VictorJuiz/thesis huggingface dataset:
Stereoselective reactions of arene chromium tricarbonyl complexes

This thesis describes the application of (arene)Cr(CO)3 methodology to the Stereoselective and enantioselective synthesis of substituted arenes. Chapter one reviews the main methods of preparation and decomplexation of (arene)Cr(CO)3 complexes and the electronic and steric influences of the Cr(CO)3 unit on the arene.
Chapter two demonstrates that the benzylic oxygen directing effect in complexation reactions operates via a direct oxygen bond to the incoming metal unit. Attachment of bulky ft-acceptor groups, such as t-butyldimethylsilyl, to the benzylic oxygen overrides this directing effect.
Chapter three describes the regioselective Cl functionalisation of the cryptopine skeleton. Complexation of dihydrocrytopine gives only a single product, the relative configuration of the product being determined using an X-ray crystal structure analysis. Subsequent alkylation of the O-methyl derivative gives Cl alkylated products.
Chapter four describes the regioselective ortho functionalisation of ephedrine and pseudoephedrine derivatives. Treatment of (1S,2R)-(N,O-dimethylpseudoephedrine) Cr(CO)3 with n-butyllithium leads to exclusive removal of the pro-(R) ortho proton. The observed stereoselectivity arises via
Chapter five describes the regioselective C4 and C5 functionalisation of (hydrocotarnine)Cr(CO)3. Complexation of 1-methylhydrocotarnine occurs to give exclusively the exo-1-methyl derivative. Further functionalisation to give the 1,5- and 4,5-dimethyl products is also described.
Chapter six describes the synthesis of ortho substituted (benzaldehyde)Cr(CO)3 complexes. Chiral material is available via preferential kinetic hydrolysis of, or classical separation of, the L-valinol derived imines.
Chapter seven describes the Stereoselective addition of nucleophiles to (o-anisaldehyde) Cr(CO)3 and (o-trialkylsilylbenzaldehyde)Cr(CO)3. With (o-anisaldehyde)- Cr(CO)3 the additions are completely stereoselective giving the (RR,SS) diastereoisomer. With (o-trialkylsilylbenzaldehyde)Cr(CO)3 the ratio of products is influenced by the nature of Lewis acidic species present.
Chapter eight describes the Stereoselective benzylic elaboration of (o-methoxybenzyl methyl ether)Cr(CO)3 achieved via selective removal of the exo benzylic proton from transition states with the methoxy groups anti to each other.

Advisor: Davies, S
The co-occurrence of terracotta wheelmade figures and handmade figurines in mainland Greece, Euboea, the Dodecanese, the Cyclades and the Northern Aegean islands, 1200-700 BC

This thesis addresses the lacuna in the study of Greek terracotta figures and figurines corresponding to the transitional period between the Late Bronze and Early Iron Ages (1200-700BC). It provides a comprehensive synthesis of all available data, with particular reference to material from recently excavated sites in mainland Greece and its islands (Euboea, the Northern Aegean islands, the Dodecanese and the Cyclades).
The study is framed according to the relationship between terracotta figures (those made on the potter's wheel) and figurines (those made by hand). The observation that the technological distinction between these two types is reflected in their different and separate functions has been sustained in scholarship for the past three decades, but only for the Mycenaean period. Handmade figurines and wheelmade figures occurred in different and restricted contexts in the Mycenaean world: the former in settlements, cemeteries and religious locations, and the latter exclusively in religious contexts. It is therefore inferred that they had different socially embedded values or 'meanings'. However, the extent to which such a distinction applies to figures and figurines in the Early Iron Age has hitherto not been explored. Initial evidence indicates that by the 8th century, handmade figurines and wheelmade figures were deposited together at selected sites, suggesting that their inherent socially embedded meanings were the same, and that they represented "different levels of [financial] investment in what is essentially the same category of votive".
This thesis therefore determines the levels of co-occurrence of wheelmade figures and figurines, thus identifying how distribution relates to usage. Changes are observed over time and space and between different types of functional contexts, and the meanings of these patterns are investigated. The results of this study provide a chronological and geographical overview of the distribution of figures and figurines, and also indicate that figures and figurines had consistently multivariate relevance in multiple types of contexts. The functional dichotomy of figures and figurines observed for the Mycenaean period cannot be sustained beyond 1200 BC. Moreover, study of the contexts from which the material originates indicates that the significance of secondary deposits of religious nature has been consistently overlooked, and that figures and figurines were used in an active and meaningful sense even during the act of their discard. This type of activity is a distinctive one that can be characterised and defined functionally, geographically, temporally and quantitatively. The socially embedded meaning of figures and figurines was fluid and related to an action being performed; their meaning was not linked exclusively to an aspect of the object itself, and was therefore not static.

