An dátheangachas agus an t-aitheantas: déagóirí Éireannacha sa 21ú haois

Tugann an staidéar taighde aghaidh ar an dátheangachas i bPoblacht na hÉireann agus go háirithe ar thuairimí dhaoine óga dátheangacha sa 21ú haois. Is é cuspóir an staidéir ná iniúchadh a dhéanamh ar mheonta déagóirí Éireannacha dátheangacha i leith na Gaeilge agus a gcuid aitheantais mar dhéagóirí dátheangacha. Déanann an staidéar anailís ar mheonta daltaí a fhreastalaíonn ar iar-bhunscoileanna lán-Ghaeilge. Féachtar ar thuairimí tuismitheoirí, múinteoirí agus iar-scoláirí freisin. Is í príomhcheist an staidéir seo ná: Cad iad meonta déagóirí Éireannacha dátheangacha i leith teanga na Gaeilge agus cad iad a n-aitheantais mar Éireannaigh óga dátheangacha? Baineadh úsáid as modhanna cáilíochtúla idir agallaimh, agallamh grúpa, scríbhneoireacht phearsanta agus ríomhphoist chun eolas a bhailiú i scoil an staidéir cháis. Roghnaíodh modh cainníochtúil an cheistneora náisiúnta chun cur leis an eolas. Tugann an taighde le tuiscint go mothaíonn déagóirí Éireannacha dearfach faoi theanga na Gaeilge agus faoin a gcuid aitheantais mar dhaoine dátheangacha. Léiríonn torthaí an taighde gurb ionann teanga na Gaeilge dóibh agus seoid luachmhar a sholáthraíonn buntáistí, deiseanna agus féidearthachtaí dóibh. Maidir le cruthú aitheantais, chuaigh formhór na ndéagóirí i scoil an staidéir cháis i dtreo a ndá ghrúpa teangeolaíochta agus chruthaigh siad “linguistic brokerage” (Shenk, 2008) a tharraing a taobh Gaelach is Béarla le chéile. Mothaíonn formhór na ndéagóirí dátheangacha seo go bhfuil aitheantas amháin acu ach go bhfuil an dá theanga, an dá chultúr agus an dá pháirt dá saoil mar pháirt den gcomhaitheantas sin. Ach ba léir go raibh éagsúlachtaí i measc na rannpháirtithe freisin. Tacaíonn torthaí an taighde le gnéithe den litríocht ar a rinneadh athbhreithniú chun ról lárnach na teanga i gcruthú aitheantais an déagóra a léiriú. Cuireann an taighde seo leis an réimse toisc go soláthraíonn sé eolas luachmhar agus fiúntach faoin dátheangachas agus aitheantas i bPoblacht na hÉireann sa 21ú haois.

Synthesis & characterisation of group IV semiconducting nanowires

Semiconductor nanowires, particularly group 14 semiconductor nanowires, have been the subject of intensive research in the recent past. They have been demonstrated to provide an effective, versatile route towards the continued miniaturisation and improvement of microelectronics. This thesis aims to highlight some novel ways of fabricating and controlling various aspects of the growth of Si and Ge nanowires. Chapter 1 highlights the primary technique used for the growth of nanowires in this study, namely, supercritical fluid (SCF) growth reactions. The advantages (and disadvantages) of this technique for the growth of Si and Ge nanowires are highlighted, citing numerous examples from the past ten years. The many variables involved in this technique are discussed along with the resultant characteristics of nanowires produced (diameter, doping, orientation etc.). Chapter 2 outlines the experimental methodologies used in this thesis. The analytical techniques used for the structural characterisation of nanowires produced are also described as well as the techniques used for the chemical analysis of various surface terminations. Chapter 3 describes the controlled self-seeded growth of highly crystalline Ge nanowires, in the absence of conventional metal seed catalysts, using a variety of oligosilylgermane precursors and mixtures of germane and silane compounds. A model is presented which describes the main stages of self-seeded Ge nanowire growth (nucleation, coalescence and Ostwald ripening) from the oligosilylgermane precursors and in conjunction with TEM analysis, a mechanism of growth is proposed. Chapter 4 introduces the metal assisted etching (MAE) of Si substrates to produce Si nanowires. A single step metal-assisted etch (MAE) process, utilising metal ion-containing HF solutions in the absence of an external oxidant, was developed to generate heterostructured Si nanowires with controllable porous (isotropically etched) and non-porous (anisotropically etched) segments. In Chapter 5 the bottom-up growth of Ge nanowires, similar to that described in Chapter 3, and the top down etching of Si, described in Chapter 4, are combined. The introduction of a MAE processing step in order to “sink” the Ag seeds into the growth substrate, prior to nanowire growth, is shown to dramatically decrease the mean nanowire diameters and to narrow the diameter distributions. Finally, in Chapter 6, the biotin – streptavidin interaction was explored for the purposes of developing a novel Si junctionless nanowire transistor (JNT) sensor.

