The energetics of tetrahydrocarbazole aromatization over Pd(111): A computational analysis

The carbazole moiety is a component of many important pharmaceuticals including anticancer and anti-HIV agents and is commonly utilized in the production of modern polymeric materials with novel photophysical and electronic properties. Simple carbazoles are generally produced via the aromatization of the respective tetrahydrocarbazole (THCZ). In this work, density functional theory calculations are used to model the reaction pathway of tetrahydrocarbazole aromatization over Pd(111). The geometry of each of the intermediate surface species has been determined and how each structure interacts with the metal surface addressed. The reaction energies and barriers of each of the elementary surface reactions have also been calculated, and a detailed analysis of the energetic trends performed. Our calculations have shown that the surface intermediates remain fixed to the surface via the aromatic ring in a manner similar to that of THCZ. Moreover, the aliphatic ring becomes progressively more planer with the dissociation of each subsequent hydrogen atom. Analysis of the reaction energy profile has revealed that the trend in reaction barriers is determined by the two factors: (i) the strength of the dissociating ring-H bond and (ii) the subsequent gain in energy due to the geometric relaxation of the aliphatic ring. (c) 2008 American Institute of Physics.

Reactivity of the 4d transition metals toward N hydrogenation and NH dissociation: A DFT-based HSAB analysis

The density functional theory (DFT) based hard-soft acid-base (HSAB) reactivity indices, including the electrophilicity index, have been successfully applied to many areas of molecular chemistry. In this work we test the applicability of such an approach to fundamental surface chemistry. We have considered, as prototypical surface reactions, both the hydrogenation of atomic nitrogen and the dissociative adsorption of the NH molecular radical. By use of a DFT methodology, the minimum energy reaction pathways, and corresponding reaction barriers, of the above reactions over Zr(001), Nb(110), Mo(110), Tc(001), Ru(001), Rh(111), and Pd(111) have been determined. By consideration of the chemical potential and chemical hardness of the surface metal atoms, and the principle of electronegativity equalization, it is found that the charge transferred to the NH radical during the process of dissociative adsorption correlates very well with that determined by Mulliken population analysis. Furthermore, it is found that the stability of the NH/surface transition state complex relates directly to this charge transfer and that the trend in transition state stability predicted by a HSAB; treatment correlates very strongly with that determined by DFT calculations. With regards to N hydrogenation, we find that during the course of the reaction, H loses cohesion to the surface, as it must migrate from a 3-fold hollow site to either a bridge or top site, to react with N. Partial density of states (PDOS) and Mulliken population analysis reveal that this loss of bonding is accompanied by charge transfer from H to the surface metal atoms. Moreover, by simple modeling, we show that the reaction barriers are directly proportional to this mandatory charge transfer. Indeed, it is found that the reaction barriers correlate very well with the electrophilicity index of the metal atoms.

Journal article: Children and Religion under Article 14 UNCRC: A Critical Analysis

This article examines the text of Article 14 of the UN Convention on the Rights of the Child 1989 and the work of the UN Committee on the Rights of the Child. It considers the text of the article and its travaux préparatoires; it then provides an analysis of the issues considered by the Committee: the concept of the evolving capacities of the child, freedom of religious choice, freedom of manifestation, and education. It also highlights the problems that have emerged in the Committee’s work, in the light of a theoretical framework of the right of the child to religious freedom in international law. It concludes that the Committee fails children in relation to their religion and suggests some positive steps to be taken by the Committee.

