Research Repository UCD

Friends, strangers or countrymen? The ties between citizens as colleagues

Thu, 01 Mar 2001 00:00:00 GMT

Friends, strangers or countrymen? The ties between citizens as colleagues Honohan, Iseult Some analogies are better than others for understanding the ties and responsibilities between citizens of a state. Citizens are better understood as particular kinds of colleagues than as either strangers or members of close-knit communities such as family or friends. Colleagues are diverse, separate and relatively distant individuals whose involuntary interdependence as equals in a practice or institution creates common concerns; this entails special responsibilities of communication, consideration and trust, which are capable of extension beyond the immediate group. Citizens likewise are involuntarily interdependent in political practices, and have comparable concerns and obligations that are more substantial than liberal advocates of constitutional patriotism recommend. But these are distinct from and potentially more extensible than those between co-nationals sharing a common culture, which are proposed by nationalists and some communitarians. The relationship of citizens is a more valid ground for associative obligations than others apart from family and friends.

Should Irish emigrants have votes? External voting in Ireland

Mon, 21 Nov 2011 00:00:00 GMT

Should Irish emigrants have votes? External voting in Ireland Honohan, Iseult Ireland is one of the few countries in Europe not to offer some form of suffrage to its citizens who live abroad permanently. In contrast, it has been a frontrunner in the trend towards providing more liberal voting regimes for resident noncitizens, as since 1963 it has allowed all resident for the previous six months to vote and stand in local elections. In this paper I consider the normative case for and against external voting, the current comparative context of its increasing provision among European countries, and the range of ways in which voting rights abroad combine with the extensibility of citizenship by descent abroad. Addressing the Irish case, I argue that there is no basis for a general right to vote for external citizens, but that, nonetheless, persisting connections and the rate of return migration give some reason to grant votes to first generation emigrants, if differently weighted from those of resident citizens.

Advances in pervasive health

Sun, 01 Jul 2012 00:00:00 GMT

Advances in pervasive health O'Grady, Michael J.; Caulfield, Brian; O'Hare, G. M. P. (Greg M. P.) Pervasive Health seeks to harness developments in pervasive computing technologies and harness them in the health domain. This domain may be interpreted in its widest possible sense, including the medical aspect both physical and mental, but also that of care management, education, community and occupational health. Such is the potential of pervasive computing technologies that the domain of pervasive health itself may ultimately fracture into a number of specialised domains, as the potential of the technology is being increasingly realised in practice. Indeed, this is already occurring with increased research activity being directed towards Ambient Assisted Living (AAL) in response to ongoing societal aging patterns

Supporting Problem-based Learning in Moodle using Personalised, Context- specific Learning Episode Generation

Fri, 14 Sep 2012 00:00:00 GMT

Supporting Problem-based Learning in Moodle using Personalised, Context- specific Learning Episode Generation Brabazon, Dermot; Donovan, Lynda; Melia, Mark; O'Mahony, Michael P.; Egan, Andrew; Smyth, Barry Providing learners with a list of disparate search results is not always conducive to learning. In particular, this approach lacks learning structure, and learners have to sift through lists of resources in order to make sense of them and to find the level of detail they require. In this paper we outline the Moodle Help Block, a Moodle block plug-in that provides learners with Just-In-Time context relevant learning material using a defined pedagogical strategy. The Moodle Help Block uses a combination of Semantic Web, Social Web and learning composition technology to generate learning episodes as needed by learners. The Moodle help block conducts a dialogue with the learner to extrapolate where a given learner’s knowledge gaps lie and generate learning episodes with learning material to help the learner overcome their knowledge deficit. It is thought that the Moodle Help Block can assist learners with targeted help when a teacher is not available. 1st Moodle Research Conference, Heraklion, Crete, Greece, September 14-15, 2012

Harnessing the Experience Web to Support User-Generated Product Reviews

Mon, 03 Sep 2012 00:00:00 GMT

Harnessing the Experience Web to Support User-Generated Product Reviews Dong, Ruihai; Schaal, Markus; O'Mahony, Michael P.; McCarthy, Kevin; Smyth, Barry Today, online reviews for products and services have become an important class of user-generated content and they play a valuable role for countless online businesses by helping to convert casual browsers into informed and satisfied buyers. In many respects, the content of user reviews is every bit as important as the catalog content that describes a given product or service. As users gravitate towards sites that offer insightful and objective reviews, the ability to source helpful reviews from a community of users is increasingly important. In this work we describe the Reviewer’s Assistant, a case-based reasoning inspired recommender system designed to help people to write more helpful reviews on sites such as Amazon and TripAdvisor. In particular, we describe two approaches to helping users during the review writing process and evaluate each as part of a blind live-user study. Our results point to high levels of user satisfaction and improved review quality compared to a control-set of Amazon reviews. Proceedings of the 20th International Conference, ICCBR 2012, Lyon, France, September 3-6, 2012.

Practical Problem-Based Learning in Computing Education

Sun, 01 Jul 2012 00:00:00 GMT

Practical Problem-Based Learning in Computing Education O'Grady, Michael J. Computer Science (CS) is a relatively new disciple and how best to introduce it to new students remains an open question. Likewise, the identification of appropriate instructional strategies for the diverse topics that constitute the average curriculum remains open to debate. One approach considered by a number of practitioners in CS education involves Problem Based Learning (PBL), a radical departure from the conventional lecturing format. PBL has been adopted in other domains with success, but whether these positive experiences will be replicated in CS remains to be seen. In this paper, a systematic review of PBL initiatives in undergraduate and postgraduate CS is presented from a Computing Education Research (CER) perspective. This includes analyses of a range of practical didactic issues, including the degree to which PBL has been systematically evaluated, practical problem description in the literature, as well as a survey of topics for which a PBL approach has been adopted.

Robotic UBIquitous COgnitive Network

Sun, 01 Jan 2012 00:00:00 GMT

Robotic UBIquitous COgnitive Network Amato, G.; Broxvall, M.; Dragone, Mauro; Gennaro, C.; Lopez, R.; Maguire, L.; McGinnity, T. M.; Micheli, A.; Renteria, A.; O'Hare, G. M. P. (Greg M. P.); Pecora, F. Robotic ecologies are networks of heterogeneous robotic devices pervasively embedded in everyday environments, where they cooperate to perform complex tasks. While their potential makes them increasingly popular, one fundamental problem is how to make them self-adaptive, so as to reduce the amount of preparation, pre-programming and human supervision that they require in real world applications. The EU FP7 project RUBICON develops self-sustaining learning solutions yielding cheaper, adaptive and efficient coordination of robotic ecologies. The approach we pursue builds upon a unique combination of methods from cognitive robotics, agent control systems, wireless sensor networks and machine learning. This paper briefly illustrates how these techniques are being extended, integrated, and applied to AAL applications. 3rd International Symposium on Ambient Intelligence, Salamanca, Spain, 2012

Robotic UBIquitous COgnitive Networks (RUBICON)

