One-pot two-step mechanochemical synthesis: ligand and complex preparation without isolating intermediates

Although the use of ball milling to induce reactions between solids (mechanochemical synthesis) can provide lower-waste routes to chemical products by avoiding solvent during the reaction, there are further potential advantages in using one-pot multistep syntheses to avoid the use of bulk solvents for the purification of intermediates. We report here two-step syntheses involving formation of salen-type ligands from diamines and hydroxyaldehydes followed directly by reactions with metal salts to provide the corresponding metal complexes. Five salen-type ligands 2,2'-[1,2-ethanediylbis[(E)-nitrilomethylidyne]] bisphenol, ` salenH2', 1; 2,2'-[(+/-)-1,2-cyclohexanediylbis-[(E)-nitrilomethylidyne]] bis-phenol, 2; 2,2'-[1,2-phenylenebis( nitrilomethylidyne)]-bis-phenol, ` salphenH2' 3; 2-[[(2-aminophenyl) imino] methyl]-phenol, 4; 2,2'-[(+/-)-1,2-cyclohexanediylbis[(E)-nitrilomethylidyne]]-bis[4,6-bis(1,1-dimethylethyl)]-phenol, ` Jacobsen ligand', 5) were found to form readily in a shaker-type ball mill at 0.5 to 3 g scale from their corresponding diamine and aldehyde precursors. Although in some cases both starting materials were liquids, ball milling was still necessary to drive those reactions to completion because precipitation of the product and or intermediates rapidly gave in thick pastes which could not be stirred conventionally. The only ligand which required the addition of solvent was the Jacobsen ligand 5 which required 1.75 mol equivalents of methanol to go to completion. Ligands 1-5 were thus obtained directly in 30-60 minutes in their hydrated forms, due to the presence of water by-product, as free-flowing yellow powders which could be dried by heating to give analytically pure products. The one-armed salphen ligand 4 could also be obtained selectively by changing the reaction stoichiometry to 1 : 1. SalenH(2) 1 was explored for the onepot two-step synthesis of metal complexes. In particular, after in situ formation of the ligand by ball milling, metal salts (ZnO, Ni(OAc)2 center dot 4H(2)O or Cu(OAc)(2)center dot H2O) were added directly to the jar and milling continued for a further 30 minutes. Small amounts of methanol (0.4-1.1 mol equivalents) were needed for these reactions to run to completion. The corresponding metal complexes [M(salen)] (M = Zn, 6; Ni, 7; or Cu, 8) were thus obtained quantitatively after 30 minutes in hydrated form, and could be heated briefly to give analytically pure dehydrated products. The all-at-once ` tandem' synthesis of [Zn(salen)] 6 was also explored by milling ZnO, ethylene diamine and salicylaldehyde together in the appropriate mole ratio for 60 minutes. This approach also gave the target complex selectively with no solvent needing to be added. Overall, these syntheses were found to be highly efficient in terms of time and the in avoidance of bulk solvent both during the reaction and for the isolation of intermediates. The work demonstrates the applicability of mechanochemical synthesis to one-pot multi-step strategies.

Comparative Law and European Harmonisation - a Match Made in Heaven or Uneasy Bedfellows?

Developing the controversy indicated in the heading, this article will proceed as follows. It establishes a notion of critical comparative law, by showing how comparative law may be capable of providing critique and analysis of law-making through judicial and legislative activity at a European level. This is followed by an exemplary discussion of how comparative law is actually used in relation to European harmonisation through case law, legislation and “soft law”. The question will then be asked whether and how these uses would change under a critical approach to comparative law. The discussion will focus on industrial relations and equality law.
In both fields, recent ECJ case law has proved controversial: This article submits that such controversy could partly be avoided by making better use of critical comparative law in deciding cases and in choosing adequate forms and content of legislation.

