Politically motivated former prisoner groups: community activism and conflict transformation

Aims and objectives: This study represents the first sustained quantitative and qualitative attempt to involve both Republicans and Loyalists in an investigation of the impact of imprisonment and the role of politically motivated former prisoners in the process of conflict transformation in Northern Ireland. The overall aim of the project is to examine the ways in which groups of former prisoners are involved in peace-building and conflict transformation work and to evaluate the constraints and impediments placed upon their activities by the effects of the imprisonment process, politically motivated release and residual criminalisation. In pursuing the evaluation of the role of politically motivated former prisoners working within and without their own communities, the research has six specific objectives: To trace the evolution and development of former prisoner groups; To evaluate the impacts of imprisonment and release on the personal lives of former prisoners; To assess the constraints imposed on former prisoners as agents of change by the residual criminalisation arising from their status; To determine the potential of the former prisoner community in challenging intra-community tensions and evaluate their potential and actual contribution to conflict transformation at the inter-community level; To compare and contrast the effectiveness of Loyalist and Republican former prisoners as agents of change within their own communities; To explore the notion of former prisoners as agents of social and communal transformation within broader political processes through grounding the knowledge and practical experience of the former prisoner community within the broader conceptual context of conflict transformation.

Chemistry of B1- and B10- boranes containing halogen or pseudohalogen groups

The research described in this thesis involved the chemistry of borane-species which contain one or more halide or pseudohalide groups. Both monoboron species e.g. [BH3X]- and "cluster" borane species e.g. [B10H9X]2- and I-Se B11H10 were studied. The first chapter is a review of the syntheses, properties and reactions of halide and pseudohalide species containing from one to ten boron atoms. Chapter Two is a theoretical investigation of' the electronic and molecular structures of two series of boranes i. e. [BH3X]- and [B10H9X]2- where X = H, CI, CN, NCS, SCN and N3. The calculational method used was the Modified Neglect of Differential Overlap (MNDO) method of Dewar et al. The results were compared where possible with experimental results such as the X-ray crystallographically determined structures of [BH3CI]- and [B10H10]2-. Chapter Three concerns halogenated selenaborane clusters and reports an improved synthesis of 12-Br-SeB11H10 and the first structural data for a simple non-metal containing selenaborane cage with the X-ray crystallographically determined structure of 12-1-SeB11H10. Finally, an indepth n.m.r. study of Se2B9H9 is also reported together with attempts to halogenate this compound. The last two chapters are based on single boron systems. Chapter Four concerns the synthetic routes to amine-boranes and -cyanoboranes from [BH4]- and [BH3CN]- substrates. This chapter discusses some difficulties encountered when polyamines were used in these reactions. The characterisation of an unusual ketone isolated from some of these reactions, the X-ray crystallographically determined structure of 4-dimethylamino-pyridine-cyanoborane and a new route to pyrazabole dimeric species are also discussed. The final chapter reports on work carried out at producing BH2X (X = H, CN) adducts of aminophosphines. Three routes were attempted to generate P-B and N-B bonded species with varying degrees of success. Some unusual products of these reactions are discussed including [Ph2(O) PPPh2 ] [Ph2NH]2, the structure of which was determined by X-ray crystallography.

Studies on Formica lugubris Zetterstedt in Ireland (Hymenoptera, Formicidae)

This thesis is based on studies of Formica lugubris from 1972-1975. While this species' range is diminishing in Ireland, the nests are quite common in the State plantations of South Tipperary. It is not certain that the species is indigenous. Above-ground activity occurs from late-February to the end of October; foraging begins in April. Two territorial "spring-battles" between neighbouring nests are described. Most active nests produced alatae of both sexes and flights were observed on successive June mornings above l7.5°C air temperature. Both polygyny and polycaly seem to be rare. Where the nests occur commonly, the recorded densities are similar to those reported from the continent. Most nests persisted at the same site since 1973. The nest-sites are described by recording an array of nest, soil, tree, vegetation and location variables at each site. Pinus sylvestris is the most important overhead tree. Nests seem to be the same age as their surrounding plantation and reach a maximum of c. 30 years. Nearest-neighbour analysis suggests the sites are overdispersed. Forager route-fidelity was studied and long-term absence from the route, anaesthetization and "removal" of an aphid tree had little effect on this fidelity. There were no identifiable groups of workers specifically honeydew or prey-carriers. Size-duty relationships of workers participating in adult transport are described. Foraging rhythms were studied on representative days: the numbers foraging were linearly related to temperature. Route-traffic passed randomly and an average foraging trip lasted c. four hours. Annual food intake to a nest with 25 000 foragers was estimated at approximately 75 kg honeydew and 2 million prey-items. Forager-numbers and colony-size were estimated using the capture-mark - recapture method: paint marking was used for the forager estimate and an interval radiophosphorus mark, detected by autoradiography, was used for the colony-size estimate. The aphids attended by lugubris and the nest myrmecophiles are recorded.