Wed, 22 Feb 2012 00:00:00 GMT

Robotic UBIquitous COgnitive Networks (RUBICON) Abdel-Naby, S.; Amato, G.; Bacciu, D.; Chessa, S.; Coleman, S.; Di Rocco, M.; Dragone, Mauro; Gallicchio, C.; Gennaro, C.; Guzman, R.; Lopez, R.; Lozano, H.; Maguire, L.; McGinnity, T. M.; Micheli, A.; O'Hare, G. M. P. (Greg M. P.); Pecora, F.; Ray, A.; Renteria, A.; Saffiotti, A.; Swords, D.; Vairo, C. Poster presentation at the 5th International Conference on Cognitive Systems (CogSys 2012), TU Vienna, Vienna, 22-23 February, 2012

Content on demand for fourth year advanced materials and manufacturing students

Wed, 18 Jul 2012 00:00:00 GMT

Content on demand for fourth year advanced materials and manufacturing students Brabazon, Dermot; Donovan, Lynda; Egan, Andrew; O'Mahony, Michael P.; Melia, Mark; Smyth, Barry There is growing recognition of the key role that social and informal learning play in Higher Education. There is also increasing interest in technologies that enable, capture and channel this type of learning to students at their point of need and personalised to their ability. The objective of this project was to leverage research technologies from the areas of adaptive hypermedia, social and semantic search to create an application to deliver learning resources to students tailored to their specific learning needs. In this project, some 130 digital learning resources, specific to a final year advanced materials and manufacturing module, were made available to the students via a Help Block plugin in the Moodle Virtual Learning Environment. The students were required to use the Help Block as a just-in-time learning resource to help them complete a continuous assessment assignment. The assignment required the students to select an advanced manufacturing process and associated material describing the manufacturing process steps, control and specifications and presenting the technological benefits of the process and material used relative to competing processes and materials. Post-trial, students were asked to complete a questionnaire to describe their experience with the Help Block in terms of whether it assisted them in completing the assignment, for example, and its ease of use. The system, evaluation findings, and some suggestions for future system enhancements are presented in the paper. ISEE 2012, 4th International Symposium of Engineering Education, The University of Sheffield, UK, 18th -20th July 2012

Health and Wealth on the Roller-Coaster: Ireland, 2003-2011

Wed, 01 May 2013 00:00:00 GMT

Health and Wealth on the Roller-Coaster: Ireland, 2003-2011 Madden, David (David Patrick) This paper reviews developments in income and health poverty in Ireland over the 2003-2011 period using data from the Survey of Income and Living Conditions (SILC). It also examines developments in the correlation between the two. Income poverty fell up to and including 2009, after which this trend is reversed. Health poverty shows less of a trend over the period though there is some evidence of a reduction in health inequality from 2006. Movements in bi-dimensional poverty are mostly driven by income poverty, but there is evidence of a reduction in the correlation between health and income poverty over the period.

The Mind and Stomach at War: Stress, British Society and the Second World War

Fri, 01 Jan 2010 00:00:00 GMT

The Mind and Stomach at War: Stress, British Society and the Second World War Miller, Ian

Let's accept a smaller slice of a shrinking cake. The Irish Congress of Trade Unions and Irish public sector unions in crisis

Thu, 01 Aug 2013 00:00:00 GMT

Let's accept a smaller slice of a shrinking cake. The Irish Congress of Trade Unions and Irish public sector unions in crisis Erne, Roland In April 2013, Irish public sector workers have overwhelmingly rejected a new national collective bargaining agreement in a union ballot. If a majority of union members in a majority of public sector unions within the Irish Congress of Trade Union (ICTU) had endorsed the proposed 'Croke Park 2' agreement, the public sector wage bill would have been cut by another 7 per cent with union approval, although public sector workers have already suffered a reduction in their earnings in the order of 25 per cent since 2009. This development raises two questions. First, why is there a sudden need for an additional one-billion-euro cut in Irish public sector pay? Secondly, why were the leaders of Ireland's biggest public sector unions - namely, SIPTU and IMPACT - campaigning for a 'yes' vote despite the pay cuts that the proposed deal entailed?

Book review of 'Anne Dufrense. Le salaire, un enjeu pour l'euro-syndicalisme. Histoire de la coordination des négotiations collectives nationales, Presses Universitaires de Nancy: Nancy, 2011'

Thu, 01 Aug 2013 00:00:00 GMT

Book review of 'Anne Dufrense. Le salaire, un enjeu pour l'euro-syndicalisme. Histoire de la coordination des négotiations collectives nationales, Presses Universitaires de Nancy: Nancy, 2011' Erne, Roland

Biofiltration of n-butyric acid for the control of odour

Mon, 01 Sep 2003 00:00:00 GMT

Biofiltration of n-butyric acid for the control of odour Sheridan, B. A.; Curran, Thomas P.; Dodd, V. A. Odour control from pig production facilities is a significant concern due to increased public awareness and the development of more stringent legislation to control production. Although many technologies exist, biofiltration is still the most attractive due to its low maintenance and operating costs. One of the key odour components, n-butyric acid, was selected for a laboratory scale biofilter study. It was examined as a sole carbon substrate in order to investigate the effectiveness of biofiltration in reducing n-butyric acid concentration under different operating conditions using a moist enriched woodchip medium. Three superficial gas velocities; 38.2, 76.4, and 114.6 m h−1 were tested for n-butyric acid concentrations ranging from 0.13 to 3.1 g [n-butyric acid] m−3 [air]. For superficial gas velocities 38.2, 76.4, and 114.6 m h−1, maximum elimination capacities (100% removal) of 148, 113 and 34.4 g m3 h−1, respectively, were achieved. Upon investigation of effective bed height, true elimination capacities (100% removal) of 230, 233 and 103 g m−3 h−1, respectively, were achieved at these superficial gas velocities. Averaged pressure drops for superficial gas velocities 38.2, 76.4, and 114.6 m h−1 were 30, 78 and 120 Pa, respectively. It was concluded that biofiltration is a viable technology for the removal of n-butyric acid from waste exhaust air, but near 100% removal efficiency is required due to the low odour detection threshold for this gaseous compound.

