Embedding colloidal nanoparticles inside mesoporous silica using gas expanded liquids for high loading recyclable catalysts

The ability to tune the structural and chemical properties of colloidal nanoparticles (NPs), make them highly advantageous for studying activity and selectivity dependent catalytic behaviour. Incorporating pre-synthesized colloidal NPs into porous supports materials remains a challenge due to poor wetting and pore permeability. In this report monodisperse, composition controlled AgPd alloy NPs were synthesised and embedded into SBA-15 using supercritical carbon dioxide and hexane. Supercritical fluid impregnation resulted in high metal loading without the requirement for surface pre-treatments. The catalytic activity, reaction profiles and recyclability of the alloy NPs embedded in SBA-15 and immobilised on non-porous SiO2 are evaluated. The NPs incorporated within the SBA-15 porous network showed significantly greater recyclability performance compared to non-porous SiO2.

Health care and neoliberalism in Ireland: withholding the gift and corrupting the social contract

The health of a nation tells much about the nature of a social contract between citizen and state. The way that health care is organised, and the degree to which it is equitably accessible, constitutes a manifestation of the effects of moments and events in that country's history. Using four case studies, this thesis uses a historical genealogical approach to explain the evolution of Ireland's particular version of health care provision. The total social fact of the gift relationship, central to all human relations, will be used to form a theoretical and conceptual framework on which to build an analysis of Ireland's health and welfare conditions. Additionally, social contract theory will enable an examination of the role of solidarity in relation to social expectations around health care provision. Through the analysis of these cases, the complex matrix of the influential forces that have shaped current conditions are exposed and revealed, enabling a critical understanding of the extent of acquiescence to the inequitable system that arguably exists. The vulnerability of citizens in need of care to the external and global effects of market forces and neoliberalism, therefore, becomes central to any argument for state-provided health and welfare. The hegemony of such forces can be seen to influence the manner in which the idea of individual self-reliance, in place of collective solidarity, is conceptualised and subsequently infiltrated into a range of aspects of the social world. For example, the particular discourse of the market and of economic concerns succeeds in shaping understandings of responsibilities around central areas of health and welfare. Similarly the 'possessor principle' can be seen to be misplaced within the context of health and social care, but yet has become normalised within this discourse. Within this matrix of complex influencing factors, the welfare state struggles to impose a balance between market values and social values. Responsibilities of the state to support and compensate its citizens for the ills of the market have become devalued, as the core values of classical liberalism have become distorted beyond recognition, leaving instead bare neoliberal concerns. This thesis traces the genealogical origins of this transition within the recent history of Irish health care and thereby reveals the embedding of individualism in place of solidarity, the on going reneging of the social contract and the corruption of the gift relationship.

Oxidation-reduction potential and its influence on Cheddar cheese quality

Oxidation-reduction (redox) potential is a fundamental physicochemical parameter that affects the growth of microorganisms in dairy products and contributes to a balanced flavour development in cheese. Even though redox potential has an important impact on the quality of dairy products, it is not usually monitored in dairy industry. The aims of this thesis were to develop practical methods for measuring redox potential in cheese, to provide detailed information on changes in redox potential during the cheesemaking and cheese ripening and how this parameter is influenced by starter systems and to understand the relationship between redox potential and cheese quality. Methods were developed for monitoring redox potential during cheesemaking and early in ripening. Changes in redox potential during laboratory scale manufacture of Cheddar, Gouda, Emmental, and Camembert cheeses were determined. Distinctive kinetics of reduction in redox potential during cheesemakings were observed, and depended on the cheese technology and starter culture utilised. Redox potential was also measured early in ripening by embedding electrodes into Cheddar cheese at moulding together with the salted curd pieces. Using this approach it was possible to monitor redox potential during the pressing stage. The redox potential of Emmental cheese was also monitored during ripening. Moreover, since bacterial growth drives the reduction in redox potential during cheese manufacture and ripening, the ability of Lactococcus lactis strains to affect redox potential was studied. Redox potential of a Cheddar cheese extract was altered by bacterial growth and there were strain-specific differences in the nature of the redox potential/time curves obtained. Besides, strategies to control redox potential during cheesemaking and ripening were developed. Oxidizing or reducing agents were added to the salted curd before pressing and results confirmed that a negative redox potential is essential for the development of sulfur compounds in Cheddar cheese. Overall, the studies described in this thesis gave an evidence of the importance of the redox potential on the quality of dairy products. Redox potential could become an additional parameter used to select microorganisms candidate as starters in fermented dairy products. Moreover, it has been demonstrated that the redox potential influences the development of flavour component. Thus, measuring continuously changes in redox potential of a product and controlling, and adjusting if necessary, the redox potential values during manufacture and ripening could be important in the future of the dairy industry.