The synthesis and biological evaluation of lanostane and cholestane-type natural products

The main objective of this thesis is to outline the synthetic chemistry involved in the preparation of a range of novel lanostane and cholestane derivatives, and subsequent investigation into their biological activity in cancer cells. The biological results obtained throughout the project have driven the strategic synthesis of new compounds, in an effort to optimise the anti cancer potential of lanostane and cholestane derivatives. The first chapter begins with an overview of steroidal compounds and details a literature review of the natural sources of these moieties, as well as their biosynthesis and reported synthetic derivatives. The biological activity of interesting natural and synthetic analogues is also discussed. In addition, an insight into some currently prescribed pharmaceutical compounds, with functional groups relevant to this project, is presented. The second chapter discusses the methods employed for the synthesis of these novel lanostane and cholestane derivatives, and comprises three main sections. Firstly, various oxidation products of lanosterol are synthesised, mainly via epoxidations of the C-8,9 and C- 24,25 alkenes, and also allylic oxidations at these positions. Secondly, amine derivatives of lanosterol are formed by cleaving the lanostane side chain, thereby yielding a new cholestane nucleus, and performing several reductive aminations on the resulting key aldehyde intermediates. Various amines such as piperidine, morpholine, diethylamine and aniline are employed in the reductive amination reactions to yield novel cholestane steroids with amine side chains. Finally, starting from stigmasterol and proceeding with the same methodology of cleaving the steroidal side chain and subsequently performing reductive aminations, novel cholestane derivatives of the biologically active amines are synthesised. The cytotoxicity of these compounds against CaCo-2 and U937 cell lines is presented in terms of percentage viability of cells, IC50 value and apoptosis. The MTT assay is used to determine the percentage viability of cells, and the IC50 data is generated from the MTT results. Apoptosis is measured in terms of fold increase relative to a carrier control. In summary, the compounds formed are discussed in terms of chemical synthesis, spectroscopic interpretation and biological activity. The main reaction pathways involved in the chemistry within this project are various oxidations and reductive amination. The final chapter is a detailed account of the full experimental procedures for the compounds synthesised during this work, including characterisation using spectroscopic and analytical data.