Synthesis of iminophosphine and phosphinoiminol cyclometallated Pt (II) and Pt (IV) chloro complexes and studies into their biological and photophysical properties

This thesis focuses on the synthesis and analysis of novel chloride based platinum complexes derived from iminophosphine and phosphinoamide ligands, along with studies on their reactivity towards substitution and oxidation reactions. Also explored here are the potential applications of these complexes for biological and luminescent purposes. Chapter one provides an extensive overview of platinum coordination chemistry with examples of various mixed donor ligands along with the history of platinum anticancer therapy. It also looks at metals in medicine, both for biological functions as well as for therapeutic purposes and gives a background to some other applications for platinum complexes. Chapter two outlines the design and synthetic strategies employed for the development of novel platinum (II) chloride complexes from iminophosphine and phosphinoamide ligands. Also reported is the cyclometallation of these complexes to form stable tridentate mixed donor platinum (II) compounds. In Chapter three the development of a direct method for displacing a chloride from a platinum metal centre with a desired phosphine is reported. Numerous methods for successful oxidation of the platinum (II) complexes will also be explored, leading to novel platinum (IV) complexes being reported here also. The importance of stabilisation of the displaced anion, chloride, by the solvent system will also be discussed in this chapter. Chapter four investigates the reactivity of the platinum (II) complexes towards two different biomolecules to form novel platinum bio-adducts. The potential application of the platinum (II) cyclometallates as chemotherapeutics will also be explored here using in-vitro cancer cell testing. Finally, luminescence studies are also reported here for the ligands and platinum complexes reported in chapter two and three to investigate potential applications in this field also. Chapter five provides a final conclusion and an overall summary of the entire project as well as identifying key areas for future work.

Fas ligand expression and tumour immune evasion; the role of prostaglandin E2 and the EP1 receptor

Background and Aim: During carcinogenesis, tumours develop multiple mechanisms to evade the immune system and suppress the anti-tumour immune response. Upregulation of Fas Ligand (FasL/CD95L) expression may represent one such mechanism. FasL is a member of the tumour necrosis factor superfamily that triggers apoptotic cell death following ligation to its receptor Fas. Numerous studies have demonstrated upregulated FasL expression in tumor cells, with FasL expression associated with numerous pro-tumorigenic effects. However, little is known about the mechanisms that regulate FasL expression in tumours. The cyclooxgenase (COX) signalling pathway may play an important role in colon carcinogenesis, via the production of prostaglandins, in particular PGE2. PGE2 signals through four different receptor subtypes, EP1 – EP4. Thus, the aim of this study was to investigate the effect of targeting the PGE2-FasL signaling pathway. Results: (i) PGE2 induces FasL expression via the EP1 receptor in colon cancer cells. (ii) Suppression of FasL expression in colon tumour cells in vivo significantly delays and reduces tumour growth. (iii) Blocking EP1 receptor signaling, or suppression of the EP1 receptor in colon tumour cells, reduces tumour growth in vivo. Suppression of tumour growth correlates in part with suppression of FasL expression. (iv) The reduction in tumour growth is associated with an improved anti-tumour immune response. Tumour infiltration by Treg cells and macrophages was reduced, and the cytotoxic activity of CTL generated from splenocytes isolated from these mice increased. Conclusion: 1) Targeting FasL expression by blocking PGE2-EP1 receptor signalling reduces tumour development in vivo. 2) The mechanism is indirect but is associated with an increased anti-tumour immune response. Thus, unraveling the mechanisms regulating FasL expression and the pro-tumorigenic effects of the EP1 receptor may aid in the search for new therapeutic targets against colon cancer.

Synthesis, characterisation and applications of group IV nanocrystals

Group IV materials such as silicon nanocrystals (Si NCs) and carbon quantum dots (CQDs) have received great attention as new functional materials with unique physical/chemical properties that are not found in the bulk material. This thesis reports the synthesis and characterisation of both types of nanocrystal and their application as fluorescence probes for the detection of metal ions. In chapter 2, a simple method is described for the size controlled synthesis of Si NCs within inverse micelles having well defined core diameters ranging from 2 to 6 nm using inert atmospheric synthetic methods. In addition, ligands with different molecular structures were utilised to reduce inter-nanocrystal attraction forces and improve the stability of the NC dispersions in water and a variety of organic solvents. Regulation of the Si NCs size is achieved by variation of the surfactants and addition rates, resulting high quality NCs with standard deviations (σ = Δd/d) of less than 10 %. Large scale production of highly mondisperse Si NC was also successfully demonstrated. In chapter 3, a simple solution phase synthesis of size monodisperse carbon quantum dots (CQDs) using a room temperature microemulsion strategy is demonstrated. The CQDs are synthesized in reverse micelles via the reduction of carbon tetrachloride using a hydride reducing agent. CQDs may be functionalised with covalently attached alkyl or amine monolayers, rendering the CQDs dispersible in wide range of polar or non-polar solvents. Regulation of the CQDs size was achieved by utilizing hydride reducing agents of different strengths. The CQDs possess a high photoluminescence quantum yield in the visible region and exhibit excellent photostability. In chapter 4, a simple and rapid assay for detection of Fe3+ ions was developed, based on quenching of the strong blue-green Si NC photoluminescence. The detection method showed a high selectivity, with only Fe3+ resulting in strong quenching of the fluorescence signal. No quenching of the fluorescence signal was induced by Fe2+ ions, allowing for solution phase discrimination between the same ion in different charge states. The optimised sensor system showed a sensitive detection range from 25- 900 μM and a limit of detection of 20.8 μM