Studies of Laurencia Natural Products and Some Synthetic Bicyclic Molecules by X-Ray Analysis

This thesis is divided into three sections. In Section I some theoretical aspects of the diffraction of X-rays by crystals and some techniques of X-ray structure analysis are introduced and discussed briefly. The structure analyses of two natural products are described in Section II and of three synthetic organic molecules containing bicyclic ring systems are described in Section III. The natural products described in Section II, laurencin and laurinterol, were both isolated from the Laurencia species of seaweed and were unusual as bromine-containing natural products. Unambiguous determination of their constitutions by chemical and spectroscopic techniques had proved impossible and no details of their stereochemistries were available. In each case the X-ray investigation has established the structure and both absolute stereochemistries were determined by consideration of anomalous dispersion effects. In the case of laurinterol, as a result of the determination of the absolute stereochemistry, the absolute stereochemistries of the chemically related compounds aplysin and aplysinol have been determined, and it has been proved that laurinterol, aplysin and aplysinol have the same absolute stereochemistry at their common centres as the natural products laurene and cuparene. This has allowed speculation on the possibility of a biological precursor common to all five compounds. The investigations of two bicyclo[2,2,2]octane derivatives and a bicyclo[3,2,2]nonene derivative have been described in Section III. There has been considerable controversy in the literature as to the conformation of the bicyclo[2,2,2]octane molecule, the possibilities being the eclipsed conformation as opposed to the staggered or twisted D3 conformation. The investigation of one of the bicyclo[2,2,2]octane derivatives was undertaken specifically to study this problem, and the results prove unambiguously that in the solid state the twisted or staggered D3 conformation is favoured with 5 dihedral angles between substituents on the bridges. The second bicyclo[2,2,2]-octane derivative was an adduct of unknown structure. The analysis has revealed the structure and the results show that despite the presence of many substituents and sp2 hybridised centres, the second bicyclo[2,2,2]octane skeleton reflects the same conformational trends as the first. The bicyclo[3,2,2]-nonene system was investigated because it was of conformational interest. In this case it has been shown that no twisting of the bicyclic ring system takes place, but that strain is relieved by ring-flattening with accompanying valency-angle distortions. The three conformations have been discussed in one chapter with an accompanying discussion of those strain effects which are generally considered to be conformation-determining

Differently unequal: Zooming-in on the distributional dimensions of the crisis in euro area countries

This paper discusses how income inequality developed during the current crisis in euro area countries, as well as the role played by each income source. Based on an extended definition of income - including additional components which do not appear in the standard Eurostat definitions - we complement the information provided by the Gini index and quantile ratios by computing an alternative inequality indicator, developed by Zenga (2007), and its decomposition by income source. While broadly confirming the distributional effect of the crisis documented in previous studies, we find that in specific countries the level of inequality appears higher when alternative measures are taken into account, and that the rise of inequality since 2008 has not been as modest as the previous studies would suggest. The paper further looks at how the distribution of income has evolved during the crisis by income quantile groups (i.e. 'zooming-in'). The results point to varying contribution of labour income in 2011 compared to 2007. In addition, while the impact of individual households' characteristics shows a non-linear pattern across income quantile groups before the crisis, such dispersion has decreased in 2011.We argue that, on the basis of our analysis, not only euro area countries are "differently unequal" in that inequality has developed in a very peculiar way in different countries, but also because it needs to be tackled at a finer level of analysis

Native Birdlife in Hawke’s Bay: application of the river values assessment system (RiVAS and RiVAS+)

This report presents an application of the River Values Assessment System for existing value (RiVAS) and for potential value (RiVAS+) to native birdlife in the Hawkes Bay Region. A workshop was held in Napier on 3rd October 2011 to apply the method. This Hawkes Bay Region bird report needs to be read in conjunction with the method and with the first native bird application reports (see Hughey et al. 2010 and Gaze et al. 2010).Ministry of Science and Information, and Hawkes Bay Regional Counci

Effect of end group functionalisation of small molecules featuring the fluorene-thiophene-benzothiadiazole motif as emitters in solution-processed red and orange organic light-emitting diodes

A series of red fluorescent materials (compounds 1-4), which each contain the symmetric fluorene-thiophene-BT-thiophene-fluorene core, is presented along with their performance in solution-processed OLED devices. Extending the molecular conjugation through end-capping with additional fluorene units (compound 2), or through incorporation of donor functionalities (compounds 3 and 4) improves OLED performance relative to the parent compound 1. Notably, incorporating triphenylamine donor groups in compound 3 led to solution-processed OLED devices operating with a peak luminance of 2888 cd m −2 and a low turn-on voltage (3.6 V)

Public perceptions of cancer: a qualitative study of the balance of positive and negative beliefs

