VictorJuiz/thesis huggingface dataset:
Processing and properties of nanostructured thin film energy storage devices

A spray deposition manufacturing route has been developed for the fabrication of carbon nano-structured and micro-structured energy storage devices in a thin film format, with controlled film thickness, homogeneous film surface morphology and high electrochemical performance for both supercapacitors and lithium ion battery anodes. Three types of low cost commercially available carbon materials (graphite, activated carbon and carbon black) have been investigated, and electrodes characterised in terms of surface morphology, surface chemistry, microstructure and electrochemical properties.
By using ball milling, CO2 activation and adding suitable carbon conductive additives, nano-graphite-based film electrodes (one meter long and ~ 3 µm thickness) have been fabricated, with excellent ion transport and low electrical resistance (< 1.8 Ω). Specific capacitance of 110 F/g at a scan rate of 100 mV/s in 1 M H2SO4 was achieved.
The high rate performance of activated carbon-based electrodes ( ~2 µm thickness) has been enhanced by reducing the contact resistance of electrode/current collector interface and building a well-interconnected and hierachical meso/macro-porous structure. A specific capacitance of over 120 F/g at a scan rate of 600 mV/s or 20 A/g current density in 1 M H2SO4 was achieved.
The performance of carbon black-based electrodes (~4 µm thickness) in different electrolytes has been studied in both two- and three-electrode cells. High specific capacitances of 260 F/g at 1 A/g was achieved in 6 M KOH, together with energy and power densities of 21 kW/kg and 18 Wh/kg in 1 M Na2SO4.
Finally, graphite-based electrodes for rechargeable lithium-ion batteries have also been fabricated with controlled film thickness from ~ 900 nm to ~ 40 µm and 98% capacity retention of 371 mA/g after 20 cycles.
Spray deposition has been demonstrated to have the potential for scalability in the manufacture of carbon-based thin film electrodes with competitive properties.

Keywords: supercapacitor
Advisor: Grant, P
Risk and protective factors for the psychological well-being of children orphaned by AIDS in Cape Town, South Africa

Background: Orphanhood is a major consequence of the HIV/AIDS epidemic in sub-Saharan Africa. There is little evidence concerning psychological problems for AIDS-orphaned children. This thesis explores the relationship between orphanhood status and mental health. It also examines mediating influences of environmental risk and protective factors, and interactions between factors, on children’s psychological problems. Methods: 1200 isiXhosa-speaking children were interviewed, using standardised questionnaires, in deprived urban settlements of Cape Town. A qualitative stage with 60 AIDS-orphaned children, 42 caregivers and 20 professionals explored participant perceptions of risk and protective factors. A quantitative stage compared 1025 AIDS-orphaned children to control groups of other-orphans and non-orphans. Data were analysed with t-tests, chi-sq, anovas, regression and log-linear analyses. The study took place in collaboration with Cape Town Child Welfare. Results: AIDS-orphaned children reported more depression (p<.001), peer relationship problems (p<.001), post-traumatic stress (p<.001), suicidal ideation (p<.05), delinquency (p<.001) and conduct problems (p<.001) than other-orphans and non-orphans. Anxiety showed no differences. Compared to Western norms, AIDS-orphaned children showed higher levels of internalising problems and delinquency, but lower levels of conduct problems. These differences remained when controlling for socio-demographic factors. A number of factors strongly mediated the relationship between AIDS-orphanhood and mental health. These include poverty-related factors (food, education and social security, p<.001). caregiving-related factors (caregiver illness, p<.001, excessive housework p<.001, being a streetchild, p<.001) and AIDS-related stigma (p<.001). Cumulative effects were also found. Food insecurity and AIDS-related stigma interacted to raise likelihood of disorder from 19% to 83%, and orphanhood status and bullying interacted to raise likelihood from 12% to 76%. Conclusions: This thesis shows clear evidence of heightened psychological problems amongst AIDS-orphaned children. It also indicates mediating factors and points to areas of possible intervention. The South African Ministry of Social Development plans to scale up the study to a national survey of AIDS-orphanhood.

