VictorJuiz/thesis huggingface dataset:
The synthesis and characterisation of metal complexes containing chemically reduced bipyridyl ligand systems

This thesis describes the synthesis and characterisation of metal complexes that contain chemically reduced bipyridyl ligands. The crystal structures of twenty-six novel complexes are reported alongside detailed discussions on the electronic and spectroscopic effects and trends associated with the different oxidation states within these species.
Chapter One introduces the isomers of bipyridine and their redox chemistry, the concept of non-innocent ligands and the spectroscopic techniques that are currently used in determining ligand oxidation states. Subsequently, examples of main group, transition metal, lanthanide and actinide species that contain or may contain reduced forms of the ligand are discussed.
Chapter Two details the synthesis and structural characterisation of alkali metal salts of singly and doubly reduced forms of the three commercially available bipyridine isomers. The effects of this reduction are investigated with the aim of developing diagnostic fingerprints for each of the ligand oxidation states.
Chapter Three discusses the synthesis of an homologous series of compounds of the form [M(2,2'-bipy)(mes)2]n– where M = Cr, Mn, Fe, Co, Ni and n = 0, 1. Trends in magnetism, bonding and electronic structure are investigated with reference to theoretical calculations and the diagnostic fingerprints identified in the previous chapter.
Chapter Four describes the synthesis and characterisation of three compounds containing the isostructural motif [Zn2(4,4'-bipy)(mes)4]n– where n = 0, 1, 2. Structural and spectroscopic changes are discussed and com- pared to theoretical calculations.
Chapter Five contains descriptions of the spectroscopic techniques employed in the above research and synthesis routes to all compounds featured in this thesis.

Keywords: 4'-bipy
Mossbauer spectroscopy.
2'-bipy
2'-bipyridine
structural chemistry
radical
non-innocent ligand
crystallography
4'-bipyridine
X-ray crystallography
DFT
non-innocence
magnetochemistry
Advisor: Goicoechea, J
The je-ne-sais-quoi

The purpose of this thesis is to analyse the je-ne-sais-quoi through its history and its pre-history. When we are moved by something we cannot identify, but whose effects we cannot fail to recognize, how should we try and come to terms with our experience? The je-ne-sais-quoi rises to prominence as a keyword in such discussions during the period studied. This thesis offers the first full-length study of the word and its significance to literary and philosophical writing of that period. It traces its precursors, its rise as a noun in mid-seventeenth-century France and England, and its fall from grace. Previous historical work has generally restricted the word's application to aesthetics; this study examines its significance in the philosophy of nature and the passions as well as culture. It combines historical method and philosophical enquiry to inform the close analysis of examples. The aim is to consider what the je-ne-sais-quoi is and how it finds expression in writing.
A fourfold thesis is proposed, (i) The lexical je-ne-sais-quoi, in its core meaning, refers to an inexplicable force with sudden and vital effects, (ii) This force remains ever on the move by unsettling sedimented words, passing through current ones, and abandoning these as they too undergo sedimentation, (iii) The word history of the je-ne-sais-quoi,/em> encapsulates this movement. The term is first used to unsettle its semantic precursors (by Descartes and others), becomes current in writing of the mid-seventeenth century (that of Corneille and Pascal in particular), but soon settles into the sediment of polite culture (as Méré, Bouhours, and English Restoration comedy show), (iv) Returning the word to the mobile non-substantival forms of its pre-history in Montaigne, to whom a chapter-length study is devoted, uncovers a form of writing that captures the force of the je-ne-sais-quoi better than the settled word itself. The task of literature is to lend form to the je-ne-sais-quoi by naming it in its inexplicable reality and by describing how it falls, like a disaster, into our experience.