Intelligent Assembly Time Analysis Using a Digital Knowledge-Based Approach

The implementation of effective time analysis methods fast and accurately in the era of digital manufacturing has become a significant challenge for aerospace manufacturers hoping to build and maintain a competitive advantage. This paper proposes a structure oriented, knowledge-based approach for intelligent time analysis of aircraft assembly processes within a digital manufacturing framework. A knowledge system is developed so that the design knowledge can be intelligently retrieved for implementing assembly time analysis automatically. A time estimation method based on MOST, is reviewed and employed. Knowledge capture, transfer and storage within the digital manufacturing environment are extensively discussed. Configured plantypes, GUIs and functional modules are designed and developed for the automated time analysis. An exemplar study using an aircraft panel assembly from a regional jet is also presented. Although the method currently focuses on aircraft assembly, it can also be well utilized in other industry sectors, such as transportation, automobile and shipbuilding. The main contribution of the work is to present a methodology that facilitates the integration of time analysis with design and manufacturing using a digital manufacturing platform solution.

An analysis of geometric uncertainty calculations for prostate radiotherapy in clinical practice.

Margins are used in radiotherapy to assist in the calculation of planning target volumes. These margins can be determined by analysing the geometric uncertainties inherent to the radiotherapy planning and delivery process. An important part of this process is the study of electronic portal images collected throughout the course of treatment. Set-up uncertainties were determined for prostate radiotherapy treatments at our previous site and the new purpose-built centre, with margins determined using a number of different methods. In addition, the potential effect of reducing the action level from 5 mm to 3 mm for changing a patient set-up, based on off-line bony anatomy-based portal image analysis, was studied. Margins generated using different methodologies were comparable. It was found that set-up errors were reduced following relocation to the new centre. Although a significant increase in the number of corrections to a patient's set-up was predicted if the action level was reduced from 5 mm to 3 mm, minimal reduction in patient set-up uncertainties would be seen as a consequence. Prescriptive geometric uncertainty analysis not only supports calculation and justification of the margins used clinically to generate planning target volumes, but may also best be used to monitor trends in clinical practice or audit changes introduced by new equipment, technology or practice. Simulations on existing data showed that a 3 mm rather than a 5 mm action level during off-line, bony anatomy-based portal imaging would have had a minimal benefit for the patients studied in this work.

Convergence and tracking analysis of a variable normalised LMF (XE-NLMF) algorithm

The least-mean-fourth (LMF) algorithm is known for its fast convergence and lower steady state error, especially in sub-Gaussian noise environments. Recent work on normalised versions of the LMF algorithm has further enhanced its stability and performance in both Gaussian and sub-Gaussian noise environments. For example, the recently developed normalised LMF (XE-NLMF) algorithm is normalised by the mixed signal and error powers, and weighted by a fixed mixed-power parameter. Unfortunately, this algorithm depends on the selection of this mixing parameter. In this work, a time-varying mixed-power parameter technique is introduced to overcome this dependency. A convergence analysis, transient analysis, and steady-state behaviour of the proposed algorithm are derived and verified through simulations. An enhancement in performance is obtained through the use of this technique in two different scenarios. Moreover, the tracking analysis of the proposed algorithm is carried out in the presence of two sources of nonstationarities: (1) carrier frequency offset between transmitter and receiver and (2) random variations in the environment. Close agreement between analysis and simulation results is obtained. The results show that, unlike in the stationary case, the steady-state excess mean-square error is not a monotonically increasing function of the step size. (c) 2007 Elsevier B.V. All rights reserved.

Solid-state analysis of low-melting 1,3-dialkylimidazolium hexafluorophosphate salts (ionic liquids) by combined x-ray crystallographic and computational analyses

The interactions of ions in the solid state for a series of representative 1,3-dialkylimidazolium hexafluorophosphate salts (either ionic liquids or closely related) have been examined by crystallographic analysis, combined with the theoretical estimation of crystal-packing densities and lattice-interaction energies. Efficient close-packing of the ions in the crystalline states is observed, but there was no compelling evidence for specific directional hydrogen-bonding to the hexafluorophosphate anions or the formation of interstitial voids. The close-packing efficiency is supported by the theoretical calculation of ion volumes, crystal lattice energies, and packing densities, which correlated well with experimental data. The crystal density of the salts can be predicted accurately from the summation of free ion volumes and lattice energies calculated. Of even more importance for future work, on these and related salts, the solid-state density of 1,3-dialkylimidazolium hexafluorophosphate salts can be predicted with reasonable accuracy purely on the basis of on ab initio free ion volumes, and this allows prediction of lattice energies without necessarily requiring the crystal structures.