The influence of diet crude protein level on odour and ammonia emissions from finishing pig houses

Sun, 01 Feb 2004 00:00:00 GMT

The influence of diet crude protein level on odour and ammonia emissions from finishing pig houses Hayes, E. T.; Leek, A. B. G.; Curran, Thomas P.; Dodd, V. A.; Carton, O. T.; Beattie, V. E.; O'Doherty, J. V. Feed trials were carried out to assess the influence of crude protein content in finishing pig diets on odour and ammonia emissions. Eight pigs (4 boars and 4 gilts), average initial weight 70.8 kg (s.e. 3.167) were housed in two pens that were isolated from the rest of a pig house at University College Dublin Research Farm, Newcastle, Dublin, Ireland. Four diets containing 130, 160, 190 and 220 g kg−1 crude protein were fed during six four-week feeding periods (one treatment per room). The first week of the feeding periods served to allow odour build up in the pens and as a dietary adjustment period. The pens had partially slatted floors that were cleaned and had all the manure removed after each four-week period. Odour and ammonia concentrations were measured on days 9, 14, 16, 21 and 23 of each trial period. Odour samples were collected in Nalophan bags and analysed for odour concentration using an ECOMA Yes/No olfactometer. The odour threshold concentration was calculated according to the response of the olfactometry panel members and was displayed in OuE m−3, which referred to the physiological response from the panel equivalent to that elicited by 40 ppb v−1n-butanol evaporated in 1 m3 of neutral gas. Ammonia concentrations in the ventilation air were measured using Dräger tubes. The odour emission rates per animal for the 130, 160, 190 and 220 g kg−1 crude protein diets were 12.1, 13.2, 19.6 and 17.6 OuE s−1 animal−1, respectively (P<0.01). The odour emission rate per livestock unit (500 kg) for the 130, 160, 190 and 220 g kg−1 crude protein diets were 77.6, 80.0, 115.8 and 102.9 OuE s−1 LU−1, respectively (P<0.01). The ammonia emission rates per animal for the 130, 160, 190 and 220 g kg−1 crude protein diets were 3.11, 3.89, 5.89 and 8.27 g d−1 animal−1, respectively (P⩽0.001). There was no significant difference in the average daily intake and the average daily gain for the four diets (P>0.05). Manipulation of dietary crude protein levels would appear to offer a low cost alternative, in relation to end-of-pipe treatments, for the abatement of odour and ammonia emissions from finishing pig houses

SE—Structures and Environment: Biofiltration of Odour and Ammonia from a Pig Unit—Biofiltration of Odour and Ammonia from a Pig Unit—a pilot-scale Study

Tue, 01 Aug 2000 00:00:00 GMT

SE—Structures and Environment: Biofiltration of Odour and Ammonia from a Pig Unit—Biofiltration of Odour and Ammonia from a Pig Unit—a pilot-scale Study Sheridan, B. A.; Curran, Thomas P.; Dodd, V. A.; Colligan, J. A pilot-scale biofiltration unit was constructed at a pig finishing building on the University College Dublin research farm. The biofiltration system was investigated over three trial periods. Exhaust air from a single pen was extracted by a variable speed centrifugal fan and passed through a humidifier and biofilter. A 0·5 m depth of woodchips of over 20 mm screen size was used as the biofilter medium. The moisture content of the medium was maintained at 64±4% (wet weight basis) for trial one and 69±4% (wet weight basis) for trials two and three using a load cell method. The volumetric loading rate varied from 769 to 1898 m3 [air] m−3 [medium] h−1 during the three trial periods. Odour and ammonia removal efficiencies ranged from 77 to 95% and 54 to 93%, respectively. The pH of the biofilter leachate remained between 6 and 8 throughout the experimental periods. The pressure drop across the biofilter ranged from 14 to 64 Pa. It is concluded that a wood chip media particle size >20 mm is suitable for use in biofiltration systems on intensive pig production facilities. This will minimize the pressure drop on the system fans to reduce overall operation costs. It is recommended that a filter bed moisture content (wet weight basis) of greater than 63% be used to maintain overall efficiency. An efficient air moisturizing system (humidification and bed sprinkling) along with a properly designed air distribution system must be incorporated in the overall design when operating at such high volumetric loading rates.

A dispersion modelling approach to determine the odour impact of intensive poultry production units in Ireland

Sun, 01 Oct 2006 00:00:00 GMT

A dispersion modelling approach to determine the odour impact of intensive poultry production units in Ireland Hayes, E. T.; Curran, Thomas P.; Dodd, V. A. The use of atmospheric dispersion modelling has become more common for the determination of odour impacts from existing poultry production facilities and the assessment of setback distances for new facilities. Setback distances for broiler, layer and turkey units were determined using the atmospheric dispersion model ISCST3 and the Environmental Protection Agency (EPA, Ireland) recommended criterion (C98.1-h <= 6.0 ou(E) m(-3)) and a new odour annoyance criterion (C-98,C-1-h <= 9.7 ou(E) m(-3)) developed in this study. For a typical size unit in Ireland, maximum setback distances of 660, 665 and 1035 in were calculated for 40,000 broilers, 40,000 layers and 10,000 turkeys respectively at the current limit (C-98,C-1-h <= 6.0 ou(E) m(-3)). However, if the suggested odour impact criterion (C-98,C-1-h <= 9.7 ou(E) m(-3)) is implemented, the maximum setback distances decrease to 460, 500 and 785 in for broilers, layers and turkeys, respectively.

Odour and ammonia emissions from intensive pig units in Ireland

Mon, 01 May 2006 00:00:00 GMT

Odour and ammonia emissions from intensive pig units in Ireland Hayes, E. T.; Curran, Thomas P.; Dodd, V. A. Odour and ammonia emissions were measured at four intensive pig units in Ireland. Odour samples were collected on-site and analysed for odour concentration using an olfactometer. Ammonia concentrations in the exhaust ventilation air were measured using a portable sensor. The geomean odour emission rates over the four pig units were 17.2, 44.4, 4.3, 9.9 and 16.8 ouE s−1 animal−1 for dry sows, farrowing sows, first stage weaners, second stage weaners and finishers, respectively. The mean ammonia emission rates, measured at two of the units, were 12.1, 17.1, 1.4, 2.9 and 10.0 g d−1 animal−1 for dry sows, farrowing sows, first stage weaners, second stage weaners and finishers, respectively. In general, the odour and ammonia emission rates were comparable to those reported in literature, although some odour emission rate figures were noticeably lower for finishing pigs in this study. The variability in the data highlights the need for individual site assessment.

Courting, but not always serving: Perverted Burkeanism and the puzzle of Irish Parliamentary Cohesion

Sat, 01 Sep 2012 00:00:00 GMT

Courting, but not always serving: Perverted Burkeanism and the puzzle of Irish Parliamentary Cohesion Farrell, David M.; Mair, Peter; Ó Muineacháin, Séin; Wall, Matthew Paper originally prepared for Parties as Organizations and Parties as Systems, a workshop to mark the retirement of R. Kenneth Carty, UBC, Vancouver, May 19-21, 2011

Odour and ammonia emissions from intensive poultry units in Ireland

Mon, 01 May 2006 00:00:00 GMT

Odour and ammonia emissions from intensive poultry units in Ireland Hayes, E. T.; Curran, Thomas P.; Dodd, V. A. Odour and ammonia emissions were measured from three broiler, two layer and two turkey houses in Ireland. The broiler units gave a large range of odour and ammonia emission rates depending on the age of the birds and the season. A considerable variation between the odour and ammonia emission rates was evident for the two layer units which may have been due to the different manure handling systems utilised in the houses. There was relatively little difference in the odour and ammonia emissions from the two turkey houses. As a precautionary principle, odour emission rates utilised in atmospheric dispersion models should use the maximum values for broilers and turkeys (1.22 and 10.5 ou(E) s(-1) bird(-1) respectively) and the mean value for the layers depending on the manure handling system used (0.47 or 1.35 ou(E) s(-1) bird(-1).

