Polyelectrolyte-functionalized ionic liquid for electrochemistry in supporting electrolyte-free aqueous solutions and application in amperometric flow injection analysis

As a green process, electrochemistry in aqueous solution without a supporting electrolyte has been described based on a simple polyelectrolyte-functionalized ionic liquid (PFIL)-modified electrode. The studied PFIL material combines features of ionic liquids and traditional polyelectrolytes. The ionic liquid part provides a high ionic conductivity and affinity to many different compounds. The polyelectrolyte part has a good stability in aqueous solution and a capability of being immobilized on different substrates. The electrochemical properties of such a PFIL-modified electrode assembly in a supporting electrolyte-free solution have been investigated by using an electrically neutral electroactive species, hydroquinone ( HQ) as the model compound. The partition coefficient and diffusion coefficient of HQ in the PFIL film were calculated to be 0.346 and 4.74 X 10(-6) cm(2) s(-1), respectively. Electrochemistry in PFIL is similar to electrochemistry in a solution of traditional supporting electrolytes, except that the electrochemical reaction takes place in a thin film on the surface of the electrode. PFILs are easily immobilized on solid substrates, are inexpensive and electrochemically stable. A PFIL-modified electrode assembly is successfully used in the flow analysis of HQ by amperometric detection in solution without a supporting electrolyte.

Ion channel behavior of amphotericin B in sterol-free and cholesterol- or ergosterol-containing supported phosphatidylcholine bilayer model membranes investigated by electrochemistry and spectroscopy

Amphotericin B (AmB) is a popular drug frequently applied in the treatment of systemic fungal infections. In the presence of ruthenium (II) as the maker ion, the behavior of AmB to form ion channels in sterol-free and cholesterol- or ergosterol-containing supported phosphatidylcholine bilayer model membranes were studied by cyclic votammetry, AC impedance spectroscopy, and UV/visible absorbance spectroscopy. Different concentrations of AmB ranging from a molecularly dispersed to a highly aggregated state of the drug were investigated. In a fixed cholesterol or ergosterol content (5 mol %) in glassy carbon electrode-supported model membranes, our results showed that no matter what form of AmB, monomeric or aggregated, AmB could form ion channels in supported ergosterol-containing phosphatidylcholine bilayer model membranes. However, AmB could not form ion channels in its monomeric form in sterol-free and cholesterol-containing supported model membranes. On the one hand, when AmB is present as an aggregated state, it can form ion channels in cholesterol-containing supported model membranes; on the other hand, only when AmB is present as a relatively highly aggregated state can it form ion channels in sterol-free supported phosphatidylcholine bilayer model membranes. The results showed that the state of AmB played an important role in forming ion channels in sterol-free and cholesterol-containing supported phosphatidylcholine bilayer model membranes.

A study of the dependence of ferrocene diffusion on electrolyte concentration and size in a polymer medium using non-steady-state chronoamperometry

This article describes a quantitative study of the diffusion rate of ferrocene(Fc) dissolved in ploy(ethylene glycol)(PEG) medium containing MClO(4)(M = Li+, Na+, Bu(4)N(+), Hx(4)N(+)). The apparent diffusion coefficient D-app and the active concentration c(a) of Fc were simultaneously measured by using non-steady-state chronoamperometry. The D-app and c(a) of Fc have been estimated in PEG containing different concentrations and sizes of supporting electrolyte, and the dependence of D-app on ferrocene concentrations has been observed. The values of D-app decrease with increasing concentrations of Fc, increasing concentrations of LiClO4 or the ratio (O:Li) and also with 4 decreasing cation radius of the electrolyte. The temperature dependencies conform to a simple free volume model. The concentration and size of the counterion dependencies of the diffusion rate are similar to the behavior of their dependencies of ionic conductivity in polyelectrolyte.

Motor Control and Learning by the State Space Model

A model is presented that deals with problems of motor control, motor learning, and sensorimotor integration. The equations of motion for a limb are parameterized and used in conjunction with a quantized, multi-dimensional memory organized by state variables. Descriptions of desired trajectories are translated into motor commands which will replicate the specified motions. The initial specification of a movement is free of information regarding the mechanics of the effector system. Learning occurs without the use of error correction when practice data are collected and analyzed.

