs are shown to agree well with experimental data.
The model is optimized for capturing the thermodynamic and mechanical changes associated with duplex formation from single strands. Considerable attention is therefore given to ensuring that single-stranded DNA behaves physically, an approach which differs from previous attempts to model DNA. As a result, the model is the first in which an explicit stacking transition is present in single strands, and also the only coarse-grained model to date to capture both hairpin formation within a single strand and duplex formation between strands.
The scope of the model is demonstrated by simulating DNA tweezers, an iconic nanodevice -- the first time that coarse-grained modelling has been applied to dynamic DNA nanotechnology. The simulations suggest that branch migration during toehold-mediated strand displacement -- a central feature of many nanomachines -- does not have a flat free-energy profile, as is generally assumed. This finding may help to explain the observed dependence of displacement rate on toehold length.
Finally, the operation of a two-footed DNA walker on a single-stranded DNA track is considered. The model suggests that several aspects of the walker will reduce its efficiency, including a tendency to bind to an undesired site on the track. Several design modifications are suggested to improve the operation of the walker.
Literary citizenship and the politics of language: the Galician literary field between 1939 and 1965
Keywords: Galician literature
Galician language
bilingualism
translation
literary history

My thesis, Literary Citizenship and the Politics of Language: The Galician Literary Field between 1939 and 1965, is the first attempt to examine the building process of Galician national literature by focusing on one of its constitutive elements, the linguistic criterion. Drawing on Mario Santana's concept of literary citizenship, which can be defined as membership of a literary community, it pays attention to the development of the idea that Galician literary citizenship is language specific, in other words, that to be a member of the national literature, writers have to write in Galician. It does so by focusing on one of the most neglected periods in Galician and Spanish Studies (1939–1965).
Chapter one, 'Going Public: The Adventure of Galician Publishing, 1939–1965', presents the first ever account of the publishing world in the studied period. Chapter two, 'From Region to Nation: Galician Literary Studies', argues that the main battleground in the definition of Galician literary citizenship was the field of Galician literary studies, where the concept of literary citizenship was naturalised and then institutionalised. Chapter three, 'Negotiating Identities', explores writers' language choices, paying special attention to those who wished to earn a language-specific Galician literary citizenship. Apart from native and exophonic writers, the chapter addresses writers who did so through translation. Chapter four, 'No Man's Land: Female Writing and Language', argues that female writers had a double-edged experience in the literary field. The patriarchal literary institutions were interested in their symbolic capital but they exercised firm control over them. The conclusion, 'A New raison d'être for Galician Literary Studies', summarises the main argument put forward by this thesis, that to understand fully the development of Galician literary citizenship, literature must be studied outside the national framework.
Synthesis and trifluoromethylation of allylsilanes
Keywords: trifluoromethylation
metal catalysis
organosilanes

The first part of this thesis presents a novel approach for synthesising enantioenriched cyclic allylsilanes via asymmetric ring-closing metathesis (ARCM). The second part of this thesis focuses on the reactivity of allylsilanes in electrophilic trifluoromethylation under transition metal and photoredox catalysis.
Chapter 1 provides a general introduction to existing methods for preparing compounds containing Si-stereogenic centres. The motivation for using ARCM to form Si-stereogenic centres is discussed. To set the stage for this work, the development of olefin metathesis as a tool in organic synthesis is briefly summarised.
Chapter 2 describes the synthesis of various prochiral silicon-containing trienes and their reactivity in Ru-, Mo- and W-catalysed ring-closing metathesis. . Following extensive screening of chiral catalysts, few catalysts were identified that enabled selective ARCM to access Si-stereogenic products in up to 98% ee. A systematic investigation of the relationship between the structure of the starting material (i.e., hydrocarbon chain length, steric and electronic properties of the silicon substituents) and the resulting efficacy in ARCM was undertaken, the results from these experiments are discussed. Importantly, this study represents the first example in which ARCM has been successfully used to desymmetrise prochiral substrates to form a new chiral Si centre (Scheme 1).
Chapter 3 provides a general introduction to the field of trifluoromethylation, with a special focus on recent applications of transition metal catalysts in Csp2–CF3 and Csp3–CF3 bond formation. A myriad of effective nucleophilic, electrophilic and radical trifluromethylating reagents have been developed during the past several years; the properties of these reagents and their compatibility with various modes of catalysis are summarised to provide a context for the second part of this thesis research.
Chapter 4 presents two novel methods for effecting trifluoromethylation of allylsilanes . First, it was discovered that the combination of an electrophilic trifluoromethlyating reagent and a copper catalyst effectively mediated trifluoromethylation of allylsilanes. The silicon substituent was crucial for improving the nucleophilicity of the substrate and dictating the regioselectivity of the Csp3–CF3 bond-forming step. With this method, alkyl or aryl substitution at the β-position of the allylsilane was critical for reactivity. Second, in a complementary study, it was found that copper could be replaced by a ruthenium photocatalyst and visible light. This latter method allowed for trifluoromethylation of substrates that were ineffective with copper catalysis. Mechanistic studies of both reaction systems were undertaken, and plausible reaction pathways for both reactions are proposed.
Chapter 5 gives full experimental procedures and characterisation data for all compounds.
Collisional and photoexcitation of transition metal clusters
Keywords: transition metal cluster copper Cu rhodium Rh DFT