Assessment of the influence of media particle size on the biofiltration of odorous exhaust ventilation air from a piggery facility

Sun, 01 Sep 2002 00:00:00 GMT

Assessment of the influence of media particle size on the biofiltration of odorous exhaust ventilation air from a piggery facility Sheridan, B. A.; Curran, Thomas P.; Dodd, V. A. Two pilot scale biofiltration systems were constructed and installed at the University College Dublin Research Farm, Lyons Estate. Experimental units consisting of two pens in a 12 pen pig house were sealed off from other pens. Air from each pen was extracted and treated separately in two biofiltration systems. Wood chips larger than 20 mm were selected as the medium for biofiltration system 1, whereas chips of between 10 and 16 mm were used in biofiltration system 2. The moisture content of the media was maintained at 69±4% (w.w.b.) using a load cell method. The volumetric loading rates ranged from 769 to 1847 m3 [gas] m-3 [medium] h-1 over a 63-day experimental period. Both biofilters reduced odour between 88% and 95%. Ammonia removal efficiencies ranged from 64% to 92% and 69% to 93% for biofiltration systems 1 and 2, respectively. Sulphur-containing compounds were reduced between 9-66% and -147-51% across biofiltration systems 1 and 2. The pH of the biofilters' leachate remained between 6 and 8. Pressure drop for biofilter 2 was 16 Pa greater than that of biofilter 1 at the maximum volumetric loading rate of . It is recommended that a wood chip media particle size greater than 20 mm be used for large scale operation of a biofiltration system on intensive pig production facilities to reduce the development of anaerobic zones and to minimize pressure drop on the system fans.

Transitioning to resilience and sustainability in urban communities

Tue, 23 Apr 2013 00:00:00 GMT

Transitioning to resilience and sustainability in urban communities Collier, Marcus; Nedović-Budić, Zorica; Aerts, Jeroen; Connop, Stuart; Foley, Dermot; Foley, Karen; Newport, Darryl; McQuaid, Siobhán; Slaev, Aleksander; Verburg, Peter Adapting to the challenges of rapid urban growth and societal change will require mechanisms for efficient transitioning to an embedded resilience. This has become central to the exploration of methods for achieving truly sustainable urban growth. However, while transitioning and resilience are useful descriptors, they can be abstract or conflicting ideals and their meanings obscured by a lack of concrete examples, both being barriers to many planning objectives. In this paper, we hold a lens over key issues in transitioning to resilience in urban areas by outlining emerging challenges that may offer directions towards operationalising how cities might transition to a more resilient future, while ensuring that communities are at the center of the process. The emerging and challenging areas – geospatial ICT, green infrastructure planning, novel design using collaborative responses, climate planning, limiting urban sprawl and short-circuit economic approaches – are explored as viable facets for devising and sustaining urban transition strategies. We conclude with a discussion on the need for developing a synergistic approach in practice to facilitate transition.

Quaternarized pdppz: synthesis, DNA-binding and biological studies of a novel dppz derivative that causes cellular death upon light irradiation.

Sat, 01 Jan 2011 00:00:00 GMT

Quaternarized pdppz: synthesis, DNA-binding and biological studies of a novel dppz derivative that causes cellular death upon light irradiation. Elmes, Robert B.P.; Erby, Marialuisa; Cloonan, Suzanne M.; Quinn, Susan J.; Williams, D. Clive; Gunnlaugsson, Thorfinnur The quaternarized pdppz derivative 1 was shown to bind strongly to DNA with concomitant changes in its ground and excited state photophysical properties. Furthermore, the compound also showed rapid cellular uptake, and induced apoptosis upon light irradiation in various cancer cell lines after 24 hours of incubation.

Synthesis and photophysical evaluations of fluorescent quaternary bipyridyl-1,8-naphthalimide conjugates as nucleic acid targeting agents

Mon, 16 Jan 2012 00:00:00 GMT

Synthesis and photophysical evaluations of fluorescent quaternary bipyridyl-1,8-naphthalimide conjugates as nucleic acid targeting agents Ryan, Gary J.; Elmes, Robert B.P.; Quinn, Susan J.; Gunnlaugsson, Thorfinnur A family of organic molecules containing the DNA intercalating chromophores, 4-nitro- and 4-amino 1,8-naphthalimide, conjugated to a diquat derivative by an ‘orthogonal’ phenyl spacer have been prepared and characterised. Their binding interactions with double-stranded DNA were studied by a variety of spectroscopic techniques. These charged organic compounds are found to exhibit excellent binding affinities to DNA with binding constants comparable to those exhibited by metal complexes.

A comparative picosecond transient infrared study of 1-methylcytosine and 5'-dCMP that sheds further light on the excited states of cytosine derivatives

Tue, 01 Mar 2011 00:00:00 GMT

A comparative picosecond transient infrared study of 1-methylcytosine and 5'-dCMP that sheds further light on the excited states of cytosine derivatives Keane, Páraic M.; Wojdyla, Michal; Doorley, Gerard W.; Watson, Graeme W.; Clark, Ian P.; Greetham, Gregory M.; Parker, Anthony W.; Towrie, Michael; Kelly, John M.; Quinn, Susan J. The role of N1-substitution in controlling the deactivation processes in photoexcited cytosine derivatives has been explored using picosecond time-resolved IR spectroscopy. The simplest N1-substituted derivative, 1-methylcytosine, exhibits relaxation dynamics similar to the cytosine nucleobase and distinct from the biologically relevant nucleotide and nucleoside analogues, which have longer-lived excited-state intermediates. It is suggested that this is the case because the sugar group either facilitates access to the long-lived (1)n(O)Ï * state or retards its crossover to the ground state.

Ultrafast IR spectroscopy of polymeric cytosine nucleic acids reveal the long-lived species is due to a localised state

Wed, 22 Feb 2012 00:00:00 GMT

Ultrafast IR spectroscopy of polymeric cytosine nucleic acids reveal the long-lived species is due to a localised state Keane, Páraic M.; Wojdyla, Michal; Doorley, Gerard W.; Kelly, John M.; Clark, Ian P.; Parker, Anthony W.; Greetham, Gregory M.; Towrie, Michael; Magno, Luís M.; Quinn, Susan J. The decay pathways of UV-excited cytosine polymers are investigated using picosecond time-resolved infrared spectroscopy. Similar yields of a non-emissive (1)nÏ * state are found in the single-stranded dC(30) polymer as in the dCMP monomer, but with a longer lifetime in the polymer (80 ps vs. 39 ps). A longer lifetime is also found in the d(CpC) dinucleotide. No evidence of excimer states is observed, suggesting that localised (1)nÏ * excited states are the most significant intermediates present on the picosecond timescale.