Griping, bitching and speaking your mind: defamation and free expression on the internet

Diane Rowland, Griping, Bitching and Speaking Your Mind: Defamation and Free Expression on the Internet, Pennsylvania State Law Review Symposium Issue 110, no. 3 (2006): 519?538; RAE2008

Protein Docking by the Underestimation of Free Energy Funnels in the Space of Encounter Complexes

Similarly to protein folding, the association of two proteins is driven by a free energy funnel, determined by favorable interactions in some neighborhood of the native state. We describe a docking method based on stochastic global minimization of funnel-shaped energy functions in the space of rigid body motions (SE(3)) while accounting for flexibility of the interface side chains. The method, called semi-definite programming-based underestimation (SDU), employs a general quadratic function to underestimate a set of local energy minima and uses the resulting underestimator to bias further sampling. While SDU effectively minimizes functions with funnel-shaped basins, its application to docking in the rotational and translational space SE(3) is not straightforward due to the geometry of that space. We introduce a strategy that uses separate independent variables for side-chain optimization, center-to-center distance of the two proteins, and five angular descriptors of the relative orientations of the molecules. The removal of the center-to-center distance turns out to vastly improve the efficiency of the search, because the five-dimensional space now exhibits a well-behaved energy surface suitable for underestimation. This algorithm explores the free energy surface spanned by encounter complexes that correspond to local free energy minima and shows similarity to the model of macromolecular association that proceeds through a series of collisions. Results for standard protein docking benchmarks establish that in this space the free energy landscape is a funnel in a reasonably broad neighborhood of the native state and that the SDU strategy can generate docking predictions with less than 5 � ligand interface Ca root-mean-square deviation while achieving an approximately 20-fold efficiency gain compared to Monte Carlo methods.

Breaking ranks: the emergence of representative associations in the Irish armed forces 1989-1992

This study contexualises the relationship between the armed forces and the civil authority in Ireland using and revising the theoretical framework advanced by Huntington. It tracks the evolution of the idea of a representive body for soldiers in the late 1980s, to the setting up of statutory associations under the Defence Amendment Act 1990. The study considers Irish soldiers political agitation and their use of peaceful democratic activities to achieve their aims. It highlights the fundamental policy arguments that were made against the idea of representation for the army and positions those arguments in the study of civil-military relations. Utilising unique access to secret Department of Defence files, it reveals in-depth ideological arguments advanced by the military authories in Ireland against independent representation. This thesis provides an academic study of the establishment of PDFORRA. It answers key questions regarding the change in the position of Irish government who were categorically opposed to the idea of representation in the army. It illustrates the involvement of other agencies such as the European Organisation of Military Associations (Euromil) reveals reciprocal support by the Irish associations to other emerging groups in Spain. Accessing as yet unpublished Department of Defence files, study analyses tension between the military authorities and the government. It highlights for the first time the role of enlisted personnel in the shaping of new state structures and successfully dismmisses Huntingtons theoretical contention that enlisted personnel are of no consequence in the study of civil-military relations. It fills a gap in our understanding, identified by Finer, as to how politicisation of soldiers takes place. This thesis brings a new dimension to the discipline of civil-military relations and creates new knowledge that will enhance our understanding of an area not covered previously.

Genteel revolutionaries: the lives of Anna and Thomas Haslam

The lives of Thomas and Anna Haslam were dedicated to the attainment of women's equality. They were feminists before the word was coined. In an era when respectable women were not supposed to know of the existence of prostitutes, Anna became empowered to do the unthinkable, not only to speak in public but to discuss openly matters sexual and to attack the double standard of sexuality which was enshrined in the official treatment of prostitutes. Their life-long commitment to the cause of women's suffrage never faltered, despite the repeated discouragement of the fate of bills defeated in the House of Commons. The Haslams represented an Ireland which did not survive them. While they were dedicated to the union with Westminster, they worked happily with those who applied themselves to its destruction. Although in many ways they exemplified the virtues of their Quaker backgrounds, they did not subscribe to any organised religion. Despite living in straitened circumstances, they were part of an urban intellectual elite and participated in the social and cultural life of Dublin for over fifty years. It is tempting to speculate how the Haslams would have fared in post independence Ireland. Hanna Sheehy Skeffington who had impeccable nationalist credentials, was effectively marginalised. It is likely that they would have protested against discriminatory legislation in their usual law abiding manner but, in a country which quickly developed an overwhelmingly Roman Catholic ethos, would they have had a voice or a constituency? Ironically, Thomas's teaching on chastity would have found favour with the hierarchy; his message was disseminated in a simple and more pious manner in numerous Catholic Truth Society pamphlets. The Protestant minority never sought to subvert the institutions of the state, was careful not to criticise and kept its collective head down. Dáil Éireann was not bombarded with petitions for the restoration of divorce facilities or the unbanning of birth control. Those who sought such amenities obtained them quietly 'in another jurisdiction.' Fifty years were to pass before the condom wielding 'comely maidens' erupted on to the front pages of the Sunday papers. They were, one imagines, the spiritual descendants of the militant rather than the constitutional suffrage movement. "Once and for all we need to commit ourselves to the concept that women's rights are not factional or sectional privileges, bestowed on the few at the whim of the many. They are human rights. In a society in which the rights and potential of women are constrained no man can be truly free." These words spoken by Mary Robinson as President of Ireland are an echo of the principles to which the Haslams dedicated their lives and are, perhaps, a tribute to their efforts.