The properties of transition metal clusters differ from those of both atomic and bulk size regimes. Such clusters are incompletely understood and potentially useful, making them attractive targets for further study.
The very smallest clusters studied in this thesis (CuO, Cu2 and Cu3) have been investigated with velocity map imaging. 1+1' photodissociation of CuO X 2Π3/2 was observed, via the C, D, E, F and H states of CuO. CuO&ast; was photodissociated to form Cu(2D3/2) + O(1D2). D0(CuO) was determined to be 3.041±0.030 cm-1. Non-resonant three-photon Cu2 photodissociation occurred throughout the energy range studied to produce one ground-state and one highly-excited copper atom,Cu&ast;. Cu&ast; was ionised by a single additional visible photon. Nearly all Cu&ast; atoms with internal energies between 41000 and 53000 cm-1 were observed. D0(Cu2) has been calculated to be 1.992±0.037 eV.
Features arising from photodissociation of Cu3 were observed in the Cu&plus; and Cu2&plus; ion yield spectra and images. Their structure was ill-resolved due to uncertainties in the internal energy of both parent Cu3 and product Cu2. These features correspond to single-photon dissociation of Cu3 to produce metastable D-states of the copper atom and vibrationally excited Cu2. One series of features implies a previously-unobserved state of either Cu2 or Cu3.
RhnN2O&plus; and RhnON2O&plus; (n=5, 6) were collisionally activated in collision-induced dissociation (CID) experiments with Ar and 13CO. These experiments were carried out in a Fourier Transform Ion Cyclotron Resonance(FT-ICR)spectrometer. Argon collisions induced both N2O desorption and N2O reduction. The branching ratios observed reproduced those seen in prior IR-MPD experiments. 13CO was observed to chemisorb to the cluster upon collision, activating not only N2O desorption and reduction but also CO oxidation. Formation of CO2 was noted to be particularly rapid on the n=5 cluster compared to the n=6 cluster.
Reactions of RhnN2O&plus; (n=4-6) clusters were also activated by black body radiation. This technique is known as BIRD - black-body induced infrared radiative dissociation. These studies revealed that the N2O desorption barrier exceeds the N2O reduction barrier on all clusters studied, but that the entropic favourability of desorption increases its rate relative to reduction with increasing cluster internal energy. The BIRD rate was much reduced upon cooling the ICR cell to 100 K. A further test of the BIRD mechanism increased the number of N2O ligands and hence the absorption rate. An approximately linear increase in the dissociation rate of Rhn(N2O)m&plus; was observed with index m. Deviations from linearity were caused by variations in the N2O desorption rate. In the case of Rh5(N2O)m&plus;, desorption rates corresponded closely to N2O binding energies calculated by density functional theory. The system was modelled using a master equation approach.
Complications and failures of secondary prevention in acute ischaemic  stroke
Keywords: secondary prevention
Stroke