Dublin’s ephemeral and imaginary architectures

In 1989, the Irish architectural practice O’Donnell and Tuomey were commissioned to build a temporary pavilion to represent Ireland at the 11 Cities/11 Nations exhibition at Leeuwarden in the Netherlands. Citing Peter Smithson, John Tuomey suggested the pavilion, which drew inspirations from the forms and materials of the modern Irish barn, embodied an intention ‘not just to build but to communicate’. Its subsequent reassembly for the inauguration of the Irish Museum of Modern Art in the courtyard of the seventeenth-century Royal Hospital Kilmainham in Dublin in 1991, drew comparisons between the urban sophistication of this colonial building, its svelte new refit, and the rural expression of O’Donnell + Tuomey’s barn. It was, one critic recently noted, as if ‘a wedding had been crashed by a country cousin who had forgotten to clean his boots’.
It has been argued that temporary or ephemeral pieces of architecture, unburdened by the traditional constraints of firmitas or utilitas, have the ability to offer a concise distillation of meaning and intention. Approaching the qualities of rhetoric, such architectures share similarities with the monument and yet differ in fundamental ways. Their rapid construction in lightweight materials can allow for an almost instantaneous negotiation of zeitgeist. And, unlike the monument, from the outset the space and form of these installations is designed to disappear.
This paper analyses the ephemeral architectures of Dublin in the modern period contextualising their qualities and intentions as they manifest themselves across colonial, post-colonial and contemporary epochs. It finds origins in the theatrical sets of the late eighteenth century and traces their movements into the semi-public sphere of the pleasure garden and finally into the theatre of the streets. It is here that temporary architecture in the city has been at its most potent, allowing the amplification or subversion of the meanings of much larger spaces. Historically, much of Dublin’s most conspicuous instances of ephemeral architecture have been realised as a means of articulating mass spectacle in political, religious or nationalistic events. And while much of this has sought to confirm dominant ideologies, it has also been possible to discern moments of opposition.
The contemporary period, however, has arguably witnessed a shift in ephemeral architectures from explicitly representing ‘positive ideologies’ towards something more oblique or nebulous. This turn towards abstraction in form and space has rendered an especially communicative form of architecture particularly elusive. By examining continuities within the apparent disjuncture between historical and contemporary examples, this paper begins to unpick the language of recent ephemeral architecture in Dublin and situate it within wider global trends where political and economic imperatives are often simultaneously obscured and expressed in public space by a vocabulary of universality. As Jurgen Habermas has suggested, the contemporary value given to the transitory and the ephemeral ‘discloses a longing for an undefiled, immaculate and stable present’.

Austerity and Reform of the Irish Public Administration

The impact of the global financial crisis has been particularly severe in Ireland, and the 2008-14 period has been one defined by considerable state retrenchment. It has, however, also given rise to a period of unprecedented public service reform, and particularly following the election of a government with a strong reforming mandate in 2011. In this paper, the context and content of the reforms are examined along institutional, financial and politico-administrative dimensions respectively. A final section discusses the politics of reform in a time of crisis.

Psychosocial interventions to improve quality of life and emotional wellbeing in newly diagnosed cancer patients

Title
Psychosocial interventions to improve quality of life and emotional wellbeing for recently diagnosed cancer patients.

Background
Despite clear guidelines recommending the provision of emotional support for cancer patients, we do not know how best to address psychological distress in this group.

Aim
To assess the effects of psychosocial interventions to improve quality of life (QoL) and general psychological distress newly diagnosed cancer patients.

Methods
We searched electronic sources for RCTs of psychosocial interventions or ‘talking therapies’ with individual newly diagnosed cancer patients. Only trials measuring QoL and general psychological distress were included. Meta-analyses examined subgroups by outcome measurement, mode of delivery and discipline of trained helper.

Results
Thirty trials met the criteria. No significant effects were observed for QoL at 6-months (SMD 0.11; 95% CI -0.00 to 0.22) except when using cancer-specific measures (SMD 0.16; 95% CI 0.02 to 0.30). Sub-group analyses revealed that psycho-educational, nurse-delivered interventions improved QoL (SMD 0.23; 95% CI 0.04 to 0.43). General psychological distress as assessed by ‘mood measures’ improved (SMD - 0.81; 95% CI -1.44 to -0.18), but heterogeneity was a factor.

Discussion and conclusion
Psychosocial interventions vary in format and content, raising concerns about heterogeneity, despite appearing to have a beneficial impact on cancer-specific QoL and mood. Future research should concentrate on screening for emotional support needs and identifying common elements within interventions that are of value. Authors should carefully select outcome measures that are appropriately sensitive to change.

Psychosocial interventions to improve quality of life and emotional wellbeing in newly diagnosed cancer patients

Title
Psychosocial interventions to improve quality of life and emotional wellbeing for recently diagnosed cancer patients.

Background
Despite clear guidelines recommending the provision of emotional support for cancer patients, we do not know how best to address psychological distress in this group.

