VictorJuiz/thesis huggingface dataset:
Studies of the reactions of perfluoroarylborane Lewis acids with transition metal compounds

This thesis describes the preparation of strongly electrophilic boranes and their reactivity with transition metal compounds.
Chapter One presents an overview of the reactivity of boron-containing Lewis acids as found in the literature focusing primarily on reactions of electrophiles containing a boron-perfluoroaryl bond that are of synthetic rather than catalytic interest.
Chapter Two presents studies into the reactivity of boranes of the general formula RB(C6F5)2 [R = (C6F5), Ph, H or Cl] with some metallocene hydrides. The previously synthesised adduct [(η5-C5H5)2Mo(H)(η1-HB(C6F5)3)] has been further investigated and the analogous adduct of HB(C6F5)2 is also reported. The zwitterionic compounds [(η5-C5H4B(C6F5)2R)(η5-C5H5)WH3] {R = (C6F5), Ph, H or Cl*} and [(η5-C5H4B(C6F
5)3)(η5-C5H5)ReH2] are described and have been fully characterised (* indicates that an X-ray crystal structure was obtained). Investigations into the reactivity of these compounds towards competing Lewis bases have been undertaken and reveal that the rhenium zwitterion is considerably more stable than the tungsten analogues.
Chapter Three presents reactions between B(C6F5)3 and transition metal nitrido complexes. B(C6F5)3 reacts directly with a number of nitrido compounds; [{(C66F5)3BN}Re(PR3)(S2CNR'2)2] (R3 = MePh2 and R' = Et*; R3 = Me2Ph and R' = Me*), [{(C6F5)3BN}ReCl(PMePh2)2(S2CNMe2)], [{(C6F5)3BN}Mo(S2CNR2)3] (R = Me or Et) and [{(C66F5)3BN}Os(1,2-S2C6H4)2][nBu4N] have all been prepared (* indicates that an X-ray crystal structure has been obtained). The reactivity of these adducts towards competing Lewis bases has been probed revealing a range of stabilities over the three metals considered. The adduct of an osmium nitrido compound has also been reacted with competing Lewis acids and the compound [{(C6F5)3BN}Os(1,2- (S)(SMe)C6H4)(1,2-S2C6H4)] has been made and characterised by NMR spectroscopy.
Chapter Four describes the synthesis of Lewis acids containing a boronperfluoroaryl bond. Firstly, modified literature preparations of RB(C6F5)2 [R = (C6F5), Cl or H] are reviewed. Attempts to prepare the new Lewis acid BAr'3 [Ar' = (3,5- C6H3(CF3)2)] are described, including the synthesis and characterisation of the new tin reagent nBu3SnAr'. Additionally, the new electrophile B(C6H5)(C6F5)2 has been prepared using either nBu3Sn(C6F5) or [LiC6F5] as the source of (C6F5).
Chapter Five contains experimental details for the thesis, characterising data for new compounds are presented in Chapter Six and details of the X-ray crystal structures may be found in the Appendices.
The commission of the peace, 1675-1720

In the period from 1675 to 1720, the Justices of the peace in the English and Welsh counties were appointed by royal authority delegated to the Lord Chancellor. The Chancellor thus possessed a formidable instrument of patronage, which he operated both by power of appointment and by power of dismissal. This patronage extended principally to a class of persons of considerable influence within the political nation of the seventeenth and eighteenth centuries, that is, the country gentry.
It has long been surmised that, within the period under review, the local patronage of the Chancellor was employed to secure political advantage. Such a purpose might be defensive, to safeguard the state against those not wholly committed to the Anglican Church, the principles of the Revolution of 1688, or the Hanoverian Succession; or it might be aggressive, to reward friends with, and deprive enemies a local authority which it was generally thought to be both honourable and desirable to exercise. The commission of the peace was thus a means by which changes in central policy, and shifts in central power, were extended into the localities. In a period when Parliamentary and electoral politics, and, to a lesser but still important extent, ministerial politics, became influenced by distinctions of party, it is a reasonable hypothesis that local politics became similarly influenced through the medium of appointments to the local magistracy.
The object of this study has been to confirm or deny this hypothesis. To do so, it is necessary to measure how widespread the regulations of the county commissions of the peace were; there were fifty-five counties, one county palatine, and two liberties analagous to counties (besides several small liberties and corporations) for which separate commissions of the peace were issued. Substantial changes in any one of these might attract attention from contemporaries of a kind which would give a possibly misleading impression that similar changes took place in other counties as well. It is also necessary to measure the relative scale of the alterations that were made. The bench of magistrates varied in size in different counties at the same time and in the same county at different times. The commission of the peace for a given county could be remodelled by adding names to the list of gentlemen who were empowered to act as justices, or by omitting names from it. Such remodelling can only be put in perspective in the context of the total length of the list at the time that the regulation took place, furthermore, it is of importance to ascertain the precise timing of changes in the commissions, in order to judge how far such changes originated in changes at the centre of politics, and how far the changes at the local level themselves resulted in political consequences of wider significance, in, for instance, general elections.
[See pdf. for full abstract]
Models of complex adaptive systems with underlying network structure