Stroke is a leading cause of death and the most common cause of disability in adults in the United Kingdom. Several treatments are effective in preventing stroke in the long term after TIA and minor ischaemic stroke, including aspirin, other antiplatelet agents, and blood pressure lowering drugs, statins and anticoagulation in atrial fibrillation. However, failure of secondary prevention to prevent recurrent vascular events is still a major clinical problem, as is the risk of bleeding associated with antiplatelet agents and anticoagulants.
This thesis determines the risks associated with urgent secondary prevention in the acute phase after TIA and minor stroke, particularly the reduction in risk of early recurrent stroke, the risk of bleeding with combination of aspirin and clopidogrel in the acute phase and whether or not there is a rebound increase risk of ischaemic stroke or recurrent TIA after withdrawal of a short course of clopidogrel.
I have shown that urgent and early treatment of ischaemic stroke with secondary prevention leads to an 80% reduction in recurrent stroke. I have also shown that an increased bleeding risk exists among aspirin naïve patients treated with combination antiplatelet medications compared to those already treated with aspirin. My work has also shown that discontinuation of clopidogrel following treatment for 30 days or more does not lead to a rebound increase in ischaemic stroke.
Bleeding events are a frequent complication of antiplatelet treatment in TIA and ischaemic stroke. I have shown that the long term risk of bleeding in a population study treated with antiplatelets is 6% per 100 person years. Using this information I identified risk factors for bleeding to develop a clinical baseline bleeding model to identify those at higher risk of bleeding. Age was identified as a significnant risk factor for both bleeding and recurrent ischaemic risk. In addition, bleeding events are associated with higher rates of fatality and disability in the older population.
Finally, I have shown that the time trends in stroke recurrence differ depending on the presenting event i.e TIA or stroke. Stroke recurrence risk after minor stroke is delayed compared with TIA, and remains high during the late phase despite current best medical treatment. Blood pressure control and atrial fibrillation are risk factors for late stroke recurrence identifying the unmet need for better detection and treatment potentials to reduce late recurrent stroke.
Cooperating to compete: the role of regional powers in global nuclear governance  
Keywords: Regional Powers
Nuclear Policies
Global Order
Nuclear Order

This thesis explores the role of regional powers in the development of regional nuclear regimes. Its central argument is that the devise of regional nuclear regimes through the leadership of regional powers is driven by both functional and strategic reasons. Functionally, regional nuclear institutions serve to provide more tailored solutions to respond to nuclear risks emerging at the local level. Strategically, the formation of sub-global institutions enables regional powers to exercise considerable influence on nuclear governance processes at both regional and global levels. And in situations where regional powers are dissatisfied with the global nuclear-institutional status quo, regional nuclear institution-building provides an incomparable opportunity to question that status quo and challenge, albeit indirectly, the preferences of the United States, their main architect.
The type of leadership provided by regional powers in the establishment of regional nuclear regimes is affected dynamically by two relationships: the regional powers' relation with the United States and their relation with secondary regional players. The former relation is defined as 'global nuclear alignment' and refers to the degree of proximity of the regional power towards U.S. nuclear preferences. The latter is defined as 'regional embeddedness' and captures the degree of convergence of regional powers' nuclear preferences with those of its most proxy regional contender, as well as the level of commitment shown by the regional power vis-à-vis regional integration.
The thesis argues that when both relations are low, divergence of the regional nuclear regime from global nuclear institutions is most acute. Conversely, when only one of the relations is high, the regional nuclear regime tends to converge with global nuclear institutions, either in goals or in methods. The theoretical framework is applied to investigate three cases of regional leadership as provided by Brazil, Indonesia and France in the establishment of the regional nuclear regimes in their respective regions.
Non-invasive associative plasticity induction in a cortico-cortical pathway of the human brain
Keywords: hand function
neuroplasticity
neuroimaging
stroke
brain stimulation
connectivity
motor function