Aim
To assess the effects of psychosocial interventions to improve quality of life (QoL) and general psychological distress newly diagnosed cancer patients.

Methods
We searched electronic sources for RCTs of psychosocial interventions or ‘talking therapies’ with individual newly diagnosed cancer patients. Only trials measuring QoL and general psychological distress were included. Meta-analyses examined subgroups by outcome measurement, mode of delivery and discipline of trained helper.

Results
Thirty trials met the criteria. No significant effects were observed for QoL at 6-months (SMD 0.11; 95% CI -0.00 to 0.22) except when using cancer-specific measures (SMD 0.16; 95% CI 0.02 to 0.30). Sub-group analyses revealed that psycho-educational, nurse-delivered interventions improved QoL (SMD 0.23; 95% CI 0.04 to 0.43). General psychological distress as assessed by ‘mood measures’ improved (SMD - 0.81; 95% CI -1.44 to -0.18), but heterogeneity was a factor.

Discussion and conclusion
Psychosocial interventions vary in format and content, raising concerns about heterogeneity, despite appearing to have a beneficial impact on cancer-specific QoL and mood. Future research should concentrate on screening for emotional support needs and identifying common elements within interventions that are of value. Authors should carefully select outcome measures that are appropriately sensitive to change.

Living in the Landscape: Essays in Honour of Graeme Barker

This edited volume reflects on the multitude of ways by which humans shape and are shaped by the natural world, and how Archaeology and its cognate disciplines recover this relationship. The structure and content of the book recognize Graeme Barker’s pioneering contribution to the scientific study of human-environment interaction, and form a secondary dialectic between his many colleagues and past students and the academic vista which he has helped define. The volume comprises 22 thematic papers, arranged chronologically, each a presentation of front-line research in their respective fields. They mirror the scope of Barker’s legacy through a focus on transitions in the human-environment relationship, how they are enacted and perceived. The assembled chapters illustrate how climate, demographic, subsistence, social and ecological change have affected cultures from the Palaeolithic to Historical, from North Africa and West-Central Eurasia to Southeast Asia and China. They also chronicle the innovations and renegotiated relations that communities have devised to meet and exploit the many shifting realities involved with Living in the Landscape.

Distinguishing Species of Geoemyclid and Trionychid Turtles from Shell Fragments:Evidence from the Pleistocene at Niah Caves, Sarawak

Fragments of chelonian carapace and plastral dermal plates are well-represented from archaeological sites in the world's dry and wet tropics. However, although these bones are easily identified at an element level, few archaeological reports have explored the potential of using features of form and surface sculpturing as a way to refine that identification to genus or species. The ability to achieve such a refinement would benefit environmental and human subsistence strategy models alike. The objective of the current paper was to isolate recurrent and readily visible surface characteristics on the dermal plates from a selection of commonly occurring Southeast Asian hard- and soft-shelled turtles. Using these criteria, analysis is made of the chelonian assemblage from pre- and post-Last Glacial Maximum (LGM) cultural deposits in the West Mouth of Niah Cave. Copyright (C) 2009 John Wiley & Sons, Ltd.

Activity and coke formation of nickel and nickel carbide in dry reforming: A deactivation scheme from density functional theory

Dry reforming is a promising reaction to utilise the greenhouse gases CO2 and CH4. Nickel-based catalysts are the most popular catalysts for the reaction, and the coke formation on the catalysts is the main obstacle to the commercialisation of dry reforming. In this study, the whole reaction network of dry reformation on both flat and stepped nickel catalysts (Ni(111) and Ni(211)) as well as nickel carbide (flat: Ni3C(001); stepped: Ni3C(111)) is investigated using density functional theory calculations. The overall reaction energy profiles in the free energy landscape are obtained, and kinetic analyses are utilised to evaluate the activity of the four surfaces. By careful examination of our results, we find the following regarding the activity: (i) flat surfaces are more active than stepped surfaces for the dry reforming and (ii) metallic nickel catalysts are more active than those of nickel carbide, and therefore, the phase transformation from nickel to nickel carbide will reduce the activity. With respect to the coke formation, the following is found: (i) the coke formation probability can be measured by the rate ratio of CH oxidation pathway to C oxidation pathway (r(CH)/r(C)) and the barrier of CO dissociation, (ii) on Ni(111), the coke is unlikely to form, and (iii) the coke formations on the stepped surfaces of both nickel and nickel carbide can readily occur. A deactivation scheme, using which experimental results can be rationalised, is proposed. 