Keywords: mental health
South Africa
HIV
orphan
AIDS
Advisor: Gardner, F
Catalyst for coalition

This thesis explores the Anglo-American supply relationship, 1939-1941, and the ability of these two nations to wage a coalition war immediately after the Japanese attack on Pearl Harbor. Organisationally, the first chapters of the thesis look at the impact of the Great War and the interwar period on this relationship. The remaining chapters are devoted to the evolution of the supply relationship between September 1939 and December 1941.
The evidence found in British and American archives indicates that early supply discussions, conducted under the supervision of Arthur Purvis and Henry Morgenthau, established a common ground for Anglo-American co-operation during the early days of the Second World War. The fall of France prompted the British Government to seek much closer ties with the United States. However, in mid-1940 many senior US officials insisted that America should concentrate on its own defence against the Nazi threat because of the likelihood of Britain's defeat. By the end of 1940, the American defence planners were more confident of Britain's ability to survive, and therefore they were willing to consider the creation of Anglo-American defence plans. At the same time President Roosevelt requested Congressional approval for the Lend-Lease Act, to ensure the British Government could still acquire US war supplies even if it lacked the dollars to pay for them.
Because of the inability of US industry to produce adequate war materiel for the British effort and American rearmament, representatives from the two countries were forced to work closely together to determine production and allocation priorities. Moreover, since these decisions influenced the fighting capability of British and American forces, war planners rather than civilians officials began to make these supply decisions. Subsequently, British and American officials determined that their efforts should be based on a joint strategy. Ultimately this realisation inspired the creation of the Victory Programme, which effectively acknowledged that supply needs, strategic considerations, and an overall commitment to defeat Germany and its allies were indistinguishable. Thus the supply relationship, 1939-1941, provided the foundation for the Anglo-American wartime coalition against Hitler.
A space for song: Ovid's metapoetic landscapes

This study seeks to renew interest in the poetically constructed landscapes of Ovid’s Metamorphoses. Far from existing as mere background to the epic, close investigation and analysis reveals the reflective relationship and mutually exerted force between landscape and narrative. Detailed readings show how the landscapes are created in order to reveal Ovid’s poetic programme, especially as concerns the intersection of genre; landscape descriptions are read as interpretive strategies for understanding the crossing of genres that comprise Ovid’s hyper-Alexandrian epic. I argue for this interest as indicated to the reader by three points of departure made by the poet that show up against the background of his interconnected patterning of narrations. These are choices demanding exegesis beyond mere recognition, and are designed to reveal a purposeful agenda that focuses attention upon the descriptions of the natural world. The first chapter explores the construction of Thessalian Tempe in Book 1, made prominent by Ovid’s mythological placement of Daphne as a Thessalian nymph. Tempe represents a landscape consequentially shaped by the narrative of Apollo and Daphne, memorialising topographically the intersection of the ‘high’ and ‘low’ genres of epic and elegy exemplified in their interaction. This narrative influence over the landscape is explored in this programmatic tale, and Tempe’s metapoetic construction is argued for using Callimachus’ Hymn to Delos as a poetic model, focusing on the figure of the Peneus common to both texts. The second chapter focuses on Helicon in Book 5, and examines the finely-drawn relationship between the contest songs and Helicon’s position as the contest prize across the complex layers of narrative space, demonstrating how the inspiratory springs of Helicon provide the narrative motivation for the contest songs and tracing the generic topography of Calliope’s song. The third chapter offers a new interpretation of Orpheus’ grove as an atmospheric doublet of the Underworld, examined through the patterning of meaning imposed by the dual meaning of umbra, and identifies Ovid’s transformation of a literary topos.