Child Welfare Interventions: Patterns of Social Work Practice

Some 10 years ago one of the authors embarked on a research study examining the potential for social workers to shift from a child protection to a child welfare practice orientation (Spratt, 2000; 2001; Spratt and Callan, 2004). The research reported here develops that work; examining how social workers respond to ‘child care problems’ (CCPs). The results indicate that Northern Irish Health and Social Services Trusts (equivalent to Local Authorities in England and Wales) have responded to social policy goals to balance the protection of a lesser number of children whilst meeting the welfare needs of the greater by reducing the number of referrals designated ‘child protection investigations’ (CPIs) and increasing the number of CCPs. Closer analysis reveals, however, that a filtering system has been developed by social workers to address perceived child protection risks within CCP cases. Paradoxically, this leads to early closure of the more concerning cases, with service provision largely confined to the least concerning. The authors argue that the ways in which social workers balance social policing and supportive functions in practice may indicate possible responses to an increase in referred families anticipated within Every Child Matters (Chief Secretary to the Treasury, 2003).

Developing critical social work in theory and in practice: child protection and communicative reason

This paper argues that a critical analysis of the ideologies that inform contemporary child care has been missing from the ‘re-focusing debate’. Such an analysis points up the necessity of reasserting a critical social work position in order to provide a basis for reconstructing practice and engaging with other social actors and their ideologies in an open and creative fashion compatible with Habermas’ aspiration of ‘communicative reason’.

Recent policy initiatives in early childhood and the challenges for the social work profession

The Labour Government in the UK has announced, as part of its launch of The Children's Plan, that it 'wants to make this country the best place in the world for children and young people to grow up' in. This latest Plan is further evidence of the surge of interest that there has been in children (and, in particular, early childhood) over the last ten years in the UK and indeed elsewhere. Many of the recent policy and practice initiatives have implications for social workers working with young children. Yet, social work as a profession, in comparison with education, has remained relatively silent on these initiatives and it is hard to find any critical analysis of these developments in terms of either their underlying discourses or their implications for social workers. This article sets out to address these gaps by providing a critical analysis of: what types of knowledge regarding the early years have gained political currency; why and how this is the case; and what the implications are for the role and practices of social workers. The article proposes that discourses of 'need' and 'provision' mask more powerful discourses of economics, social control and risk avoidance, and it concludes by advocating more critically reflexive social work practice with young children and their families.

The use of cues for attention in ancient Greek art: aspects that influence concentration in the work of art and its elements

The goal of this study is to identify cues for the cognitive process of attention in ancient Greek art, aiming to find confirmation of its possible use by ancient Greek audiences and artists. Evidence of cues that trigger attention’s psychological dispositions was searched through content analysis of image reproductions of ancient Greek sculpture and fine vase painting from the archaic to the Hellenistic period - ca. 7th -1st cent. BC. Through this analysis, it was possible to observe the presence of cues that trigger orientation to the work of art (i.e. amplification, contrast, emotional salience, simplification, symmetry), of a cue that triggers a disseminate attention to the parts of the work (i.e. distribution of elements) and of cues that activate selective attention to specific elements in the work of art (i.e. contrast of elements, salient color, central positioning of elements, composition regarding the flow of elements and significant objects). Results support the universality of those dispositions, probably connected with basic competencies that are hard-wired in the nervous system and in the cognitive processes.