Excited state behaviour of substituted dipyridophenazine Cr(III) complexes in the presence of nucleic acids

Fri, 01 Jan 2010 00:00:00 GMT

Excited state behaviour of substituted dipyridophenazine Cr(III) complexes in the presence of nucleic acids Wojdyla, Michal; Smith, Jayden A.; Vasudevan, Suni; Quinn, Susan J.; Kelly, John M. The photophysics and photochemistry of [Cr(phen)2(dppz)]3+ and its 11,12-substituted derivatives [Cr(phen)2(X2dppz)]3+ {X = Me or F} have been studied in the presence of purine nucleotides or DNA using steady state and time-resolved absorption and luminescence spectroscopy. 5'-Adenosine monophosphate (5'-AMP) shows only a weak interaction with the excited states of each complex. By contrast they are efficiently quenched by 5'-guanosine monophosphate (5'-GMP), consistent with photo-induced electron transfer. Laser flash photolysis spectroscopy in the presence of 5'--GMP suggests that both forward and back electron-transfers are rapid. All complexes also display a strong affinity for DNA and evidence for both static and dynamic quenching mechanisms is provided.

Incandescent Porous Carbon Microspheres to Light up Cells: Solution Phenomena and Cellular Uptake

Sun, 01 Jan 2012 00:00:00 GMT

Incandescent Porous Carbon Microspheres to Light up Cells: Solution Phenomena and Cellular Uptake Duffy, Paul; Magno, Luís M.; Yadavc, Rahul B.; Roberts, Selene K.; Ward, Andrew D.; Botchway, Stanley W.; Colavita, Paula E.; Quinn, Susan J. Carbon based materials are attractive for biological applications because of their excellent biocompatibility profile. Porous carbons with high specific surface area are particularly interesting because it is possible in principle to leverage their properties to deliver high drug payloads. In this work, porous carbon microspheres with high specific surface area were prepared and studied in solution and in cells. Raman optical tweezer trapping of microspheres, excited by 532 nm, results in graphitization and incandescence in solvents that display poor heat conduction. Fluorescence confocal microscopy imaging was used to demonstrate the uptake of fluorescently labelled microspheres by cells and the ability to leverage their optical absorptivity in order to cause carbon graphitization and cell death.

Photophysical studies of CdTe quantum dots in the presence of a zinc cationic porphyrin

Mon, 24 Sep 2012 00:00:00 GMT

Photophysical studies of CdTe quantum dots in the presence of a zinc cationic porphyrin Keane, Páraic M.; Gallagher, Shane A.; Magno, Luís M.; Leising, Miriam J.; Clark, Ian P.; Greetham, Gregory M.; Towrie, Michael; Gun'ko, Yurii; Kelly, John M.; Quinn, Susan J. The photophysical properties of 2.3 nm thioglycolic acid (TGA) coated CdTe quantum dots (QDs) prepared by a reflux method have been studied in the presence of cationic meso-tetrakis(4-N-methylpyridyl) zinc porphyrin (ZnTMPyP4). Addition of the CdTe QDs to the porphyrin in H2O results in a marked red-shift and hypochromism in the porphyrin absorption spectrum, indicative of a non-covalent binding interaction with the QD surface. Only low equivalents of the quantum dot were required for complete quenching of the porphyrin fluorescence revealing that one quantum dot may quench more than one porphyrin. Similarly addition of porphyrin to the quantum dot provided evidence for very efficient quenching of the CdTe photoluminescence, suggesting the formation of CdTe'porphyrin aggregates. Definitive evidence for such aggregates was gathered using small angle X-ray spectroscopy (SAXS). Ultrafast transient absorption data are consistent with very rapid photoinduced electron transfer (1.3 ps) and the resultant formation of a long-lived porphyrin species.

'Let's Look at it Objectively': Why Phenomenology Cannot Be Naturalized

Mon, 01 Jul 2013 00:00:00 GMT

'Let's Look at it Objectively': Why Phenomenology Cannot Be Naturalized Moran, Dermot In recent years there have been attempts to integrate first-person phenomenology into naturalistic science. Traditionally, however, Husserlian phenomenology has been resolutely anti-naturalist. Husserl identified naturalism as the dominant tendency of twentieth-century science and philosophy and he regarded it as an essentially self-refuting doctrine. Naturalism is a point of view or attitude (a reification of the natural attitude into the naturalistic attitude) that does not know that it is an attitude. For phenomenology, naturalism is objectivism. But phenomenology maintains that objectivity is constituted through the intentional activity of cooperating subjects. Understanding the role of cooperating subjects in producing the experience of the one, shared, objective world keeps phenomenology committed to a resolutely anti-naturalist (or ‘transcendental’) philosophy.

Mortgage-related issues in a crisis economy: evidence from rural households in Ireland

Wed, 01 May 2013 00:00:00 GMT

Mortgage-related issues in a crisis economy: evidence from rural households in Ireland Murphy, Enda; Scott, Mark J. The recent economic crisis has demonstrated the extent to which households are exposed to the financialisation of advanced economies. Much of the debate surrounding the reasons for the crisis has centred on the role of neoliberal policies and particularly lax mortgage lending practices among financial institutions. This paper explores how neoliberal ideas were applied to property and development during the Irish house-building boom. Drawing on questionnaire survey data across five case study locations, it examines the mortgage practices of rural households during the boom period and their existing conditions in the current burst. In addition, the impacts and consequences of the neoliberalisation of the rural mortgage market for rural households within the context of the failure of these policies, a major housing crash and a neoliberal policy fix based on severe austerity measures is examined. Our results point towards the extreme hardship and stress being felt by rural households and highlight, through the lens of rural housing, the extent to which the practices and consequences of neoliberal policy in the mortgage arena are varied spatially in rural areas.

Practical Experience with Woody Biomass in a Down-Draft Gasifier

Fri, 01 Feb 2013 00:00:00 GMT

Practical Experience with Woody Biomass in a Down-Draft Gasifier Wolff, Deidre; Walsh, Eilín; McDonnell, Kevin Gasification is the cleanest method of obtaining energy from fossil fuels, but with increasing awareness of depleting fossil fuel reserves attention has shifted towards renewable sources of energy. Any carbonaceous material can be gasified to generate high-value end-products from otherwise potentially low-value materials. Gasification can also generate energy from purpose-grown bioenergy crops, and Ireland has an ideal climate to produce woody biomass for energy generation. This update outlines some preliminary results from an investigation into the most suitable woody feedstock for small-scale localised gasification to produce a synthetic gas suitable for use in internal combustion engines. Argentinean- and German-standard wood pellets and Irish-grown willow chips were gasified in a down-draft gasifier. Operation of the gasifier led to the observation that the willow chips bridged within the feedstock hopper which prevented completion of gasification. Implementing a stirring bar in the feedstock hopper prevented bridging and gasification was then successful. Collection of the gas produced during gasification of willow chip was unsuccessful, however gas composition analysis indicates pellets which meet the German-standard are more suitable than Argentinean-standard pellets for use in a down-draft gasifier; work is underway to determine the composition of willow-derived synthetic gas to determine the most suitable feedstock for decentralised gasification by rural communities in Ireland as part of smart farming systems.