Keywords: landscape
Ovid
ancient epic
Advisor: Leigh, M
Multisensory processing in the human brain

Perception has traditionally been studied as a modular function where different sensory systems operate as separate and independent modules. However, multisensory integration is essential for the perception of a coherent and unified representation of the external world that we experience phenomenologically. Mounting evidence suggests that the senses do not operate in isolation but that the brain processes and integrates information across modalities. A standing debate is at what level in the processing hierarchy the sensory streams converge, for example, if multisensory speech information converges first in higher-order polysensory areas such as STS and is then fed back to sensory areas, or if information is already integrated in primary and secondary sensory areas at the early stages of sensory processing. The studies in this thesis aim to investigate this question by focussing on the spatio-temporal aspects of multisensory processing, as well as investigating phonetic and non-phonetic integration in the human brain during auditory-visual speech perception.
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**NOTE: There is a missing section of the abstract at the foot of the scan of p.4. is this a reflection of the original or a technical glitch?**

Advisor: Calvert, G
The Italian involvement in Greece from the third century to 167 BC

The thesis begins with the question of who were those who appealed to Rome in 230 to provide the pretext for the First Illyrian War. This is followed by an analysis of the mechanics of trade and travel to Greece, and the conditions to be encountered there; also of the honorific inscriptions which provide much of the evidence for the presence. This evidence is then assessed for Delphi, the sanctuaries of Asklepios, Aitolia and other less cohesive presences. The conclusions are in terms of Rome's dealings with Greece up to and including the First Illyrian War, as affected by her allies' presence in Greece.
There follows an excursus on the development of early Latin literature, its motivations, themes and relevance in historical context. The period of the Second Punic War is then analysed to see if and how traffic continued to frequent Greece, and how Rome's policy developed from the stance which she had taken in 230.
This leads to a consideration of the causes of the Second Makedonian War, and of the differing policies of Flamininus and Scipio Africanus as revealed by their honours, dedications and letters in Greece. The subsequent Italian presence in Delphi, Thessaly, Aitolia, Thrace, the Aigæian, Boiotia and elsewhere is then assessed in its historical context. There is then a broad overview of the presence on Delos throughout the period, with the emphasis on the Syro-Aitolian War and the freeing of the port in 166.
Bacteriorhodopsin/phospholipid interactions - a study by ³¹P- and ²H-NMR

Two methods were used to produce exogenous lipid/bR complexes. A detergent method (Huang et al., 1980) reconstituted bR into DMPC or DMPG bilayers, free of all endogenous purple membrane lipids as shown by high resolution 31 P-NMR. A novel biological detergent-free method employed bovine liver non-specific lipid transfer protein (nsTP) to mediate addition of DMPC to purple membrane, while retaining 76 - 86% of the endogenous purple membrane phospholipids.
The variations with temperature of 2H-NMR quadrupole splittings for the DMPC choline α- and β-methylene CD2 segments were similar to those for protein-free lipid (Gaily et al., 1975) implying that temperature dependent changes in segmental amplitudes of motion within the choline group are preserved in the presence of bR. Incorporation of small quantities of bR increased the amplitudes of segmental motion within the choline headgroup relative to that of pure lipid, but increasing the bR content induced an ordering effect.
The choline α- and β-methylene segment quadrupole splittings showed a linear variation with protein content at constant temperature. This is consistent with freeze fracture electron microscopy data, which shows the bR particles to be dispersed at all lipid/protein ratios, when quenched from temperatures above the phase transition. Applying a fast two site exchange model to the 2H-NMR data, values between 12 and 15 were calculated for the number of boundary lipids for bR (26,000 Mr) in DMPC bilayers free of purple membrane lipids.
From ESR data, for delipidated bR in DMPC and DMPG bilayers at temperatures above the phase transition, the number of boundary lipids calculated were 18 - 21, which is consistent with the bR being monomeric, as also observed in DMPC bilayers with all the purple membrane lipids retained (Cherry et al., 1978). The purple membrane lipids thus appear to mediate crystallization of the bR particles into a hexagonal lattice at temperatures slightly below the exogenous lipid phase transition.