Larval development of the pedunculate barnacles Octolasmis angulata Aurivillius 1894 and Octolasmis cor Aurivillius 1892 (Cirripedia: Thoracica: Poecilasmatidae) from the gills of the mud crab, Scylla tranquebarica Fabricius, 1798

Detailed studies of larval development of Octolasmis angulata and Octolasmis cor are pivotal in understanding the larval morphological evolution as well as enhancing the functional ecology. Six planktotrophic naupliar stages and one non-feeding cyprid stage are documented in details for the first time for the two species of Octolasmis. Morphologically, the larvae of O. angulata and O. cor are similar in body size, setation patterns on the naupliar appendages, labrum, dorsal setae-pores, frontal horns, cyprid carapace, fronto-lateral gland pores, and lattice organs. Numbers of peculiarities were observed on the gnathobases of the antennae and mandible throughout the naupliar life-cycle. The setation pattern on the naupliar appendages are classified based on the segmentation on the naupliar appendages. The nauplius VI of both species undergoes a conspicuous change before metamorphosis into cyprid stage. The cyprid structures begin to form and modify beneath the naupliar body towards the end of stage VI. This study emphasises the importance of the pedunculate barnacle larval developmental studies not only to comprehend the larval morphological evolution but also to fill in the gaps in understanding the modification of the naupliar structures to adapt into the cyprid life-style.

New suburbia: designing in urban resilience by closing resource cycles

By utilising a research by design methodology, the paper develops a process-based and phased design to develop a new emergent form to these neighbourhoods, one in which new productive systems are embedded into the city, at a small-scales. These include a peak-load hydro-electric project in Ligoneal; a productive landscape in Glen Cairn and a city-wide energy refurbishment utilising neighbourhood waste streams.

The three projects illustrate different ways in which place-based solutions can enact urban transformation through a process of rigorous visualisation of process, and its attendant changes in content and form of the neighbourhood, These designs, based around a process-based strategy plan, allow for a roadmap for development to be created that could change the modus operandi of an area over a relatively short period of time,. The paper demonstrates that even modest investments of productive technologies at a local scale can fundamentally change the form and the economic and environmental operation of the city in the future, and create a new resilient city, one that can have resilience built-in. This resilience allows the neighbourhood to be less externally dependent on resources, economically active and more socially just.

Economic Ideas and the Political Construction of the Financial Crash of 2008

This article is a short introduction to a special section on economic ideas and the political construction of the financial crash. It begins by explaining why economic ideas and the politics of appeals to certain ideas are so integral to the historical significance of the crash of 2008 and the question of whether it can be considered a crash at all. The first section covers the literature on ideas and economic crisis. The second section highlights that the contribution of the special section is to engage in a stock taking exercise of the empirical and conceptual patterns concerning the politics of ideational change underway in the areas of: comparative fiscal policy; monetary policy and Euro zone debt management; capital controls; and financial and securities market regulation and standard setting. The final section outlines the structure of this special section and content of the individual articles.

Improving appropriate polypharmacy for older people in primary care: selecting components of an evidence-based intervention to target prescribing and dispensing.

Background
The use of multiple medicines (polypharmacy) is increasingly common in older people. Ensuring that patients receive the most appropriate combinations of medications (appropriate polypharmacy) is a significant challenge. The quality of evidence to support the effectiveness of interventions to improve appropriate polypharmacy is low. Systematic identification of mediators of behaviour change, using the Theoretical Domains Framework (TDF), provides a theoretically robust evidence base to inform intervention design. This study aimed to (1) identify key theoretical domains that were perceived to influence the prescribing and dispensing of appropriate polypharmacy to older patients by general practitioners (GPs) and community pharmacists, and (2) map domains to associated behaviour change techniques (BCTs) to include as components of an intervention to improve appropriate polypharmacy in older people in primary care.

Methods
Semi-structured interviews were conducted with members of each healthcare professional (HCP) group using tailored topic guides based on TDF version 1 (12 domains). Questions covering each domain explored HCPs’ perceptions of barriers and facilitators to ensuring the prescribing and dispensing of appropriate polypharmacy to older people. Interviews were audio-recorded and transcribed verbatim. Data analysis involved the framework method and content analysis. Key domains were identified and mapped to BCTs based on established methods and discussion within the research team.