Advisor: Professor Ian Maclean, T
Non-equilibrium dynamics of reaction-diffusion systems

Fluctuations are known to radically alter the behaviour of reaction-diffusion systems. Below a certain upper critical dimension dc , this effect results in the breakdown of traditional approaches, such as mean field rate equations. In this thesis we tackle this fluctuation problem by employing systematic field theoretic/renormalisation group methods, which enable perturbative calculations to be made below dc.
We first consider a steady state reaction front formed in the two species irreversible reaction A + B → Ø. In one dimension we demonstrate that there are two components to the front - one an intrinsic width, and one caused by the ability of the centre of the front to wander. We make theoretical predictions for the shapes of these components, which are found to be in good agreement with our one dimensional simulations. In higher dimensions, where the intrinsic component dominates, we also make calculations for its asymptotic profile. Furthermore, fluctuation effects lead to a prediction of asymptotic power law tails in the intrinsic front in all dimensions. This effect causes high enough order spatial moments of a time dependent reaction front to exhibit multiscaling.
The second system we consider is a time dependent multispecies reaction-diffusion system with three competing reactions A+A → Ø, B + B → Ø, and A + B → Ø, starting with homogeneous initial conditions. Using our field theoretic formalism we calculate the asymptotic density decay rates for the two species for d ≤ dc. These calculations are compared with other approximate methods, such as the Smoluchowski approach, and also with previous simulations and exact results.
Some problems in differential operators

We consider a formally self-adjoint elliptic differential operator in ℝn, denoted by τ. T0 and T are operators given by τ with specific domains. We determine conditions under which T0 is essentially self-adjoint, introducing the topic by means of a brief historical survey of some results in this field.
In Part I, we consider an operator of order 4, and in Part II, we generalise the results obtained there to ones for an operator of order 2m. Thus, the two parts run parallel.
In Chapter 1, we determine the domain of T0*, denoted by D(T0*), where T0* denotes the adjoint of T0, and introduce operators T0 and T which are modifications of T0 and T.
In Chapter 2, we use a theorem of Schechter to give conditions under which T0 is essentially self-adjoint.
Working with the operator T, in Chapter 3 ve show that we can approximate functions u in D(T0*) by a particular sequence of test-functions, which enables us to derive an identity involving u, Tu and the coefficient functions of the operator concerned.
In Chapter 4, we determine an upper bound for the integral of a function involving a derivative of u in D(T0*) whose order is half the order of the operator concerned, and we use the identity from the previous chapter to reformulate this upper bound.
In Chapter 5, we give conditions which are sufficient for the essential self-adjointness of T0. In the main theorem itself, the major step is the derivation of the integral of the function involving the particular derivative of u in D(T0*) whose order is half the order of the operator concerned, referred to above, itself as a term of an upper bound of an integral we wish to estimate. Hence, we can employ the upper bound from Chapter 4. This "sandwiching" technique is basic to the approach we have adopted.
We conclude with a brief discussion of the operators we considered, and restate the examples of operators which we showed to be essentially self-adjoint.

Advisor: McLeod, J
H°°-design and the improvement of helicopter handling qualities

This thesis presents the results of a study into the use of Hꝏ-optimization for the design of feedback control laws for improving the handling qualities of a Lynx helicopter. An important improvement to the Hꝏ-optimization procedure is the reduction in the number of iterative steps in the γ-iteration before convergence to the optimal γ. Some new algorithms are derived which significantly reduce the computation time for the γ-iteration. Both 2-block and 4-block cases are considered.
Control laws are designed for precise control of pitch and roll attitude, yaw rate and heave velocity. Analysis of the raw helicopter showed the need for a stability augmentation system as the dynamic characteristics of the unaugmented helicopter do not comply with military helicopter handling qualities requirements. Results from current research on helicopter handling qualities were used as guidelines in order to define the required dynamic characteristics. A six-degree of freedom nonlinear simulation was used to analyse the helicopter dynamic time histories.
A possible solution to the problem of incorporating helicopter handling qualities in the design of robust controllers is to use a two-degree of freedom controller structure. This is illustrated using both H2 and Hꝏ-optimization.
A piloted simulation study to assess the effectiveness of advanced control laws was initiated at RAE, Bedford.The trials were carried out in the single seat cockpit flight simulator, at the Flight Research Division and represent the first ever real-time piloted simulation using a Hꝏ-controller.