This thesis explores the effect of different types of underlying network structure on the dynamical behaviour of a competitive population - a situation encountered in many real-world complex systems. In the first part of the thesis, I focus on generic, but abstract, multi-agent systems. I start by presenting analytic and numerical results for a population of heterogeneous, decision-making agents competing for some limited global resource, in which connections arise unintentionally between agents as a by-product of their strategy choices. I show that accounting for the resulting groups of strongly-correlated agents - in particular, the crowds and so-called 'anticrowds' - yields an accurate analytic description of the systems dynamics. I then introduce a local communication network between the agents, enabling them to intentionally share information among themselves. Such an interaction network leads to highly non-trivial dynamics, forcing a trade-off between individual and global success. Introducing corruption into the information being exchanged between agents, gives rise to a novel phase transition. I then provide a quantitative analytic theory of these various numerical results by generalizing the Crowd-Anticrowd formalism to include such local interactions.
In the second part of the thesis, I consider a real-world system which also features competitive populations and networks - a cancer tumour, which contains cancerous cells competing for space and nutrients in the presence of an underlying vasculature structure. To simplify the analysis and comparison to real clinical data, the model chosen is far simpler than that discussed in the first part of the thesis - however despite its simplicity, the model is shown to yield remarkably good agreement with empirical findings. In addition, the model shows how different treatment methods can lead to a wide variety of unexpected re-growth behaviours of the tumour.
A population-based cohort study of coronary heart disease after a myocardial infarction : six-year follow-up

Background: Despite well-documented improvements in short-term prognosis after a myocardial infarction, longer-term outcomes and health service costs are poorly defined.
Aim: To provide a comprehensive account of the progression of coronary heart disease (CHD) after a myocardial infarction in the subsequent six to seven years. The long-term consequences and associated factors were examined in several separate but interrelated follow-up studies focusing on the following areas:
(i) Mortality; (ii) socioeconomic status as a predictor of mortality; (iii) non-fatal CHD progression and preventive treatment; (iv) psychological health; and (v) health service use and cost.
Methods: The patient cohort consisted of 1118 Oxfordshire residents aged 30 to 79 years diagnosed with a myocardial infarction in 1994-95 identified by the Oxford Myocardial Infarction Incidence Study (OXMIS). Studies undertaken:
(1) Analyses of OXMIS databases, adding data from 1995 to 2001, with emphasis on 613 long-term survivors.
(2) Review of hospital and general practice casenotes for 606 survivors.
(3) Postal questionnaire study of 266 seven-year survivors.
Main Results: By six years, amongst 28-day survivors:
(1) 13% had died of CHD with no significant gender or socioeconomic differences.
(2) 51% had experienced another non-fatal coronary event, of which 37% occurred within the first year. Subsequent annual rates reduced substantially, but continued at 4% per year. Most coronary preventive medications were initiated at either hospital discharge or within the first year. After hospital discharge, CHD health service costs for the first year were £1700 per patient. From the third year onwards, these annual costs reduced to £600.
(3) At seven years, the prevalence of poor psychological health was 15%. Patients with current angina symptoms were twice as likely to be emotionally distressed as those with no angina.
Conclusion: In 28-day infarct survivors, the first year was the time of highest risk for subsequent CHD events and associated health service costs. Nevertheless, risk of CHD mortality in the cohort was higher than that of the general population over the following five years.
Secular policy enforcement during the personal rule of Charles I : the administrative work of parish officers in the 1630s