Objectives: Cancer's insidious onset and potentially devastating outcomes have made it one of the most feared diseases of the 20th century. However, advances in early diagnosis and treatment mean that death rates are declining, and there are more than 30 million cancer survivors worldwide. This might be expected to result in more sanguine attitudes to the disease. The present study used a qualitative methodology to provide an in-depth exploration of attitudes to cancer and describes the balance of negative and positive perspectives. Design: A qualitative study using semistructured interviews with thematic analysis. Setting: A university in London, UK. Participants: 30 participants (23–73 years), never themselves diagnosed with cancer. Results: Accounts of cancer consistently incorporated negative and positive views. In almost all respondents, the first response identified fear, trauma or death. However, this was followed—sometimes within the same sentence—by acknowledgement that improvements in treatment mean that many patients can survive cancer and may even resume a normal life. Some respondents spontaneously reflected on the contradictions, describing their first response as a ‘gut feeling’ and the second as a more rational appraisal—albeit one they struggled to believe. Others switched perspective without apparent awareness. Conclusions: People appear to be ‘in two minds’ about cancer. A rapid, intuitive sense of dread and imminent death coexists with a deliberative, rational recognition that cancer can be a manageable, or even curable, disease. Recognising cancer's public image could help in the design of effective cancer control messages

The 1930s as black mirror: Visions of historical repetition in the global financial press, 2007-2009

Media coverage of the recent financial crisis has referred extensively to various past crises, and in particular to the events of the 1930s. This article suggests that the idea of the Great Depression has effectively come to function as a kind of historical ‘black mirror’ – a quasi-object within which conjuncture and historical representation interact to produce an image of capitalist history itself. Focusing on the journalistic output of four key financial publications, I trace how portrayals of the 1930s have evolved over the course of the crisis. I find that while the 1930s are frequently and consistently invoked in ways that purport to reveal the historicity of the crisis, these representations produce an oscillation between different visions of historical repetition, which in turn underpin competing interpretations of the crisis as it unfolds. In so doing, I argue, appeals to the 1930s have simultaneously served to conceal and disclose the constitutive relation of historical imagination to historical process – a double move that has had the paradoxical effect of both securing and undermining the reproduction of finance capitalism as we have come to know it

Comprehensive study of antiretroviral drug permeability at the cervicovaginal mucosa via an in vitro model

Funding: This work was supported by the European Union’s Seventh Programme for research, technological development and demonstration under grant agreement No 305316 as part of the MOTIF (Microbicides Formulation Through Innovative Formulation for Vaginal and Rectal Delivery) project. Acknowledgments: We thank all members of the MOTIF consortium for helpful discussions and exchange of ideas during the course of this study.Peer reviewedPublisher PD

Junior Recital, Aaron Bottoms, trumpet

The presentation of this junior recital will fulfill in part the requirements for the Bachelor of Music degree in Performance. Aaron Bottoms studies trumpet with Kevin Maloney

Fast Reconnection in a Two-Stage Process

Magnetic reconnection plays an essential role in the generation and evolution of astrophysical magnetic fields. The best tested and most robust reconnection theory is that of Parker and Sweet. According to this theory, the reconnection rate scales with magnetic diffusivity lambda as lambda^0.5. In the interstellar medium, the Parker-Sweet reconnection rate is far too slow to be of interest. Thus, a mechanism for fast reconnection seems to be required. We have studied the magnetic merging of two oppositely directed flux systems in weakly ionized, but highly conducting, compressible gas. In such systems, ambipolar diffusion steepens the magnetic profile, leading to a thin current sheet. If the ion pressure is small enough, and the recombination of ions is fast enough, the resulting rate of magnetic merging is fast, and independent of lambda. Slow recombination or sufficiently large ion pressure leads to slower merging which scales with lambda as lambda^0.5. We derive a criterion for distinguishing these two regimes, and discuss applications to the weakly ionized ISM and to protoplanetary accretion disks.Comment: 21 pages, 13 figures, submitted to Ap

SHORT syndrome due to a novel de novo mutation in PRKCE (Protein Kinase Cɛ) impairing TORC2-dependent AKT activation.

SHORT syndrome is a rare, recognizable syndrome resulting from heterozygous mutations in PIK3R1 encoding a regulatory subunit of phosphoinositide-3-kinase (PI3K). The condition is characterized by short stature, intrauterine growth restriction, lipoatrophy and a facial gestalt involving a triangular face, deep set eyes, low hanging columella and small chin. PIK3R1 mutations in SHORT syndrome result in reduced signaling through the PI3K-AKT-mTOR pathway. We performed whole exome sequencing for an individual with clinical features of SHORT syndrome but negative for PIK3R1 mutation and her parents. A rare de novo variant in PRKCE was identified. The gene encodes PKCε and, as such, the AKT-mTOR pathway function was assessed using phospho-specific antibodies with patient lymphoblasts and following ectopic expression of the mutant in HEK293 cells. Kinase analysis showed that the variant resulted in a partial loss-of-function. Whilst interaction with PDK1 and the mTORC2 complex component SIN1 was preserved in the mutant PKCε, it bound to SIN1 with a higher affinity than wild-type PKCε and the dynamics of mTORC2-dependent priming of mutant PKCε was altered. Further, mutant PKCε caused impaired mTORC2-dependent pAKT-S473 following rapamycin treatment. Reduced pFOXO1-S256 and pS6-S240/244 levels were also observed in the patient LCLs. To date, mutations in PIK3R1 causing impaired PI3K-dependent AKT activation are the only known cause of SHORT syndrome. We identify a SHORT syndrome child with a novel partial loss-of-function defect in PKCε. This variant causes impaired AKT activation via compromised mTORC2 complex function