Advisor: Postlethwaite, I
Metabolic and endocrine effects of surgery and anaesthesia in the human newborn infant

This project was designed to investigate the ability of newborn infants to respond to surgical stress and to consider alternative methods of anaesthetic management in view of their hormonal and metabolic response.
Concentrations of blood metabolites (glucose, lactate, pyruvate, alanine, acetoacetate, 3-hydroxybutyrate, glycerol, non-esterified fatty acids, triglycerides) and plasma hormones (insulin, glucagon, noradrenaline, adrenaline, aldosterone, corticosterone, cortisol, 11-deoxycorticosterone, 11-deoxycortisol, progesterone, 17-hydroxyprogesterone, cortisone) were measured in blood samples drawn before and after surgery, at 6, 12 and 24 hours postoperatively. Urinary total nitrogen and 3-methylhistidine/ creatinine ratios were measured for 3 days postoperatively. Peri-operative management was standardised and severity of surgical stress was assessed by a scoring method.
In a preliminary study of 29 neonates, substantial hormonal and metabolic changes demonstrated the ability of neonates to mount a stress response to surgery. Compared to adult responses, the magnitude of these changes was greater but their duration was remarkably short-lived. Significant differences were found between preterm and term neonates, and between neonates given different anaesthetic management.
Randomised controlled trials were designed for studying the effects of : (1) halothane anaesthesia in 36 neonates undergoing general surgical procedures, (2) fentanyl anaesthesia in 16 preterm neonates undergoing ligation of patent ductus arteriosus, (3) high-dose fentanyl anaesthesia in 13 neonates undergoing cardiac surgery.
On comparing the responses of neonates within each trial, the stress response of neonates given halothane or fentanyl anaesthesia was diminished; their :
(a) catecholamine responses were decreased or abolished,
(b) glucocorticoid responses were suppressed,
(c) changes in blood glucose and gluconeogenic precursors were decreased,
(d) postoperative analgesic requirements were reduced, and
(e) their clinical condition after surgery was more stable.
The neonatal response was related to the severity of surgical stress, as assessed by the scoring method.
Thus, hormonal and metabolic changes following surgery in preterm and term neonates are distinctly different from those of adult patients; the lack of adequate anaesthesia may cause an accentuation of the stress response.

Advisor: Williamson, D
Aynsley-Green, A
Baum, J
RAB-A2a dependent membrane traffic in Arabidopsis thaliana

Rab GTPases are major regulatory proteins of vesicle traffic and thus responsible for membrane identity, vesicle targeting and vesicle fusion. The angiosperm Rab GTPase family is grouped into eight clades (Rab-A to Rab-H) that are broadly conserved in animals and yeasts. It has been proposed that the Rab-A clade has diversified in land plants giving rise to six plant- specific structural subclasses, Rab-A1 to Rab-A6. Previous work suggests that the Arabidopsis Rab-A2 and Rab-A3 proteins define a novel endosomal compartment that lies on a pathway between the Golgi and the plasma membrane. In dividing cells, the Rab-A2/A3 compartment is implicated in biosynthetic traffic to the cell plate but it is unclear what traffics through this compartment in non-dividing cells.
In this project, I investigated a range of membrane trafficking pathways in Arabidopsis thaliana. These were probed for dependency on RAB-A2a function, using the dominant negative approach combined with fluorescent marker technology. The data presented in this thesis suggests that RAB-A2a acts on a protein recycling pathway that is used by PIN2:GFP.