Associative plasticity, which involves modification of synaptic strength by coactivation of two synaptic inputs, has been demonstrated in many species. Here I explore whether it is possible to induce associative plasticity within a corticocortical pathway in the human brain using a novel protocol that activates two brain areas repeatedly with double-site transcranial magnetic stimulation (TMS). The pathway between ventral premotor cortex (PMv) and primary motor cortex (M1) which computes hand movements for precision grasp was manipulated.
First, I selectively potentiated physiological connectivity between the stimulated brain areas. The effects as assessed with paired-pulse TMS were in accordance with principles of spike timing-dependent plasticity (STDP), pathwayspecific and showed a different pattern of expression during rest and during performance of a naturalistic prehension task. Furthermore, I demonstrated that effects evolved rapidly, lasted for up to three hours and were reversible.
In a follow-up study, the protocol‘s effects on network interactions were investigated using functional magnetic resonance imaging (fMRI), specifically focussing on functional connectivity of network nodes within the wider parietofrontal circuit controlling reaching-and-grasping. The study demonstrated that functional connectivity was causally modified between stimulated nodes and that those changes in coupling also affected parallel, functionally-related pathways. Comparison of neurophysiological (paired-pulse TMS) and functional (fMRI) connectivity between individuals revealed a linear relationship of these connectivity indices; the first can assess the physiological nature of the interaction, whereas the latter can elucidate global network effects, making the techniques complementary.
Neurophysiological interactions of ipsilesional and contralesional PMv-M1 were tested in chronic subcortical stroke patients during grasping. Patients showed a diminished facilitatory influence of ipsilesional PMv on M1 compared to healthy controls which might contribute to their motor disability. Application of paired-associative TMS “normalised“ the reduced effective influence of ipsilesional PMv on M1 and this effect correlated with the patient‘s potential to improve their dexterity.
Unfair prices in contracts in English and French law
Keywords: unfair prices
contracts
lesion
laesio enormis
salvage contracts
sale of reversions
Article 1674

When and why can parties escape from a contract on the ground that the price is unfair? This question is considered in a comparative and historical perspective in English and French law. The general rule in both systems is that the parties are free to determine the price and they are then bound by their contract. One well known exception in French law, which derives from Roman law, is Article 1674 of the Code civil which allows a vendor to rescind a contract for the sale of land if the price agreed in the contract is less than five-twelfths of the fair price. It is generally thought that there are no analogous rules in English law. However, the law on this subject is in fact considerably more complex and more colourful than this simple contrast would suggest.
Numerous rules on unfair prices in contracts were created in French law by the legislature and the courts since the promulgation of the Code civil in 1804. In English law, courts intervened in contracts on the ground of an unfair price in a few instances in the nineteenth century. However, only the rule on unfair prices in salvage contracts has survived until today. In both systems, the policies of preserving family wealth, protecting weak parties and giving special treatment to certain parties for economic, political, social or cultural reasons underpin these rules.
There are two principal conclusions. First, freedom of contract is much less extensive in French law than in English law. This is evident in the numerous rules on unfair prices in contracts in French law and in the primacy of the remedy of altering the price rather than rescission. Secondly, while in theory, French courts play a much less significant role than English courts in the development of law, the creation and abolition of certain rules on unfair prices in contracts by French courts shows that judicial creativity in French law can be much less constrained in practice than in English law.
Characterisation of Nespas, a non-coding imprinted RNA
Keywords: imprinting
long non-coding RNA

Nespas is the non-coding antisense transcript of the imprinted Gnas cluster; it is expressed from the paternal allele and is located on mouse distal chromosome 2. In this thesis new transcripts of >10 kb and 0.8 kb have been identified. The 0.8 kb transcript is a spliced variant that is retained in the nucleus and its 3’ end lies approximately 30 kb from the start site. Transcription from the Nespas promoter does not proceed beyond this point. A collection of previously known splice variants have also been detected and are exported to the cytoplasm. Nespas is expressed in the embryo during the second half of gestation and peaks at 13.5 dpc. Nespas is imprinted in the placenta at 11.5, 15.5 and 17.5 dpc. The Nespastm4Jop allele, to truncate the Nespas transcript 10.5 kb from the start site, has been transmitted through the germline and a breeding colony established. Preliminary analysis shows Nespas has a regulatory function. A second targeting construct to truncate Nespas 12.5 kb from the start site has been designed and assembled to investigate whether the 3’ end of the Nespas transcript that is transcribed upstream of the Nesp promoter is required for Nespas-mediated silencing of Nesp.