Genetic differentiation of Euterpe edulis Mart. populations estimated by AFLP analysis

Heart-of-palm (Euterpe edulis Mart.) is a wild palm with a wide distribution throughout the Atlantic Rainforest. Populations of E. edulis represent important renewable natural resources but are currently under threat from predatory exploitation. Furthermore, because the species is indigenous to the Atlantic Rainforest, which is located in the most economically developed and populated region of Brazil, social and economic pressures have devastated heart-of-palm forests. In order to estimate the partitioning of genetic variation of endangered E. edulis populations, 429 AFLP markers were used to analyse 150 plants representing 11 populations of the species distribution range. Analysis of the genetic structure of populations carried out using analysis of molecular variance (AMOVA) revealed moderate genetic variation within populations (57.4%). Genetic differentiation between populations (F-ST = 0.426) was positively correlated with geographical distance. These results could be explained by the historical fragmentation of the Atlantic coastal region, together with the life cycle and mating system The data obtained in this work should have important implications for conservation and future breeding programmes of E. edulis.

Communication, recognition and social work: Aligning the ethical theories of Habermas and Honneth

The modern world is replete with ethical challenges of Orwellian proportions. The violation of human rights and misrecognition of identities are two of the most pressing examples. In this paper, the ethical theories of Habermas and Honneth are aligned as a way of addressing these specific challenges within social work. It is suggested that these theories are complementary, mutually rectifying and concordant at the meta-ethical level of analysis. The alignment is also justified, pargmatically, through the construction of three hypothetical vignettes demonstrating different kinds of practice dilemmas. The need for egalitarian communication and the imperative to recognise human identity in all its dimensions subsequently emerge as the two foundation stones for ethical deliberation in social work.

Can physical activity modulate pancreatic cancer risk?:a systematic review and meta-analysis

Numerous epidemiological studies have examined the association between physical activity and pancreatic cancer; however, findings from individual cohorts have largely not corroborated a protective effect. Among other plausible mechanisms, physical activity may reduce abdominal fat depots inducing metabolic improvements in glucose tolerance and insulin sensitivity, thereby potentially attenuating pancreatic cancer risk. We performed a systematic review to examine associations between physical activity and pancreatic cancer. Six electronic databases were searched from their inception through July 2009, including MEDLINE and EMBASE, seeking observational studies examining any physical activity measure with pancreatic cancer incidence/mortality as an outcome. A random effects model was used to pool individual effect estimates evaluating highest vs. lowest categories of activity. Twenty-eight studies were included. Pooled estimates indicated a reduction in pancreatic cancer risk with higher levels of total (five prospective studies, RR: 0.72, 95% CI: 0.52-0.99) and occupational activity (four prospective studies, RR: 0.75, 95% CI: 0.59-0.96). Nonsignificant inverse associations were seen between risks and recreational and transport physical activity. When examining exercise intensity, moderate activity appeared more protective (RR: 0.79, 95% CI: 0.52-1.20) than vigorous activity (RR: 0.97, 95% CI: 0.85-1.11), but results were not statistically significant and the former activity variable incorporated marked heterogeneity. Despite indications of an inverse relationship with higher levels of work and total activity, there was little evidence of such associations with recreational and other activity exposures.

History of Child Welfare and Protection Social Work in Northern Ireland: Finding Continuity amongst Discontinuity in Case Files from 1950-1968

This article reports on research carried out on 200 child welfare files from the largest welfare authority in Northern Ireland from 1950-1968. The literature review provides a commentary on some of the major debates surrounding child welfare and protection social work from the perspective of its historical development. The report of the research which follows offers an insight into one core, and less well-known period of child welfare history in Northern Ireland between the two Children and Young Persons Acts (1950 & 1968). Using a method of discourse analysis influenced by Michel Foucault, a detailed description of the nature of practice is offered. This paper is offered as a work in progress, with further work being planned for dissemination of more detailed analysis of the method and outcomes. The research seeks to ask a few core questions based on problems identified in the present with our current understandings of child welfare and protection histories. While recognising the limitations of this study and the need for broader analysis of the wider context surrounding child welfare practice at the moment, it is argued that some salient conclusions can be drawn about continuity and discontinuity in practice which are of interest to practitioners and students of child welfare social work.