Keywords: Rab-GTPases
membrane traffic
PIN2
recycling
Advisor: Moore, I
Preston, G
The peopling of Southern Africa: a genetics approach

Human populations in Africa have high levels of genetic, cultural and linguistic diversity. Despite this, only a small proportion of African populations have been studied from a genetics perspective. There is a particular dearth of information for Southern Africa, even though this region is one of the few places where hunter-gatherer, pastoralist and farmer populations remain, and where interaction between these groups can be studied. This thesis analyses novel populations from Lesotho, Namibia and South Africa, for both maternal and paternal markers, in order to provide a more accurate understanding of the history of this region. Analysis of biodemographic data for these populations highlights signatures of specific cultural traits. Interestingly, contrary to expectations, results indicate that in the patrilocal Basotho there are no differences in within and between area mtDNA and NRY variation, despite observations of a higher female than male migration rate. Females move preferentially at shorter distances than males, minimising the impact of the higher female migration rate. Further analysis of the Southern African samples indicates that the genetic composition of these populations is different to previously studied populations from Sub-Saharan Africa. Notably, there is a significantly higher maternal hunter-gatherer component, potentially as a result of an archeologically defined static frontier which existed along the Maloti/Drakensberg escarpment. Analysis of Namibian samples provides additional information about the history of populations with different lifestyles in the region, with support for a link between Southern Africa pastoralists and East Africa, while other Namibian populations appear genetically different from previously studied populations. Overall, this work demonstrates the diversity of populations in Southern Africa, improves understanding of the history of this region, and also emphasises the value of having access to geographically and ethnically well-defined samples.

Keywords: African human population genetics
molecular anthropology
Advisor: Capelli, C
The spin structure of the baryons

Baryons are considered in the Nonrelativistic Quark Model (NQM) to be bound states of three valence quarks. Each quark has two possible spin eigenstates in the restframe of the baryon whose spin is fully carried by quarks. The baryon wavefunctions are connected through SU(6) symmetry rotations. For a long time, the measured magnetic moments of the baryons appeared to be in agreement with the NQM predictions.
However, recent experiments which are examining the spin structure of the baryons show the failure of several NQM predictions.
The so-called 'spin crisis' arose from the interpretation of the EMC deep inelastic scattering measurement of ∫ gp1 that the quark spins in the proton appeared to sum up to (almost) zero.
In this thesis it will be demonstrated that the spin problem is not a phenomenon restricted to quasi-massless current quarks in the high energy limit. Symmetry arguments are used to examine the baryon magnetic moments and reveal that we can observe massive but pointhke constituent quarks, with a characteristic mass ratio mu = md ≃ 2andfrasl;3ms. Surprisingly they do not contribute much to the baryon spin either. This analysis is free of the ambiguity arising from the UA(1} gluon anomaly which makes it impossible to calculate precisely the spin sum of the current quarks. One important finding in our analysis is the observation that the effects of SU(6) breaking hyperfine spin-spin interactions (which cause well-known splittings in the baryon masses) can be seen in the environment dependence of the constituent quark masses. The effective mass of a quark cannot be independent of its surrounding energy since the mass of the baryon is distributed amongst its constituents.
Consistent with the hypothesis that different quark masses do not impose SU(3) breaking on the baryon wavefunctions is the observation of induced 'second class' form factors. The way in which SU(3) breaking alters the gAandfrasl;gV ratios in semileptonic hyperon decays will be discussed and strong evidence for a new value of F/D is given, which is close to its SU(6) value. This value is derived independently from the baryon β-decays and from their magnetic moments. Dynamical models are discussed which might explain the observed polarised strangeness 'inside' the proton, and the almost vanishing quark spin sum.