This thesis explores the impact of the Caroline reform policies during the Personal Rule on the organisation, work-load, and morale of parish officers. In addition to suggesting a national approach to the study of local government, it examines the enforcement of the Book of Orders, Ship Money, and the Perfect Militia at the parochial level during the 1630s. The sources employed include the rich correspondence between the Privy Council and county governors (JPs, Sheriffs, Deputy Lieutenants), and all available parish officers' accounts from thirty-nine English counties and corporate towns.
It is argued that the pattern of response to national policies was strongly influenced by communal values, and the administrative standards and individual character of local officeholders. The enforcement of the Caroline reform policies depended on their political acceptability and the ability of the Privy Council and county governors to coerce parish officers. While the Book of Orders was generally welcome in the localities, its implementation was adapted to local necessities and the administrative inertia of both JPs and parish officers. The supervision of the enforcement was restricted by the extreme dependency of superiors on information from parish officers. The administration of Ship Money was thwarted by local assessment disputes, economic depression, and political opposition. Its collection met with significant difficulties from the very start, and ceased under the pressure communities exerted on their officers. Far from being perfect, the militias maintained their standard under the constant supervision of the Deputy Lieutenants. The control of parishes over their officers was emphasised during the recruitment for the Scots' Wars and the collection of Coat and Conduct Money, both of which were causes of the failure of the English army.
In conclusion, this thesis proposes that the response to national policies in early modern England varied considerably from community to community. A voluntary and highly decentralised system of local government was unsuitable to enforce contentious policies against the will of the population. The 1630s saw the partial breakdown of local government which significantly contributed to the collapse of the Personal Rule in 1640.
QCD processes and hadron production in high energy e+e- annihilation

A study is presented of general features of the reaction e+e-→ hadrons. The data are interpreted in terms of current models of the underlying QCD and hadronisation processes. These models are outlined in detail and their predictions are compared with most of the available experimental data collected between 12.0 and 46.8 GeV mean centre of mass energies.
The model arbitrary parameters were optimised to give a generally good description of the global properties of the large hadronic event sample accumulated by the TASSO detector at 35 GeV: The Lund O(α2s) model describes properties in the event plane very well, but is deficient in the properties transverse to this plane. The Webber LLA model gives a good description of the transverse observables, but overestimates those quantities in the plane. The Lund LLA + O(α2s) model provides a good representation of the transverse properties but underestimates some quantities in the plane, though the discrepancy is much smaller than for the LLA model.
The evolution of the observables as a function of c.m. energy between 12.0 and 41.5 GeV is generally well described, the Lund LLA + O(α2s) model representing the data best. It is concluded that this model is successful in reproducing accurately most features of the data because it includes QCD calculations of both hard and multiple soft gluon emission processes.
The model predictions are extended up to W = 200 GeV, where the two parton cascade models give similar predictions of the event properties which differ significantly from those of the 0(α2s) model.
Top quark production is simulated at W = 200 GeV for a top mass of 60 GeV/c2 and the distributions of thrust, aplanarity, PTin,PTout and rapidity are found to be most sensitive to its presence.
The data at 35 GeV are also analysed in terms of explicit multijet final states and compared with the QCD model calculations. The 0(α2s ) model is unable to account for the observed rates of 4- and 5- jets per event, though it reproduces the 2- and 3- jet rates reasonably well. The LLA model gives a better description of the rates of ≥ 4-jets but gives too few 3-, and too many 2-jet events. The LLA + O(α2s) model is able to reproduce all jet rates well. All the models describe the trend of the evolution of the jet rates between <√s> = 14 and 43.8 GeV.
It is shown that the rate of 3-jet events seen in the data decreases as s increases in a manner consistent with the Q2 dependence of αs as predicted by QCD.
Human brain acetylcholinesterase

Procedures for the preparative purification of human acetylcholinesterase (AChE; EC 3.1.1.7) have been examined. Chromatofocussing showed caudate nucleus and cerebrospinal fluid (CSF) AChE eluting between isoelectric points (pi) of 5.2 - 5.57, whilst isoelectric focussing (IEF) revealed heterogeneous AChE isoforms migrating between pI 4.5 - 6. Affinity chromatography proved to be better in yielding highly pure samples. The ligands used were either acridinium or procainamide, which yielded brain AChE recoveries of 10.1% and 42.8%, respectively. Various other methods were used such as gel filtration and ion-exchange chromatography on a Pharmacia SMART System.
Purified brain AChE was used as antigen to generate anti-AChE monoclonal antibodies (mAbs) by in vivo immunization. BMS-3E4, -7G10, and -9F4 reacted with erythrocyte (G2) AChE, whilst BMS-6D6 bound to brain (G4) AChE in dot blot, titration, and sedimentation experiments. Conversely, the four mAbs recognized only the G4 form and not the G2 form on immunoblotted IEF and non-denaturing Clarke gels. Deglycosylation studies suggest that the four mAbs recognize a carbohydrate epitope linked to AChE.
Four additional mAbs were raised by the novel method of in vitro immunization, using a synthetically-produced C-terminus peptide as antigen. BMS-5, -6, -7, and -8 are all IgMs which recognize soluble brain and not erythrocyte nor membrane-bound AChE in dot blots, IEF, and sedimentation analyses.
Although immunocytochemistry of the above-mentioned mAbs did not demonstrate any positive cholinergic binding, the present mAbs may still offer potential clinical and biochemical applications.
Kinship and exchange relations within an estate economy : Ditchley, 1680-1750