Characterisation of bacteriophage-host interactions in Lactococcus lactis

Lactococcus lactis is used extensively world-wide for the production of fermented dairy products. Bacteriophages (phages) infecting L. lactis can result in slow or incomplete fermentations, or may even cause total fermentation failure. Therefore, bacteriophages disrupting L. lactis fermentation are of economic concern. This thesis employed a multifaceted approach to investigate various molecular aspects of phage-host interaction in L. lactis. The genome sequence of an Irish dairy starter strain, the prophage-cured L. lactis subsp. cremoris UC509.9, was studied. The 2,250,427 bp circular chromosome represents the smallest among its sequenced lactococcal equivalents. The genome displays clear genetic adaptation to the dairy niche in the form of extensive reductive evolution. Gene prediction identified 2066 protein-encoding genes, including 104 which showed significant homology to transposase-specifying genes. Over 9 % of the identified genes appear to be inactivated through stop codons or frame shift mutations. Many pseudogenes were found in genes that are assigned to carbohydrate and amino acid transport and metabolism orthologous groups, reflecting L. lactis UC509.9’s adaptation to the lactose and casein-rich dairy environment. Sequence analysis of the eight plasmids of L. lactis revealed extensive adaptation to the dairy environment. Key industrial phenotypes were mapped and novel lactococcal plasmid-associated genes highlighted. In addition to chromosomally-encoded bacteriophage resistance systems, six functional such systems were identified, including two abortive infection systems, AbiB and AbiD1, explaining the observed phage resistance of L. lactis UC509.9 Molecular analysis suggests that the constitutive expression of AbiB is not lethal to cells, suggesting the protein is expressed in an un/inactivated form. Analysis of 936 species phage sk1-escape mutants of AbiB revealed that all such mutants harbour mutations in orf6, which encodes the major capsid protein. Results suggest that the major capsid protein is required for activation of the AbiB system, although this requires furrther investigations. Temporal transcriptomes of L. lactis UC509.9 undergoing lytic infection with either one of two distinct bacteriophages, Tuc2009 and c2, was determined and compared to the transcriptome of uninfected UC509.9 cells. Whole genome microarrays performed at various time-points post-infection demonstrated a rather modest impact on host transcription. Alterations in the UC509.9 transcriptome during lytic infection appear phage-specific, with a relatively small number of differentially transcribed genes shared between infection with either Tuc2009 or c2. Transcriptional profiles of both bacteriophages during lytic infection was shown to generally correlate with previous studies and allowed the confirmation of previously predicted promoter sequences. Bioinformatic analysis of genomic regions encoding the presumed cell wall polysaccharide (CW PS) biosynthesis gene cluster of several strains of L. lactis was performed. Results demonstrate the presence of three dominant genetic types of this gene cluster, termed type A, B and C. These regions were used for the development of a multiplex PCR to identify CW PS genotype of various lactococcal strains. Analysis of 936 species phage receptor binding protein phylogeny (RBP) and CW PS genotype revealed an apparent correlation between RBP phylogeny and CW PS type, thereby providing a partial explanation for the observed narrow host range of 936 phages. Further analysis of the genetic locus encompassing the presumed CW PS biosynthesis operon of eight strains identified as belonging to the CW PS C (geno)type, revealed the presence of a variable region among the examined strains. The obtained comparative analysis allowed for the identification of five subgroups of the C type, named C1 to C5. We purified an acidic polysaccharide from the cell wall of L. lactis 3107 (C2 subtype) and confirmed that it is structurally different from the CW PS of the C1 subtype L. lactis MG1363. Combinations of genes from the variable region of C2 subtype were amplified from L. lactis 3107 and introduced into a mutant of the C1 subtype L. lactis NZ9000 (a direct derivative of MG1363) deficient in CW PS biosynthesis. The resulting recombinant mutant synthesized a CW PS with a composition characteristic for that of the C2 subtype L. lactis 3107 and not the wildtype C1 L. lactis NZ9000. The recombinant mutant exhibited a changed phage resistance/sensitivity profile consistent with that of L. lactis 3107, which unambiguously demonstrated that L. lactis 3107 CW PS is the host cell surface receptor of two bacteriophages belonging to the P335 species as well as phages that are member of the 936 species. The research presented in this thesis has significantly advanced our understanding of L. lactis bacteriophage-host interactions in several ways. Firstly, the examination of plasmidencoded bacteriophage resistance systems has allowed inferences to be made regarding the mode of action of AbiB, thereby providing a platform for further elucidation of the molecular trigger of this system. Secondly, the phage infection transcriptome data presented, in addition to previous work, has made L. lactis a model organism in terms of transcriptomic studies of bacteriophage-host interactions. And finally, the research described in this thesis has for the first time explicitly revealed the nature of a carbohydrate bacteriophage receptor in L. lactis, while also providing a logical explanation for the observed narrow host ranges exhibited by 936 and P335 phages. Future research in discerning the structures of other L. lactis CW PS, combined with the determination of the molecular interplay between receptor binding proteins of these phages and CW PS will allow an in depth understanding of the mechanism by which the most prevalent lactococcal phages identify and adsorb to their specific host.

Reductive elimination of hypersilyl halides from zinc (II) complexes. Implications for electropositive metal thin film growth

Treatment of Zn(Si(SiMe3)3)2 with ZnX2 (X = Cl, Br, I) in tetrahydrofuran (THF) at 23 °C afforded [Zn(Si(SiMe3)3)X(THF)]2 in 83–99% yield. X-ray crystal structures revealed dimeric structures with Zn2X2 cores. Thermogravimetric analyses of [Zn(Si(SiMe3)3)X(THF)]2 demonstrated a loss of coordinated THF between 50 and 155 °C and then single-step weight losses between 200 and 275 °C. The nonvolatile residue was zinc metal in all cases. Bulk thermolyses of [Zn(Si(SiMe3)3)X(THF)]2 between 210 and 250 °C afforded zinc metal in 97–99% yield, Si(SiMe3)3X in 91–94% yield, and THF in 81–98% yield. Density functional theory calculations confirmed that zinc formation becomes energetically favorable upon THF loss. Similar reactions are likely to be general for M(SiR3)n/MXn pairs and may lead to new metal-film-growth processes for chemical vapor deposition and atomic layer deposition.

The accountability of transnational armed groups under international law

Terrorist attacks by transnational armed groups cause on average 15,000 deaths every year worldwide, with the law enforcement agencies of some states facing many challenges in bringing those responsible to justice. Despite various attempts to codify the law on transnational terrorism since the 1930s, a crime of transnational terrorism under International Law remains contested, reflecting concerns regarding the relative importance of prosecuting members of transnational armed groups before the International Criminal Court. However, a study of the emerging jurisprudence of the International Criminal Court suggests that terrorist attacks cannot be classified as a war crime or a crime against humanity. Therefore, using organisational network theory, this thesis will probe the limits of international criminal law in bringing members of transnational armed groups to justice in the context of changing methods of warfare. Determining the organisational structure of transnational armed groups, provides a powerful analytical framework for examining the challenges in holding members of transnational armed groups accountable before the International Criminal Court, in the context of the relationship between the commanders and the subordinate members of the group.