Advisor: Roberts, R
Llewellyn, C
A study of the Human Platelet Antigen 1a (HPA-1a) antibody response in neonatal alloimmune thrombocytopenia (NAIT)

Neonatal alloimmune thrombocytopenia (NAIT) is caused by maternal alloantibodies against fetal platelet antigens inherited from the father and which are absent from maternal platelets. In Caucasians, antibodies against the Leu33 (HPA-1a) polymorphism of integrin β3 (part of the platelet αIIbβ3 complex) account for >70% of cases. Antenatal screening for these antibodies does not currently take place in the UK, partly because of the absence of sensitive, predictive tests.
We hypothesized that the poor sensitivity and predictive abilities of current assays are due to the use of β3 in an inappropriate conformation, resulting in sub-optimal binding of HPA-1a antibodies. We hypothesized firstly that in vitro induced changes to αIIbβ3 might alter accessibility of the HPA-1a epitopes to alloantibodies, thus reducing assay sensitivity. Secondly, we hypothesized that HPA-1a antibodies are stimulated by, and preferentially recognise, β3 in association with αv, a molecule present on placental syncytiotrophoblasts, and that reactivity against platelet αIIbβ3 reflects only cross-reactivity with αvβ3.
Our first hypothesis was proven by demonstrating that use of the cation chelating compound EDTA, used by many diagnostic laboratories as a component of assay reagents or present in blood samples as anticoagulant, resulted in significantly reduced assay sensitivity. These findings were confirmed in an international workshop. Support for our second hypothesis was provided by demonstrating enhanced reactivity of a small panel of examples of anti-HPA-1a against αvβ3 compared to αIIbβ3 and by molecular modelling data.
We also showed that HPA-1a antibodies can inhibit platelet function by using a novel application of the ROTEM® delta thromboelastograph and an immunofluorescence assay in which we demonstrated blocking of platelet function using a monoclonal antibody, PAC-1, that binds only to activated αIIbβ3.
These studies provide possible explanations for the poor sensitivity and predictive abilities of current assays and suggest further areas for research.

Keywords: neonatal alloimmune thrombocytopenia
Blood platelets
integrins
platelet antibodies
Advisor: Roberts, D
The role of private institutional investors for the development of urban infrastructure assets

The topic of infrastructure investment has emerged as a critical public policy issue over the last thirty years as governments grapple with an infrastructure deficit that has become one of the great global challenges of our time. Through the simultaneous processes of neo-liberalisation and globalisation, the urban infrastructure landscape has emerged as an attractive investment area for large financial institutions. With the recent Global Financial Crisis further exacerbating both the funding and growth lifting needs of nations, the urgency of linking institutional investors with urban infrastructure assets is more apparent than ever.
This thesis looks at the evolving dynamics associated with the growing involvement of the financial industry in the provision of urban infrastructure assets. This is achieved by using a relational perspective, studying the interactions of financial actors, while simultaneously being aware that these decisions are made within a larger political economic context. It is argued that the complex, heterogeneous and long-term nature of institutional infrastructure investing requires a multi-disciplinary relational economic geography framework. Specifically, relational theory is used to explore the informational content and geographical structure of the infrastructure financial product, the influence of government decision-making, the corporate governance of infrastructure investments and the investment relationship between investors and financial intermediaries.
Despite exponential growth in the field over the last decade, the infrastructure financial product has a level of sophistication and obscurity that prohibits it from being classed a transparent investment area, highlighting the importance of a relational approach to investments. From the case study on Auckland International Airport Ltd., it is shown that through a relational form of light-handed regulatory contract, the government plays a central role in affecting the favourable performance of an economically significant asset. The explication of the Spanish-led ADI consortium acquisition of UK airport operating company BAA illustrates the need for ‘glocal’ infrastructure governance to incorporate a wider stakeholder perspective as well as an appropriate shareholder wealth maximisation strategy. And finally, through analysing the relationships between investment partners for the infrastructure investment process, investment consultants are playing a crucial role to help align interests and promote the long-term relational approach to investing for the infrastructure asset class.
In an age where infrastructure investment has been recognised by many nations around the world as the most important growth lifting strategy, this thesis provides a deeper understanding of how a relational approach can facilitate successful private institutional infrastructure investment.

Keywords: urban infrastructure
institutional investment
economic geography
Advisor: Clark, G