Advisor: Watts, A
Dempsey, C
Watts, T
Genetic and environmental influences on learning Chinese language and literacy skills

This thesis investigated the etiology of individual differences in Chinese language and literacy skills with a two-wave longitudinal design using a sample of 312 Chinese twin pairs aged 3 to 11 in Hong Kong. Children were individually given tasks of Chinese word reading, receptive vocabulary, phonological memory, tone awareness, syllable and rhyme awareness, rapid automatized naming, morphological awareness, and orthographic skills, as well as nonverbal reasoning and audiometric screening tests. They were tested again on the same tasks, except nonverbal reasoning, one year after the initial testing. Children’s saliva was collected to perform SNP testing for zygosity determination. Also, their demographic information, home literacy environment profile, and motivation for learning text, were obtained from parent-rated questionnaires. Overall, there were four major findings on Chinese language and literacy abilities with the effects of age and nonverbal reasoning controlled for. First, genes and environments had differential influences on various skills, and there was a possibility of different etiology in language and reading development. Second, socioeconomic status and home literacy environment were plausible mediators but not moderators of general language and reading abilities. Third, the stability of various skills across a one-year time period was mainly mediated by genetic influences, but shared environmental factors also influenced syllable and rhyme awareness. Also, new genetic and environmental factors came into play at Time 2 for word reading, and results suggested new genetic influences and new shared environmental influences emerged at Time 2 for tone awareness and morphological awareness respectively. Fourth, both genes and environments contributed to parent-rated communicative ability and motivation for learning text. Furthermore, the link between word reading and parent-rated motivation was mediated by genetic processes. The universality of the genetic and environmental origins across languages and their specificity to Chinese, as well as the implications of these findings, were discussed.

Keywords: language
reading
twin study
children
Chinese
Advisor: Bishop, D
Ho, C
Fullerene based systems for optical spin readout

Optical spin readout (OSR) in fullerene-based systems has the potential to solve the spin readout and scalability challenges in solid-state quantum information processing.
While the rich variety of chemical groups that can be linked (covalently or not) to the fullerenes opens the possibility of making large and controlled arrays of qubits, optical methods can be used to measure EPR down to a single spin thanks to the large energy of optical photons compared to the microwave ones.
After reviewing the state of the art of OSR, for which the diamond NV cen- ters constitute the benchmark, we undertake the study of fullerene-based species for OSR. An optically detected magnetic resonance (ODMR) setup was imple- mented in a commercial EPR spectrometer for this purpose. Each experimental chapter focuses on one of the molecular systems in question: a functionalised C60 fullerene with a phosphonate group (C60-phosphine), porphyrin-fullerene ar- chitectures (weakly, strongly and moderately coupled) and finally erbium-doped trimetallic nitride template (TNT) fullerenes (focusing on ErSc2N@C80).
In the C60-phosphine system, coherent optically detected magnetic resonance (ODMR) in the triplet state has been achieved. Since a large variety of organic and organometallic molecules can be attached to it both via the fullerene cage and the phosponate group, this result makes it a very useful template to study OSR molecules chemically linked to a qubit.
In the porphyrin based structures, an intermediate coupling case in the form of a trimer-fullerene host-guest complex is found to allow detection of both the porphyrin and fullerene triplet sates by CW ODMR, which makes organo-metallic complexes a possible coupling route for a qubit to an OSR component.
In the TNT fullerene, crystal field mixing makes the Er3+ inaccessible by ODMR. However, optical photons cause a mechanical rearrangement of the en- dohedral cluster which in turns impacts on the observed EPR. In particular, the dynamics of this process have been studied for the first time and hint to- wards diffusion kinetics at low pump power. An orientational selectivity has been discovered by using a polarised pump, and the time dynamics indicate the rearrangement of the matrix via difusion on a free volume around the fullerenes. This shows that the endohedral Er3+ in ErSc2N@C80 can probe the environment outside the cage.