This thesis presents original evidence on changes occurring within the exchange economy of a north-west Oxfordshire rural community during the first half of the eighteenth century. It has been suggested that capitalism began to evolve in rural areas of England during this period due to the transformation of agriculture and growth of consumerism. Thus one would expect to find evidence of a growing commercialisation of the agrarian population characterised by increased reliance upon the market and a diminution of customary exchange and self-provisioning.
Drawing evidence from the Ditchley estate accounts, the balance of monetary and nonmonetary exchange, the nature of transactions, and the role of kinship connections in mediating them, are described and analysed. It is argued that whilst the accounts do reveal significant levels of monetization and widespread use of market exchange especially after 1725, an extensive, largely non-monetized internal estate market in goods operated in parallel. These two systems appear to have been as much complementary as in competition, reflecting the high levels of integration within the local agrarian economy of the stonebrash region.
Moreover, analysis of kinship networks suggests that many seemingly monetary transactions had a social component. Market exchange at Ditchley was essentially as dependent on social relations as reciprocal exchange within the neighbourhood area. The customary economy of kinsman and neighbour continued to flourish and to complement the expanding market economy in early eighteenth-century England, because both had a moral component. For the villagers at Ditchley there was no clear dichotomy between the two.
The Labour Party and the popular front movement in Britain in the 1930s

This thesis seeks to recount the history of the British popular front movement in the 1930s, especially its relationship to the Labour Party.
The popular front tactic, involving the unity of all anti-fascists, was first proclaimed to the world by the French communists in 1934. In the following year the tactic was officially sanctioned at the seventh Congress of the Comintern, and from then until the signature of the Nazi-Soviet Pact in 1939 communist parties throughout the world sought the formation of popular fronts.
In its British form the popular front has been neglected both by historians of the 1930s and of the Labour Party. The question why the movement should not figure prominently in the former case is easily understood. It came nowhere near to attracting the support of all anti-fascists, yet alone to overthrowing the National Government. Moreover, it was a confusing movement, and it involves analysing problematical questions. Nevertheless, the movement is of interest in the general context of the 1930s for it grew to attract considerable support, not least in the Labour Party. Indeed, the reason for the popular front's neglect in the context of the Labour Party is very difficult to comprehend. The Labour Party was by far the largest opposition party and official Labour hostility played the major part in dooming the movement as a serious challenger to the government. More importantly, the movement emphasised divisions and problems within the party which can be traced back in its history, especially to the events of 1931, and which by 1959 were posing a serious threat to the party's future.
[Please see pdf. for full abstract]
Inferring the selection on genes of yeasts, schistosomes and amniotes

Research presented in this thesis focuses on using evolutionary rates to detect the fingerprint of natural selection. I have undertaken four studies that consider different branches of the eukaryotic tree: 1. Predicting positive selection in genes from five species of Saccharomyces genes. 2. Studying the constraints on both synonymous and non-synonymous sites of Saccharomyces genes. 3. Using evolutionary rate studies to investigate how schistosomes have adapted to their environment. 4. Associating gene evolution with the non-linear increase between amniotes' brain and body sizes. In the first project, I investigated protein coding sequences to identify genes and their amino acids that have been subject to positive selection. I show that Saccharomyces genes exhibiting strong evidence for positive selection are enriched in defence and growth functional categories. In the second study, I find that a set of Saccharomyces genes are both constrained at the non-synonymous sites and synonymous site, presumably to ensure the correct folding of the protein, irrespective of their expression levels. I also find that the majority of yeast genes are not biased with respect to codon usage, and investigate constraints on substitution rates at synonymous sites. The third project examines the evolutionary rates of schistosome genes. I show that stage-specific genes are under weaker selective pressures than genes expressed in many life stages. I predict that the fastest evolving stage-specific genes enable the pathogen to better adapt to its ever-changing environment. In the final project of this thesis, I ask whether evolutionary rate variation for brain-expressed/specific genes correlates with brain size (allometric) change in amniotes. I find that lineages with relatively large brains have faster evolutionary rates. However, I find that there is no region of the brain in which faster evolving genes of relatively large-brained animals are preferentially expressed.