Results
Thirty HCPs were interviewed (15 GPs, 15 pharmacists). Eight key domains were identified, perceived to influence prescribing and dispensing of appropriate polypharmacy: ‘Skills’, ‘Beliefs about capabilities’, ‘Beliefs about consequences’, ‘Environmental context and resources’, ‘Memory, attention and decision processes’, ‘Social/professional role and identity’, ‘Social influences’ and ‘Behavioural regulation’. Following mapping, four BCTs were selected for inclusion in an intervention for GPs or pharmacists: ‘Action planning’, ‘Prompts/cues’, ‘Modelling or demonstrating of behaviour’ and ‘Salience of consequences’. An additional BCT (‘Social support or encouragement’) was selected for inclusion in a community pharmacy-based intervention in order to address barriers relating to interprofessional working that were encountered by pharmacists.

Conclusions
Selected BCTs will be operationalised in a theory-based intervention to improve appropriate polypharmacy for older people, to be delivered in GP practice and community pharmacy settings. Future research will involve development and feasibility testing of this intervention.

Designing Bare Essentials: Aldi, Lidle and the architectures of cheapness

They’re cheap. They’re in every settlement of significance in Britain, Ireland and elsewhere. We all use them but perhaps do not always admit to it. Especially, if we are architects.
Over the past decades Aldi/Lidl low cost supermarkets have escaped from middle Europe to take over large tracts of the English speaking world remaking them according to a formula of mass-produced sheds, buff-coloured cobble-lock car parks, logos in primary colours, bare-shelves and eclectic special offers. Response within architectural discourse to this phenomenon has been largely one of indifference and such places remain, perhaps reiterating Pevsner’s controversial insights into the bicycle shed, on the peripheries of what we might term architecture. This paper seeks to explore the spatial complexities of the discount supermarket and in doing so open up a discussion on the architecture of cheapness. As a road-map, it takes former managing director Dieter Brandes’ treatise on the Aldi formula, Bare Essentials: the Aldi Way to Retailing, and investigates the strategies through which economic exigencies manifest themselves in a series of spatial tactics which involve building. Central to this is the idea of architecture as system rather than form and, in Aldi/Lidl’s case, the result of a spatial network of flows. To understand the architecture of the supermarket, then, it is necessary to measure the times and spaces of supply across the scales of intersection between global and local.
Evaluating the energy, economy and precision of such systems challenges the liminal position of the commercial, the placeless and especially the cheap within architectural discourse. As is well known, architectures of mass-production and prefabrication and their origins exercised modernist thinkers such as Sigfried Giedion and Walter Gropius in the early twentieth century and has undergone a resurgence in recent times. Meanwhile, the mapping of the hitherto overlooked forms and iconography of commerce in Learning from Las Vegas (1971) was extended by Rem Koolhaas et al into an investigation of the technologies, systems and precedents of retail in the Harvard Design School Guide to Shopping, thirty years later in 2001. While obviously always a criteria for building, to find writings on architecture which explicitly celebrate cheapness as a design virtue or, indeed, even iterate the word cheap is more difficult. Walter Gropius’ essay ‘How can we build cheaper, better, more attractive houses?’ (1927), however, situates the cheap within the discussions – articulated, amongst others, by Karl Teige and Bruno Taut – surrounding the minimal dwelling and the moral benefits of absence of the 1920s and 30s.
In our contemporary age of heightened consumption, it is perhaps fitting that an architecture of bare essentials is defined in retail rather than in housing, a commercial existenzminimum where the Miesian paradox of ‘less is more’ is resold as a paradigm of ‘more for less’ in the ubiquitous yet overlooked architectures of the discount supermarket.

Exploring communication between social workers, children and young people

A key issue for the social work profession concerns the nature, quality and content of communicative encounters with children and families. This article introduces some findings from a project funded by the Economic and Social Research Council (ESRC) that took place across the United Kingdom between 2013 and 2015, which explored how social workers communicate with children in their everyday practice. The Talking and Listening to Children (TLC) project had three phases: the first was ethnographic, involving observations of social workers in their workplace and during visits; the second used video-stimulated recall with a small number of children and their social workers; and the third developed online materials to support social workers. This paper discusses findings from the first phase. It highlights a diverse picture regarding the context and content of communicative processes; it is argued that attention to contextual issues is as important as focusing on individual practitioners’ behaviours and outlines a model for so doing.