Weathering the crisis? Managing democracy at a national broadcaster

With post-2008 political and economic crises as its backdrop, this inquiry into the political roles and functions of public service broadcasting (PSB) in Ireland is principally concerned with examining the capacities for and actuality of critical and counter-hegemonic professional journalistic and institutional mediations of crisis. Recognising the diversity of influences on the normative identity of Irish PSB, the dissertation adopts a sociological approach that acknowledges the systemic embedding of media institutions in the broader field of power. An initial tracing of the formative impacts of endogenous and exogenous forces on the democratic horizons of PSB suggests that the present crisis conjuncture does not represent promising terrain for engendering critical crisis and recovery imaginaries. A methodologically diverse intra-institutional empirical research agenda aims to explore at close hand Irish PSB’s contingent navigation of crisis, encompassing ethnographic observation in the newsroom, practitioner interviews and textual analysis of broadcast output. These methods afford close analysis of practices of journalistic production and reflexivity, self-conceptions of the journalistic habitus, and ideological affinities of crisis framings in broadcast output. These analyses are supplemented by a participant observation study of the possibilities for public agenda-building in a key institutional venue of public participation in broadcasting governance. The findings offer an evidential basis for the arguments that the crisis has prompted only minimal changes to professional norms and practices of representation and inclusion; that journalistic crisis framings tend toward effecting hegemonic repair by lending support to neoliberal crisis and recovery imaginaries; and that the institutional openings for the building of public counterpower are highly constrained. The overall conclusion is made that the normative democratic orientation embedded in the professional and institutional projects of public service broadcasting help render it ill-equipped to act as a re-democratising countervailing power against the democratic regressions engendered by the present crisis of democratic capitalism.

Forces of agglomeration and dispersal in rural business networks: a social network analysis

Two concepts in rural economic development policy have been the focus of much research and policy action: the identification and support of clusters or networks of firms and the availability and adoption by rural businesses of Information and Communication Technologies (ICT). From a theoretical viewpoint these policies are based on two contrasting models, with clustering seen as a process of economic agglomeration, and ICT-mediated communication as a means of facilitating economic dispersion. The study’s conceptual framework is based on four interrelated elements: location, interaction, knowledge, and advantage, together with the concept of networks which is employed as an operationally and theoretically unifying concept. The research questions are developed in four successive categories: Policy, Theory, Networks, and Method. The questions are approached using a study of two contrasting groups of rural small businesses in West Cork, Ireland: (a) Speciality Foods, and (b) firms in Digital Products and Services. The study combines Social Network Analysis (SNA) with Qualitative Thematic Analysis, using data collected from semi-structured interviews with 58 owners or managers of these businesses. Data comprise relational network data on the firms’ connections to suppliers, customers, allies and competitors, together with linked qualitative data on how the firms established connections, and how tacit and codified knowledge was sourced and utilised. The research finds that the key characteristics identified in the cluster literature are evident in the sample of Speciality Food businesses, in relation to flows of tacit knowledge, social embedding, and the development of forms of social capital. In particular the research identified the presence of two distinct forms of collective social capital in this network, termed “community” and “reputation”. By contrast the sample of Digital Products and Services businesses does not have the form of a cluster, but matches more closely to dispersive models, or “chain” structures. Much of the economic and social structure of this set of firms is best explained in terms of “project organisation”, and by the operation of an individual rather than collective form of “reputation”. The rural setting in which these firms are located has resulted in their being service-centric, and consequently they rely on ICT-mediated communication in order to exchange tacit knowledge “at a distance”. It is this factor, rather than inputs of codified knowledge, that most strongly influences their operation and their need for availability and adoption of high quality communication technologies. Thus the findings have applicability in relation to theory in Economic Geography and to policy and practice in Rural Development. In addition the research contributes to methodological questions in SNA, and to methodological questions about the combination or mixing of quantitative and qualitative methods.

Synthesis and characterization of nanocomposites based on PANI and carbon nanostructures prepared by electropolymerization

Nanocomposites based on polyaniline (PANI) and carbon nanostructures (CNSs) (graphene (G) and multiwall carbon nanotubes (MWCNTs)) were prepared by in situ electrochemical polymerization. CNSs were inserted into the PANI matrix by dispersing them into the electrolyte before the electropolymerization. Electrochemical characterization by means of cyclic voltammetry and steady state polarization were performed in order to determine conditions for electro- polymerization. Electro-polymerization of the PANI based nanocomposites was carried out at 0.75 V vs. saturated calomel electrode (SCE) for 40 and 60 minutes. The morphology and structural characteristics of the obtained nanocomposites were studied by scanning electron microscopy (SEM) and Raman spectroscopy, while thermal stability was determined using thermal gravimetric analysis (TGA). According to the morphological and structural study, fibrous and porous structure of PANI based nanocomposites was detected well embedding both G and MWCNTs. Also, strong interaction between quinoidal structure of PANI with carbon nanostructures via π–π stacking was detected by Raman spectroscopy. TGA showed the increased thermal stability of composites reinforced with CNSs, especially those reinforced with graphene.

Adopting results based management in the non-profit sector: Trócaire’s experience

The increasing emphasis on aid effectiveness, accountability and impact measurement in international development and humanitarian work has generated a requirement for high quality internal systems for the management of programmes. To help to address this requirement, Trócaire adopted Results Based Management in the 20 countries in which it works. This paper provides an overview of Trócaire’s RBM journey, including the process of embedding the new approach in the organisation, lessons learnt from this process, the subsequent benefits that are emerging at field programme level and the challenges going forward.