Identifying set-aside features for bird conservation and management in northeast Iberian pseudo-steppes

Fri, 30 Jul 2010 00:00:00 GMT

Identifying set-aside features for bird conservation and management in northeast Iberian pseudo-steppes McMahon, Barry J.; Giralt, David; Raurell, Montse; Brotons, Lluís; Bota, Gerard Capsule. Set-aside (land temporally removed from agricultural production) features and their regional locations influence steppe-bird species of conservation concern in Catalonia. Aims. To identify set-aside features important to the ecology of four ground nesting species, namely Little Bustard Tetrax tetrax, Stone-curlew Burhinus oedicnemus, Greater Short-toed Lark Calandrella brachydactyla and Calandra Lark Melanocorypha calandra. Methods. Set-aside fields were surveyed in four regions of Catalonia (northeast of Spain) for the selected species during the 2004 and 2005 breeding seasons. Set-aside habitat descriptors (e.g. size, vegetation structure) were collected. Ordination plots and information theoretic methods were used to assess the relationship between the selected bird species, set-aside features and the regions. Results. The region where the set-aside was located had a strong effect on the abundance of the selected species. In addition, vegetation coverage, field shape of set-aside and surrounding natural habitats were critical features, but with contrasting effects on the different species. Conclusion. Populations of the selected species of conservation concern could be improved by effective management of set-aside. As selected species responded differently, we recommend that management at local level should take into account the conservation value at a regional level of the protected area for each of the selected species.

A comparison of winter bird communities in agricultural grassland and cereal habitats in Ireland: implications for Common Agricultural Policy reform

Wed, 16 Jan 2013 00:00:00 GMT

A comparison of winter bird communities in agricultural grassland and cereal habitats in Ireland: implications for Common Agricultural Policy reform McMahon, Barry J.; Carnus, Tim; Whelan, John Capsule. In winter, grassland sites had greater bird numbers compared to winter cereals, but a number of species of conservation concern were exclusively recorded on winter cereals. Aims. To compare the winter bird communities in grassland and winter cereal fields. Methods. Grassland and winter cereal fields were surveyed for overwintering birds in a landscape of mixed grassland and arable agriculture. Results. Generalized Linear Models demonstrated that total bird abundance, the mean abundance of the majority of ecological groups and that of several common species, were significantly greater in grassland compared with winter cereal fields. However, a number of species of conservation concern, e.g. Skylark Aluda arvensis, were observed only on winter cereal fields. Only a minority of bird variables showed a positive response to field size. Of these, total bird species richness and the Shannon and Simpson's diversity indices showed positive significant responses to increasing field size, which may alternatively and perhaps more correctly be interpreted as a positive response to field boundary density within the farmed landscape. Conclusions. Farmland habitats are important for the provision of overwintering resources for birds, and policy directed towards bird conservation should target the management of locally significant habitat types. The implications of these findings are discussed in light of the proposed revision of the Common Agricultural Policy in 2014, particularly the proposed measure for crop diversification.

The Chemistry of Famine: Nutritional Controversies and the Irish Famine c.1845-7

Wed, 24 Oct 2012 00:00:00 GMT

The Chemistry of Famine: Nutritional Controversies and the Irish Famine c.1845-7 Miller, Ian The activities of Irish medical practitioners in relieving the impact of the Irish Famine (c.1845–52) have been well documented. However, analysis of the function of contemporary medico-scientific ideas relating to food has remained mostly absent from Famine historiography. This is surprising, given the burgeoning influence of Liebigian chemistry and the rising social prominence of nutritional science in the 1840s. Within this article, I argue that the Famine opened up avenues for advocates of the social value of nutritional science to engage with politico-economic discussion regarding Irish dietary, social and economic transformation. Nutritional science was prominent within the activities of the Scientific Commission, the Central Board of Health and in debates regarding soup kitchen schemes. However, the practical inefficacy of many scientific suggestions resulted in public associations being forged between nutritional science and the inefficiencies of state relief policy, whilst emergent tensions between the state, science and the public encouraged scientists in Ireland to gradually distance themselves from state-sponsored relief practices.

Whatever happened to the third paradigm? Exploring mixed methods research designs in sport and exercise psychology

Wed, 09 Nov 2011 00:00:00 GMT

Whatever happened to the third paradigm? Exploring mixed methods research designs in sport and exercise psychology Moran, Aidan P.; Matthews, James; Kirby, Kate In the past, quantitative and qualitative approaches to research were portrayed as being incompatible, if not mutually exclusive. More recently, however, researchers have explored the possible complementarity of these approaches through mixed methods research (MMR) the so-called third research paradigm. The purpose of this paper is to explore the nature and implications of mixed methods designs for research in sport and exercise psychology. Having sketched the nature and origins of MMR, we highlight some advantages it offers to researchers in sport and exercise psychology. After that, we conclude by identifying some barriers to progress in using mixed methods research in this latter field.

Mental imagery, action observation and skill learning

Fri, 01 Jun 2012 00:00:00 GMT

Mental imagery, action observation and skill learning Moran, Aidan P.; Campbell, Mark; Holmes, Paul; MacIntyre, Tadhg

Functional equivalence or behavioural matching? A critical reflection on 15 years of research using the PETTLEP model of motor imagery

Tue, 02 Oct 2012 00:00:00 GMT

Functional equivalence or behavioural matching? A critical reflection on 15 years of research using the PETTLEP model of motor imagery Wakefield, Caroline; Smith, Dave; Moran, Aidan P.; Holmes, Paul Motor imagery, or the mental rehearsal of actions in the absence of physical movement, is an increasingly popular construct in fields such as neuroscience, cognitive psychology and sport psychology. Unfortunately, few models of motor imagery have been postulated to date. Nevertheless, based on the hypothesis of functional equivalence between imagery, perception and motor execution, Holmes and Collins in 2001 developed the PETTLEP model of motor imagery in an effort to provide evidence-based guidelines for imagery practice in sport psychology. Given recent advances in theoretical understanding of functional equivalence, however, it is important to provide a contemporary critical reflection on motor imagery research conducted using this model. The present article addresses this objective. We begin by explaining the background to the development of the PETTLEP model. Next, we evaluate key issues and findings in PETTLEP-inspired research. Finally, we offer suggestions for, and new directions in, research in this field.