Keywords: Fullerene
ESR
EPR
Erbium
organometallic
spectroscopy
diffusion
ODMR
Advisor: Briggs, G
Taylor, R
Ardavan, A
Morton, J
Structural and functional studies on human PHD finger protein 2

Histone lysine methylation is an important post-translational modification (PTM) that can regulate gene expression in eukaryotic genomes. Histone methylation states are dynamically altered by the activity of methyl-transferases and demethylases, including the Jumonji C-domain-containing histone demethylases (JHDMs). The JHDM enzymes are members of the Fe(II) and 2-oxoglutarate (2OG) dependent dioxygenases superfamily, which utilise Fe(II) as a cofactor, and 2OG and oxygen as co-substrates to catalyse oxidative demethylation.
This thesis presents structural and functional studies on an unusual JHDM, PHF2, which has an interesting metal binding site. The proposed substrate for PHF2 is histone H3K4me3K9me2 although no definitive in vitro demethylation activity for PHF2 has yet been demonstrated. Due to the unusual composition of the catalytic site of PHF2, it is questionable whether PHF2 is able to productively bind metal ions and catalyse demethylation reactions, as do other JHDMs. In this thesis, work investigating the cofactor/co-substrate binding ability of PHF2 and its substrate peptide recognition mechanism is described. The studies used a combination of biochemical/biophysical assays and structural methods including X-ray crystallography. The results confirmed that PHF2 is able to bind to a transition metal ion and 2OG/NOG. Further investigations revealed that substrate peptide binding is mostly determined by the PHD finger; and biochemical assays suggested that the JmjC domain is not involved in peptide binding, which offers a possible explanation for the difference between the results of in vitro and cell-based demethylation activity assays.
Inhibitor screening was also carried out for PHF2, and a list of initial hits was generated. Although the results of this work are preliminary, the initial hits will serve as templates for future development of PHF2 specific inhibitors, which could be used for both drug development and as probes to investigate the biological function of PHF2.

Keywords: Kinetics
PHF2
Human
Structures
Advisor: Schofield, C
Solution reactivity studies of group 14 zintyl clusters towards organometallic reagents

The group 14 Zintl clusters [E₉]⁴⁻ (E = Ge, Sn, Pb) have been reacted with organometallic reagents in solution in the presence of alkali metal cation sequestering agents. The synthesis, characterisation and reactivity studies of the resultant complexes are reported herein.
These negatively charged clusters reductively cleave one of the M–C bonds in the group 12 homoleptic organometallic reagents MR₂ (M = Zn, Cd; R = Ph, mes, ⁱPr) to yield η⁴-coordinated functionalised clusters closo-[E₉MR]³⁻. They can also activate both of the M–C bonds in Cd(mes)₂ to form metal-bridged dimers [Ge₉CdGe₉]⁶⁻ and [Pb₉CdCdPb₉]⁶⁻. Investigating the reactivity of the functionalised cluster [E₉CdPh]³⁻ (E = Sn, Pb) towards HSn(ⁿBu)₃ results in the synthesis of the novel closo-clusters [E₉CdSn(ⁿBu)₃]³⁻.
The reaction of K₄Ge₉ with the heteroleptic organometallic reagent Fe(COT)(CO)₃ yields the metalated cluster anion [Ge₈Fe(CO)₃]³⁻, in which the nuclearity of the Zintl anion is altered upon coordination of the [Fe(CO)₃] moiety. Two side products have also been isolated as [K(2,2,2-crypt)]⁺ salts of [Fe(η³-C₈H₈)(CO)₃]⁻ and [Fe₂(η³, η′³-C16
)(CO)₆]²⁻.
In the presence of highly reduced Zintl anions, all the M–C bonds in homoleptic mid-row transition metal organometallic reagents can also be cleaved. These ‘naked’ metal atoms have templated the formation of the endohedral clusters [Fe@Ge10]³⁻, [Fe@Sn10]³⁻ and [Mn@Pb12]��⁻. These clusters adopt very different geometries and the electronic origin of their structures has been investigated in-depth by DFT calculations. Structural characterisation of some side products is also reported for: [E₉(mes)]³⁻ (E = Ge, Sn) and [Ge₉Mn(mes)]³⁻.

Keywords: metal clusters
organometallic reagents
Zintl anions
Advisor: Goicoechea, J