Keywords: votives
terracotta
figurines
Greek archaeology
Early Iron Age
religion
Late Bronze Age
Advisor: Lemos, I
Spaces of complex geodesics and related structures

On a complex n-manifold with holomorphic projective connexion, any point has a neighbourhood U of which the space of geodesies has naturally the structure of a (Hausdorff) complex (2n-2)-manifold; it is shown that the complex structure of this auxiliary space encodes, in a sense, the original projective connexion by means of a complete analytic family of and#x2119;n-1's. Rather strikingly, small deformations of the space of geodesies correspond precisely to small deformations of the projective connexion of the primary space.
Similar results are obtained concerning the space of null geodesies of a complex n-fold, n ≥ 4, with conformal connexion, a geometrical structure amounting to a holomorphic conformal structure plus a torsion tensor. For n=3 the analysis is complicated by the fact that the analytic family of submanifolds (quadrics; in this case and#x2119;1's) representing the points of the primary space fails to be complete; but it can be completed to give a 4- dimensional family, effecting a unique embedding of the original 3-fold in a 4-fold with conformal structure, of which the conformal curvature is selfdual, in such a way that the induced conformal structure is the original one and such that the conformal torsion is related to the second conformal fundamental form of the hypersurface in a canonical linear fashion. In any case, the small deformations of the complex structure of the space of null geodesies correspond precisely to the small deformations of the conformal connexion. It is shown that a space of torsion-free null geodesies admits a holomorphic contact structure, and that conversely, for n ≥ 4, the admission of a contact structure forces the conformal torsion to vanish; for n=3, the contact form constructs automatically a unique metric on the ambient 4-fold in the previously constructed self-dual conformal class which solves Einstein's equations with cosmological constant 1 and blov/s up on the 3-fold, which is a general umbilic hypersurface. These results are in turn used to show that a real-analytic 3-fold with real-analytic positive definite conformal structure and a real-analytic symmetric form of conformal weight 1 can be embedded (in a locally unique fashion) in a real-analytic 4-fold with positive-definite conformal structure for which the conformal curvature is self-dual in such a way as to realize the given structures as the first and second conformal fundamental forms of the hypersurface; and it is shown that a real analytic 3-fold with positivedefinite conformal bounds a locally unique positive-definite solution of Einstein's equations with cosmological constant -1 as its umbilic conformal infinity. By contrast, these results fail when "real-analytic" is replaced by "smooth".

Advisor: Penrose, R
MicroRNA regulation of axial patterning during Arabidopsis embryogenesis

Pattern formation is the process by which undifferentiated cells divide and differentiate to generate complex tissues and organs. In plants, pattern formation begins in embryogenesis and continues post-embryonically with the function of the meristems. microRNAs (miRNAs), which are small regulatory RNAs that repress gene expression, are involved in a variety of patterning processes in plants, including the formation and function of the meristems and establishment of polarity. For example, regulation of the class III HOMEODOMAIN-LEUCINE ZIPPER (HD-ZIP III) transcription factors by miR165/6 is not only involved in the formation and function of the meristems, but also in polarity establishment in the leaf, and in axial patterning during embryogenesis. To gain a better understanding of the role of miRNAs in embryonic patterning, I investigated the tissue-specific functions of the miRNA biogenesis protein SERRATE (SE), which is required for the regulation of the HD-ZIP IIIs via miR165/6. By expressing SE in various domains in se-5 null mutant embryos, I revealed that although SE is expressed throughout the embryonic body, tissue-specific expression of SE from either the upper or lower tier of the embryo is sufficient for correct patterning. This observation suggests a SE-dependent non-cell autonomous and bi-directional mechanism that influences patterning in Arabidopsis embryos. Furthermore, through a suppressor screen of a se-3 loss-of-function mutant allele, I identified mutants in genes that likely function upstream of SE, and downstream or in parallel of the HD-ZIP IIIs. One of those se-3 suppressors is likely to be a mutant in the BELL homeobox gene POUND-FOOLISH (PNF).