The importance of laboratory water quality for studying initial bacterial adhesion during NF filtration processes

Wed, 15 May 2013 00:00:00 GMT

The importance of laboratory water quality for studying initial bacterial adhesion during NF filtration processes Correia-Semiao, Andrea Joana; Habimana, O.; Cao, H.; Heffernan, R.; Safari, Ashkan; Casey, Eoin Biofouling of nanofiltration (NF) and reverse osmosis (RO) membranes for water treatment has been the subject of increased research effort in recent years. A prerequisite for undertaking fundamental experimental investigation on NF and RO processes is a procedure called compaction. This involves an initial phase of clean water permeation at high pressures until a stable permeate flux is reached. However water quality used during the compaction process may vary from one laboratory to another. The aim of this study was to investigate the impact of laboratory water quality during compaction of NF membranes. A second objective was to investigate if the water quality used during compaction influences initial bacterial adhesion. Experiments were undertaken with NF270 membranes at 15 bar for permeate volumes of 0.5L, 2L, and 5L using MilliQ, deionized or tap water. Membrane autopsies were performed at each permeation point for membrane surface characterisation by contact angle measurements, profilometry, and scanning electron microscopy. The biological content of compacted membranes was assessed by direct epi-fluorescence observation following nucleic acid staining. The compacted membranes were also employed as substrata for monitoring the initial adhesion of Ps. fluorescens under dynamic flow conditions for 30 minutes at 5 minutes intervals. Compared to MilliQ water, membrane compaction using deionized and tap water led to decreases in permeate flux, increase in surface hydrophobicity and led to significant buildup of a homogenous fouling layer composed of both living and dead organisms (>10⁶cells.cm−2). Subsequent measurements of bacterial adhesion resulted in cell loadings of 0.2×10⁵, 1.0×10⁵cells×cm−2 and 2.6×10⁵ cells.cm−2 for deionized, tap water and MilliQ water, respectively. These differences in initial cell adhesion rates demonstrate that choice of laboratory water can significantly impact the results of bacterial adhesion on NF membranes. Standardized protocols are therefore needed for the fundamental studies of bacterial adhesion and biofouling formation on NF and RO membrane. This can be implemented by first employing pure water during all membrane compaction proceduresand for the modelled feed solutions used in the experiment.

The Microbial Cell Factory

Wed, 14 Mar 2012 00:00:00 GMT

The Microbial Cell Factory Murphy, Cormac D. Microorganisms have been used for decades as sources of antibiotics, vitamins and enzymes and for the production of fermented foods and chemicals. In the 21st century microorganisms will play a vital role in addressing some of the problems faced by mankind. In this article three of the current applications in which microbes have a significant role to play are highlighted: the discovery of new antibiotics, manufacture of biofuels and bioplastics, and production of fine chemicals via biotransformation.

From Symbolism to Futurism: Poupées Électriques and Elettricità

Mon, 01 Jun 2009 00:00:00 GMT

From Symbolism to Futurism: Poupées Électriques and Elettricità Daly, Selena In this paper I examine how Filippo Tommaso Marinetti transformed his three-act drama Poupées Électriques (1909) into a one-act Futurist sintesi Elettricità (1913). Through the analysis of draft versions of Elettricità and of Futurist manifestos, both the process by which Marinetti enacted this textual transformation and the reasons behind the changes made to the French play in its passage to becoming an Italian playlet will be explored. A series of drafts for Elettricità, which are held at the F. T. Marinetti Papers Collection at the Beinecke Library, Yale University, uncover the progression from French original to Italian translation. Close textual analysis of the two plays will demonstrate how Marinetti sought to change elements of Poupées Électriques so that Elettricità would reflect his new Futurist world vision. The significance of many of the changes Marinetti made only becomes clear when Elettricità is contextualised within other developments in the Futurist ideology and to Marinetti's manifesto output.

Measuring evapotranspiration of hardy ornamental nursery stock: a hurdle for irrigation management

Tue, 01 Jan 2013 00:00:00 GMT

Measuring evapotranspiration of hardy ornamental nursery stock: a hurdle for irrigation management Grant, Olga Although the land area dedicated to the production of hardy ornamental nursery stock (HONS) is relatively small, the sector places considerable demands on water supplies: production is largely in pots with limited water-holding capacity, and therefore frequent irrigation is essential. It has been shown that accurate scheduling to meet crop demand (rather than over- or under-watering) benefits quality of HONS, as well as reducing water use and run-off of nutrients and pesticides. Deficit irrigation techniques, in which plants are irrigated to replace less than 100% of the water they transpire, can further control growth and may have additional advantages, for example in reducing pests and disease. Deficit irrigation, however, requires precise scheduling to minimise the risk of excessive drying of the substrate. Numerous different species and cultivars, often at different stages in the production cycle, can be grown together on a single nursery, meaning that several different irrigation schedules need to operate at once. One option is to irrigate crops on the basis of their evapotranspiration rates. In other sectors, this entails measurement of weather conditions to calculate the evapotranspiration of a reference crop, which is then multiplied by a crop-specific factor (crop coefficient) to estimate the evapotranspiration of the crop in question. Crop coefficients, however, are not generally known for HONS. Efforts to deal with this issue, as well as alternative methods of estimating evapotranspiration using gravimetric methods or remote sensing, are reviewed in this chapter.

Teaching for better learning: a blended learning pilot project with first year geography undergraduates

Tue, 21 Sep 2010 00:00:00 GMT

Teaching for better learning: a blended learning pilot project with first year geography undergraduates Moore, Niamh; Gilmartin, Mary Internationally, recognition is growing that the transition between post-primary and higher education is raising a number of challenges for both students and educators. Simultaneously with growing class sizes, resources have become more constrained and there is a new set of expectations from the “net generation” (Mohanna, 2007, p. 211) The use of e-learning in medical education, Postgraduate Medical Journal, 83, p. 211). Within this transforming context, modes of instruction that cater for different paces of learning and learning styles by combining traditional and electronic media have become increasingly important. This paper discusses the transformation of an introductory human geography module at University College Dublin using a blended learning approach that extends beyond the media used to incorporate all aspects of, and inputs into, the learning process. Our experience highlights how blended learning can aid the achievement of a range of objectives in relation to student engagement and the promotion of deeper learning. However, blended learning is not a quick-fix solution to all issues relating to new university students and our analysis draws out a more complex relationship than anticipated between blended learning and student retention that will require further examination.

Mapping the journey towards self-authorship in Geography

Mon, 16 May 2011 00:00:00 GMT

Mapping the journey towards self-authorship in Geography Moore, Niamh; Fournier, Eric J.; Hardwick, Susan W.; Healey, Mick; MacLachlan, John; Seemann, Jörn Learning is a developmental journey, and geography curriculum plays a key role in supporting student progression. In this article, we argue that the concept of ‘self-authorship’ is a useful guiding principle in supporting curriculum revision and reform. A series of international case studies illustrate how self-authorship can be enacted in different ways within geography curricula in a range of contexts. The role of a range of collaborators and the co-curriculum in supporting the student journey are highlighted. The article concludes by suggesting that the key strength of the concept is its non-prescriptive nature.