The transformation of Ireland 1958 - 93: the role of ideas in punctuating institutional path dependency at critical junctures

Ireland experienced two critical junctures when its economic survival was threatened: 1958/9 and 1986/7. Common to both crises was the supplanting of long established practices, that had become an integral part of the political culture of the state, by new ideas that ensured eventual economic recovery. In their adoption and implementation these ideas also fundamentally changed the institutions of state – how politics was done, how it was organised and regulated. The end result was the transformation of the Irish state. The main hypothesis of this thesis is that at those critical junctures the political and administrative elites who enabled economic recovery were not just making pragmatic decisions, their actions were influenced by ideas. Systematic content analysis of the published works of the main ideational actors, together with primary interviews with those actors still alive, reveals how their ideas were formed, what influenced them, and how they set about implementing their ideas. As the hypothesis assumes institutional change over time historical institutionalism serves as the theoretical framework. Central to this theory is the idea that choices made when a policy is being initiated or an institution formed will have a continuing influence long into the future. Institutions of state become ‘path dependent’ and impervious to change – the forces of inertia take over. That path dependency is broken at critical junctures. At those moments ideas play a major role as they offer a set of ready-made solutions. Historical institutionalism serves as a robust framework for proving that in the transformation of Ireland the role of ideas in punctuating institutional path dependency at critical junctures was central.

Cereal products for specific dietary requirements. Evaluation and improvement of technological and nutritional properties of gluten free raw materials and end products

Coeliac disease is one of the most common food intolerances worldwide and at present the gluten free diet remains the only suitable treatment. A market overview conducted as part of this thesis on nutritional and sensory quality of commercially available gluten free breads and pasta showed that improvements are necessary. Many products show strong off-flavors, poor mouthfeel and reduced shelf-life. Since the life-long avoidance of the cereal protein gluten means a major change to the diet, it is important to also consider the nutritional value of products intending to replace staple foods such as bread or pasta. This thesis addresses this issue by characterising available gluten free cereal and pseudocereal flours to facilitate a better raw material choice. It was observed that especially quinoa, buckwheat and teff are high in essential nutrients, such as protein, minerals and folate. In addition the potential of functional ingredients such as inulin, β-glucan, HPMC and xanthan to improve loaf quality were evaluated. Results show that these ingredients can increase loaf volume and reduce crumb hardness as well as rate of staling but that the effect diverges strongly depending on the bread formulation used. Furthermore, fresh egg pasta formulations based on teff and oat flour were developed. The resulting products were characterised regarding sensory and textural properties as well as in vitro digestibility. Scanning electron and confocal laser scanning microscopy was used throughout the thesis to visualise structural changes occurring during baking and pasta making

Biodiversity change in the Irish uplands - the effects of grazing management

As a prominent form of land use across much of upland Europe, extensive livestock grazing may hold the key to the sustainable management of these landscapes. Recent agricultural policy reform, however, has resulted in a decline in upland sheep numbers, prompting concern for the biodiversity value of these areas. This study quantifies the effects of varying levels of grazing management on plant, ground beetle and breeding bird diversity and assemblage in the uplands and lowlands of hill sheep farms in County Kerry, Ireland. Farms represent a continuum of light to heavy grazing, measured using a series of field indicators across several habitats, such as the internationally important blanket bog, home to the ground beetle, Carabus clatratus. Linear mixed effects modelling and non-metric multidimensional scaling are employed to disentangle the most influential management and environmental factors. Grazing state may be determined by the presence of Molinia caerulea or Nardus stricta, and variables such as % traditional ewes, % vegetation litter and % scrub prove valuable indicators of diversity. Measures of ecosystem functioning, e.g. plant biomass (nutrient cycling) and % vegetation cover (erosion rates) are influenced by plant diversity, which is influenced by grazing management. Levels of the ecosystem service, soil organic carbon, vary with ground beetle abundance and diversity, potentially influencing carbon sequestration and thereby climate change. The majority of species from all three taxa are found in the lowlands, with the exception of birds such as meadow pipit and skylark. The scale of measurement should be determined by the size and mobility of the species in question. The challenge is to manage these high nature value landscapes using agri-environment schemes which enhance biodiversity by maintaining structural heterogeneity across a range of scales, altitudes and habitats whilst integrating the decisions of people living and working in these marginal areas.