Keywords: Embryogenesis
Axial Patterning
Arabidopsis
Plant Genetics
miRNA
Genetic Screen
Plant Development
Advisor: Tsiantis, M
The petrology of the Buckland volcanic province, Central Queensland, Australia

Cainozoic volcanism occurs in eastern Australia as a broad zone of discontinuous, small-volume, dominantly basaltic provinces. Central volcano provinces show a strong correlation between age and latitude, younging towards the south, hence the interpretation that they are related to a mantle hotspot. Previous work has interpreted the composition of lavas from these provinces using a fourcomponent model involving material from a mantle plume, the shallow asthenosphere, continental lithosphere together with AFC processes in the lower crust.
The purpose of this thesis is to describe the petrology of the Buckland province, a relatively poorly-studied central volcano in central Queensland, and to constrain models for the petrogenesis of its lavas, assessing whether this is consistent with the four-component model outlined above. Mafic lava compositions show a wide range of silica saturation and degree of evolution. Highly undersaturated basanites are interpreted as being dominantly from the shallow asthenosphere, with the five most magnesian samples apparently containing a HIMU-like component. Comparison with experimental data demonstrates that the geochemistry of the most primitive basalts is consistent with decompressional melting within a plume whose TP lies in the range 1410-1500°C and which has an above-average Fe/Mg. Evolved mafic lavas show geochemical and petrographic evidence for polybaric assimilationfractional crystallisation in the crust. Megacrysts of plagioclase, orthopyroxene and clinopyroxene represent the extract assemblage from the lower crust (probably at pressures >10kbar, owing to the absence of olivine), while low-pressure crystallisation of olivine also took place. Both the elevation of the province (up to 1100m above sea level) and occurrence of high-pressure megacrysts are consistent with previous models of underplating at the crust-mantle boundary. Lavas from the neighbouring province of Springsure show greater evidence of AFC in the upper crust, while those from the northern part of the Mitchell province contain megacrysts of olivine which is suggestive of a slightly lower crystallisation pressure in the lower crust.
2D ultrasound elastography as a functional measure of healing of the Achilles tendon in vivo

The Achilles tendon is the largest tendon in the human body, which elastically stores and releases energy to facilitate walking and running. Tendons can suffer from a range of pathologies, most notably that of complete rupture, which affects athletes, physically active workers and the aged. There is a growing demand for in vivo methods of objectively measuring tendon health for aiding diagnosis, monitoring therapy and for assessment of new treatments. Knowledge of the changes in mechanical properties during the healing process is also limited and new methods to accurately and consistently estimate these could provide insights into the healing process and guide future research efforts.
This thesis presents the development and use of 2D ultrasound elastography, a quantitative strain estimation imaging technique, as a tool to measure changes in the tensile mechanical properties of the Achilles tendon. This technique performs frame-to-frame block matching of image texture to track motion in an ultrasound signal sequence and create a strain estimation field from the spatial derivative of the motion. Elastography in the image-lateral direction of sagittal plane scans is of particular interest as this is in line with the longitudinal axis of the tendon, but presents extra accuracy issues from out of plane motion and lower image spatial resolution. Tendon rupture also presents unique problems to image acquisition and analysis- patient pain and safety are important considerations and disruption of the ultrasound texture can make 2D motion tracking more difficult.
A new 2D elastography block matching algorithm, named `AutoQual', was developed to enable accurate tracking of motion in the image-lateral direction and reduce the impact of artefacts and errors common with damaged Achilles tendons image sequences. It was shown to outperform a multiscale block matching method when tested using ultrasound sequences from

Keywords: elastography
Achilles
ultrasound
strain
healing
rupture
tendon
Advisor: Noble, J
Thompson, M
Screening for inhibitors of and novel proteins within the homologous recombination DNA repair pathway

The homologous recombination (HR) pathway of DNA repair is essential for the faithful repair of double-stranded DNA breaks (DSBs) in all organisms and as such helps maintain genomic stability. Furthermore, HR is instrumental in the cellular response to exogenous DNA damaging agents such as those used in the clinic for chemo- and radiotherapy. HR in humans is a complex, incompletely understood process involving numerous stages and diverse biochemical activities. Advancing our knowledge of the HR pathway in humans aids the understanding of how chemo- and radiotherapies act and may be used to develop novel therapeutic strategies. Recent studies have identified inhibition of HR as one of the mechanisms via which a number of recently developed chemotherapeutics have their effect. Accordingly, the clinical potential of HR inhibitors is under investigation. My work has centred around the identification of both novel HR proteins and novel, small molecule HR inhibitors. To further these aims, I have successfully employed high-throughput RNAi and small molecule screening strategies. RNAi screens are commonly used to identify genes involved in a given cellular process via genetic loss of function, whilst small molecule, cell based screens are a powerful tool in the drug discovery process.