Production of human metabolites of the anti-cancer drug flutamide via biotransformation in Cunninghamella species

Tue, 01 Feb 2011 00:00:00 GMT

Production of human metabolites of the anti-cancer drug flutamide via biotransformation in Cunninghamella species Amadio, Jessica; Murphy, Cormac D. Fungi belonging to the genus Cunninghamella have enzymes similar to those employed by mammals for the detoxification of xenobiotics, thus they are useful as models of mammalian drug metabolism, and as a source for drug metabolites. We report the transformation of the anti-cancer drug flutamide in Cunninghamella sp. The most predominant phase I metabolites present in the plasma of humans, 2-hydroxyflutamide and 4-nitro-3-(trifluoromethyl)aniline, were also produced in Cunninghamella cultures. Other phase I and phase II metabolites were also detected using a combination of HPLC, GC–MS and 19F-NMR.

Regional integration of renewable energy systems in Ireland - The role of hybrid energy systems for small communities

Tue, 01 Jan 2013 00:00:00 GMT

Regional integration of renewable energy systems in Ireland - The role of hybrid energy systems for small communities Goodbody, Craig; Walsh, Eilín; McDonnell, Kevin; Owende, Philip Due to a lack of indigenous fossil energy resources, Ireland's energy supply constantly teeters on the brink of political, geopolitical, and geographical unease. The potential risk to the security of the energy supply combined with the contribution of anthropogenic greenhouse gas emissions to climate change gives a clear indication of Ireland's need to reduce dependency on imported fossil fuels as primary energy source. A feasibility analysis to investigate the available renewable energy options was conducted using HOMER software. The net present cost, the cost of energy, and the CO2 emissions of each potential energy combination were considered in determining the most suitable renewable and non-renewable hybrid energy system. Wind energy was shown to have the greatest potential for renewable energy generation in Ireland: wind energy was a component of the majority of the optimal hybrid systems both in stand-alone and grid-connected systems. In 2010 the contribution of wind energy to gross electricity consumption in Ireland approximated 10%, and the results of this feasibility study indicate that there is great potential for wind-generated energy production in Ireland. Due to the inherent variability of wind energy the grid-connected system results are particularly relevant, which show that in more than half of the analyses investigating electrical energy demand the incorporation of wind energy offset the CO2 emissions of the non-renewable elements to such a degree that the whole system had negative CO2 emissions, which has serious implications for Kyoto Protocol emissions limits. Ireland also has significant potential for hydropower generation despite only accounting for 2% of the gross electricity consumption in 2010. Wind and hydro energy should therefore be thoroughly explored to secure an indigenous primary energy source in Ireland.

Foster care and supported lodgings for separated asylum seeking young people in Ireland: the views of young people, carers and stakeholders

Tue, 01 Jan 2013 00:00:00 GMT

Foster care and supported lodgings for separated asylum seeking young people in Ireland: the views of young people, carers and stakeholders Ní Raghallaigh, Muireann

Functional Assessment for Predicting Charge-Transfer Excitations of Dyes in Complexed State: A Study of Triphenylamine-Donor Dyes on Titania for Dye-Sensitized Solar Cells

Thu, 13 Dec 2012 00:00:00 GMT

Functional Assessment for Predicting Charge-Transfer Excitations of Dyes in Complexed State: A Study of Triphenylamine-Donor Dyes on Titania for Dye-Sensitized Solar Cells Dev, Pratibha; Agrawal, Saurabh; English, Niall J. Time-dependent density functional theory (TD-DFT) was employed to calculate the UV/vis spectra for three of the triphenylamine (TPA)-donor dyes, TC1, L1, and LJ1, in isolation as well as when complexed with a titania nanoparticle. TPA-donor dyes are a class of promising organic dyes for use in dye-sensitized solar cells (DSSCs). The three dyes studied here are among the smallest of these molecules and provide important insight into the entire series of TPA dyes that are being explored as possible sensitizers in titania-based DSSCs. An attempt to calculate the optical spectra for these dyes within the B3LYP approximation to the exchange correlation functional produces erroneous results. However, Coulomb attenuated approximation (CAM-B3LYP) captures the correct photophysics of the dyes and produces more accurate charge-transfer excitation energies of their complexes with titania. This work shows that the extent to which a given approximation fails or succeeds to correctly predict the charge-transfer excitation energies in the isolated dyes is propagated in that it fails (or succeeds) to correctly predict the values of the excitation energies for the complexes. It is, therefore, important to determine the most appropriate functional for a dye before considering it in more complicated structures such as dye-titania complexes.

Production of the Novel Lipopeptide Antibiotic Trifluorosurfactin via Precursor-Directed Biosynthesis.

Thu, 01 Nov 2012 00:00:00 GMT

Production of the Novel Lipopeptide Antibiotic Trifluorosurfactin via Precursor-Directed Biosynthesis. O'Connor, Neil K.; Rai, Dilip K.; Clark, Benjamin R.; Murphy, Cormac D. Incorporation of fluorine into antibiotics can moderate their biological activity, lipophilicity and metabolic stability. The introduction of fluorine into an antimicrobial lipopeptide produced by Bacillus sp. CS93 via precursor-directed biosynthesis is described. The lipopeptide surfactin is synthesised non-ribosomally by various Bacillus species and is known for its biological activity. Administering 4,4,4-trifluoro-dl-valine to cultures of Bacillus sp. CS93 results in the formation of trifluorosurfactin in quantities sufficient for detection by LC–MS/MS. 19F NMR analysis of the culture supernatant revealed that the bulk of the fluorinated amino acid was transformed and thus was unavailable for incorporation into surfactin. Detection of ammonia, and MS analysis indicated that the transformation proceeds with deamination and reduction of the keto acid, yielding 4,4,4-trifluoro-2-hydroxy-3-methylbutanoic acid.

Comparative studies for evaluation of CO2 fixation in the cavity of the Rubisco enzyme using QM, QM/MM and linear-scaling DFT methods

Fri, 01 Feb 2013 00:00:00 GMT

Comparative studies for evaluation of CO2 fixation in the cavity of the Rubisco enzyme using QM, QM/MM and linear-scaling DFT methods El-Hendawy, Morad M.; English, Niall J.; Mooney, Damian A. We evaluate the minimum energy configuration (MM) and binding free energy (QM/MM and QM) of CO2 to Rubisco, of fundamental importance to the carboxylation step of the reaction. Two structural motifs have been used to achieve this goal, one of which starts from the initial X-ray Protein Data Bank structure of Rubisco's active centre (671 atoms), and the other is a simplified, smaller model (77 atoms) which has been used most successfully, thus far, for study. The small model is subjected to quantum chemical density functional theory (DFT) studies, both in vacuo and using implicit solvation. The effects of the protein environment are also included by means of a hybrid quantum mechanical/molecular mechanical (QM/MM) approach, using PM6/AMBER and B3LYP/AMBER schemes. Finally, linear-scaling DFT methods have also been applied to evaluate energetic features of the large motif, and the result obtained for the binding free energy of the CO2 underlines the importance of the accurate modelling of the surrounding protein milieu using a full DFT description.