Correlations in low dimensional quantum systems

In this thesis I present the work done during my PhD in the area of low dimensional quantum gases. The chapters of this thesis are self contained and represent individual projects which have been peer reviewed and accepted for publication in respected international journals. Various systems are considered, the first of which is a two particle model which possesses an exact analytical solution. I investigate the non-classical correlations that exist between the particles as a function of the tunable properties of the system. In the second work I consider the coherences and out of equilibrium dynamics of a one-dimensional Tonks-Girardeau gas. I show how the coherence of the gas can be inferred from various properties of the reduced state and how this may be observed in experiments. I then present a model which can be used to probe a one-dimensional Fermi gas by performing a measurement on an impurity which interacts with the gas. I show how this system can be used to observe the so-called orthogonality catastrophe using modern interferometry techniques. In the next chapter I present a simple scheme to create superposition states of particles with special emphasis on the NOON state. I explore the effect of inter-particle interactions in the process and then characterise the usefulness of these states for interferometry. Finally I present my contribution to a project on long distance entanglement generation in ion chains. I show how carefully tuning the environment can create decoherence-free subspaces which allows one to create and preserve entanglement.

Home, family and society: women of the Irish landed class, 1860-1914. A Munster case study

The thesis analyses the roles and experiences of female members of the Irish landed class (wives, sisters and daughters of gentry and aristocratic landlords with estates over 1,000 acres) using primary personal material generated by twelve sample families over an important period of decline for the class, and growing rights for women. Notably, it analyses the experiences of relatively unknown married and unmarried women, something previously untried in Irish historiography. It demonstrates that women’s roles were more significant than has been assumed in the existing literature, and leads to a more rounded understanding of the entire class. Four chapters focus on themes which emerge from the sources used and which deal with their roles both inside and outside the home. These chapters argue that: Married and unmarried women were more closely bound to the priorities of their class than their sex, and prioritised male-centred values of family and estate. Male and female duties on the property overlapped, as marriage relationships were more equal than the legislation of the time would suggest. London was the cultural centre for this class. Due to close familial links with Britain (60% of sample daughters married English men) their self-perception was British or English, as well as Irish. With the self-confidence of their class, these women enjoyed cultural and political activities and movements outside the home (sport, travel, fashion, art, writing, philanthropy, (anti-)suffrage, and politics). Far from being pawns in arranged marriages, women were deeply conscious of their marriage decisions and chose socially, financially and personally compatible husbands; they also looked for sexual satisfaction. Childbirth sometimes caused lasting health problems, but pregnancy did not confine wealthy women to an invalid state. In opposition to the stereotypical distant aristocratic mother, these women breastfed their children, and were involved mothers. However, motherhood was not permitted to impinge on the more pressing role of wife

Challengers to provisional republicanism: the official republican movement, people’s democracy and the Irish republican socialist party, 1968–98

The Provisional IRA and its political wing Sinn Féin have attracted by far the greatest scholarly interest of all the players in the Northern Irish conflict. This emphasis is perfectly legitimate, given the centrality of the Provos to so many turning-points in the conflict, from the collapse of Stormont in the early 1970s to the hunger strikes of the following decade and the ceasefires which were followed by the Belfast Agreement. My project, however, looks at political groups that at one time or another challenged the Provos for leadership of the militant, anti-state constituency in Northern Ireland (chiefly based in the Catholic working class). Although never as large or influential as the Provisional republicans, groups such as the Official IRA and the Irish Republican Socialist Party sometimes had a discernible impact on the course of events which is overlooked by most studies, and often pioneered ideas and tactics that were later adopted by the Provos themselves. The idea that republicans should embrace political action and work in broad campaigning alliances was promoted by the IRSP and socialist groups such as People’s Democracy before it was taken up by Gerry Adams and his allies, while the Official IRA supported the principle of a settlement based on democratization of the Northern Irish state, which was later accepted by Sinn Féin in the form of the Belfast Agreement. The goal of my research is to provide a novel perspective on the conflict in Northern Ireland, while engaging with theoretical debates about its character.