Keywords: small-molecule
High-throughput screening
DNA damage
RNAi
Advisor: Helleday, T
Solid state NMR studies of transition metal compounds

This thesis is concerned with a systematic study of phosphine-containing transition metal complexes and cluster compounds by high resolution solid state nmr spectroscopy, using the techniques of magic angle spinning and cross polarisation.
Previous work has indicated the potential of the solid state nmr technique to investigate a variety of materials: this is considered in the introduction to this thesis, and the reasons for choosing to study transition metal phosphine compounds are discussed.
The analysis of spinning sidebands to obtain the principle values of the shielding tensor is examined to determine how well the calculated values represent the true values. Simulations of slow MAS spectra are proposed as a means of testing and refining the calculated tensor components before attempting to correlate the shielding with structural parameters.
The results of a study of a series of crystalline phosphine-containing complexes and clusters are presented. The spectra are interpreted on the basis of the known crystal structures: in some cases separate resonances can be resolved in the solid state spectra from the distinct phosphine environments of a cluster framework, and from inequivalent sites in the unit cell. Information is obtained from the isotropic shifts, scalar couplings and the chemical shift anisotropy. Many of the compounds are fluxional in solution, some even at low temperature: whereas a number of these are found to be rigid in the solid state at room temperature, some of the crystalline compounds retain their fluxionality.
Investigations of the species formed when transition metal carbonyl clusters are anchored to oxide supports were carried out. These show the presence of several distinct phosphorus-containing species, some of which are not consistent with the simple attachment of the cluster to the surface. The unique importance of the solid state technique is demonstrated in the study of these supported species.

Advisor: Dobson, C
Cancer metabolic pathways regulated by hypoxia

Metabolic reprogramming in cancer cells provides energy and important metabolites required to sustain tumour proliferation. Hypoxia represents a hostile environment that can encourage these transformations and other adaptive responses that contribute to poor prognosis and resistance to radiation and chemotherapy. Hypoxic signatures associated with worse prognosis were previously derived in different cancer types, and led to the selection of two candidates with potential metabolic implications, namely the mir210-putuative target iron-sulfur scaffold protein ISCU and glycogen phosphorylase (PYGL). Firstly, it was verified that the hypoxia-induced miR-210 targets ISCU. Iron-sulfur clusters represent cofactors for key enzymes involved in Krebs cycle and electron transport chain. Downregulation of ISCU was associated with the induction of reactive oxygen species (ROS) and reduced mitochondrial complex I and aconitase activity, caused a shift to glycolysis in normoxia and enhanced cell survival. This indicates that the induction of a single microRNA, miR-210, can mediate a new mechanism of adaptation to hypoxia, by regulating mitochondrial function via iron-sulfur cluster metabolism and free radical generation. Secondly, it was found that changes in PYGL expression reflect a characteristic upregulation of glycogen metabolism in hypoxia in both tumour xenografts and in cancer cell lines. More specifically, hypoxia stimulates glycogen accumulation and its utilisation, as well as the concurrent upregulation of several glycogen-metabolizing enzymes such as glycogen synthase (GYS1) and PYGL. PYGL depletion led to glycogen accumulation in hypoxic cells, increased intracellular levels of ROS, and a reduction in proliferation due to a p53-dependent induction of senescence. Furthermore, depletion of PYGL was associated with markedly impaired tumorigenesis in vivo. Finally, metabolic analyses indicated that glycogen degradation by PYGL is important for the optimal functioning of the pentose phosphate pathway. Collectively, this study shows the contribution of two important pathways to the metabolic adaptations induced by hypoxia.

Keywords: glycogen
microRNA
hypoxia
Cancer metabolism
Advisor: Harris, A
Single channel Kondo physics in triple quantum dots

In this thesis we investigate a system of three tunnel-coupled quantum dots, arranged in a triangular geometry and attached to a single metallic conduction band, using both analytic and semi-analytic methods and the numerical renormalisation group technique. This is the simplest coupled quantum dot system to exhibit frustration. We study three different models of the triple quantum dot device: a mirror symmetric arrangement of dots in which only one dot is connected to the conduction band, a triple quantum dot system in which only one dot is connected to the conduction band without a plane of mirror symmetry and a mirror symmetric arrangement of quantum dots in which all three dots are coupled to the conduction band. We study these models over a wide range of parameter space, and in both the presence and absence of a magnetic field.
Both antiferromagnetic and ferromagnetic Kondo effects are observed, and in all three models we find that the system contains at least two phases, and so a number of quantum phase transitions may be observed, associated in some cases with significant changes in the low temperature conductance through the triple quantum dot device. In addition to zero-field Kondo physics, a number of field induced Kondo effects are also observed. Both first order quantum phase transitions and Kosterlitz-Thouless phase transitions are observed. We use both symmetry arguments and low energy effective models which we derive to explain and understand both the position of and type of phase boundary that is observed in each case, and perturbative methods are used to accurately predict Kondo temperatures for a wide range of systems.

Keywords: quantum dots
triple quantum dots
condensed matter theory
Advisor: Logan, DE