Structural variations in self-assembled coordination complexes of Zn(II) with hexamethylenetetramine and isomeric 2-, 3- and 4-nitrobenzoates

Three new zinc(II)-hexamethylenetetramine (hmt) complexes [Zn-2(4-nbz)(4)(mu(2)-hmt)(OH2)(hmt)] (1). [Zn-2(2-nbz)(4)(mu(2)-hmt)(2)](n) (2) and [Zn-3(3-nbz)(4)(mu(2)-hmt)(mu(2)-OH)(mu(3)-OH)](n) (3) with three isomeric nitrobenzoate, [4-nbz = 4-nitrobenzoate, 2-nbz = 2-nitrobenzoate and 3-nbz = 3-nitrobenzoate] have been synthesized and structurally characterized by X-ray crystallography. Their identities have also been established by elemental analysis: IR, NMR, UV-Vis and mass spectral studies. 1 is a dinuclear complex formed by bridging hmt with mu(2) coordinating mode. The geometry around the Zn centers in 1 is distorted tetrahedral. Paddle-wheel centrosymmetric Zn-2(2-nbz)(4) units of complex 2 are interconnected by mu(2)-hmt forming a one-dimensional chain with square-pyramidal geometries around the Zn centers. Compound 3 contains a mu(2)/mu(3)-hydroxido and mu(2)-hmt bridged 1D chain. In this complex, varied geometries around the Zn centers are observed viz, tetrahedral, square pyramidal and trigonal bipyramidal. Various weak forces, i.e. lone pair-pi, pi-pi and CH-pi interactions, play a key role in stabilizing the observed structures for complexes 1,2 and 3. This series of complexes demonstrates that although the nitro group does not coordinate to the metal center, its presence at the 2-, 3- or 4-position of the phenyl ring has a striking effect on the dimensionality as well as the structure of the resulted coordination polymers, probably due to the participation of the nitro group in 1.p.center dot center dot center dot pi and/or C-H center dot center dot center dot pi interactions.

Training pharmacists to deliver a complex information technology intervention (PINCER) using the principles of educational outreach and root cause analysis

Objective: To describe the training undertaken by pharmacists employed in a pharmacist-led information technology-based intervention study to reduce medication errors in primary care (PINCER Trial), evaluate pharmacists’ assessment of the training, and the time implications of undertaking the training. Methods: Six pharmacists received training, which included training on root cause analysis and educational outreach, to enable them to deliver the PINCER Trial intervention. This was evaluated using self-report questionnaires at the end of each training session. The time taken to complete each session was recorded. Data from the evaluation forms were entered onto a Microsoft Excel spreadsheet, independently checked and the summary of results further verified. Frequencies were calculated for responses to the three-point Likert scale questions. Free-text comments from the evaluation forms and pharmacists’ diaries were analysed thematically. Key findings: All six pharmacists received 22 hours of training over five sessions. In four out of the five sessions, the pharmacists who completed an evaluation form (27 out of 30 were completed) stated they were satisfied or very satisfied with the various elements of the training package. Analysis of free-text comments and the pharmacists’ diaries showed that the principles of root cause analysis and educational outreach were viewed as useful tools to help pharmacists conduct pharmaceutical interventions in both the study and other pharmacy roles that they undertook. The opportunity to undertake role play was a valuable part of the training received. Conclusions: Findings presented in this paper suggest that providing the PINCER pharmacists with training in root cause analysis and educational outreach contributed to the successful delivery of PINCER interventions and could potentially be utilised by other pharmacists based in general practice to deliver pharmaceutical interventions to improve patient safety.

Do phytoplankton communities evolve through a self-regulatory abundance-diversity relationship?

A small group of phytoplankton species that produce toxic or allelopathic chemicals has a significant effect on plankton dynamics in marine ecosystems. The species of non-toxic phytoplankton, which are large in number, are affected by the toxin-allelopathy of those species. By analysis of the abundance data of marine phytoplankton collected from the North-West coast of the Bay of Bengal, an empirical relationship between the abundance of the potential toxin-producing species and the species diversity of the non-toxic phytoplankton is formulated. A change-point analysis demonstrates that the diversity of non-toxic phytoplankton increases with the increase of toxic species up to a certain level. However, for a massive increase of the toxin-producing species the diversity of phytoplankton at species level reduces gradually. Following the results, a deterministic relationship between the abundance of toxic phytoplankton and the diversity of non-toxic phytoplankton is developed. The abundance–diversity relationship develops a unimodal pathway through which the abundance of toxic species regulates the diversity of phytoplankton. These results contribute to the current understanding of the coexistence and biodiversity of phytoplankton, the top-down vs. bottom-up debate, and to that of abundance–diversity relationship in marine ecosystems.

A self-similar expansion model for use in solar wind transient propogation studies

Since the advent of wide-angle imaging of the inner heliosphere, a plethora of techniques have been developed to investigate the three-dimensional structure and kinematics of solar wind transients, such as coronal mass ejections, from their signatures in single- and multi-spacecraft imaging observations. These techniques, which range from the highly complex and computationally intensive to methods based on simple curve fitting, all have their inherent advantages and limitations. In the analysis of single-spacecraft imaging observations, much use has been made of the fixed φ fitting (FPF) and harmonic mean fitting (HMF) techniques, in which the solar wind transient is considered to be a radially propagating point source (fixed φ, FP, model) and a radially expanding circle anchored at Sun centre (harmonic mean, HM, model), respectively. Initially, we compare the radial speeds and propagation directions derived from application of the FPF and HMF techniques to a large set of STEREO/Heliospheric Imager (HI) observations. As the geometries on which these two techniques are founded constitute extreme descriptions of solar wind transients in terms of their extent along the line of sight, we describe a single-spacecraft fitting technique based on a more generalized model for which the FP and HM geometries form the limiting cases. In addition to providing estimates of a transient’s speed and propagation direction, the self-similar expansion fitting (SSEF) technique provides, in theory, the capability to estimate the transient’s angular extent in the plane orthogonal to the field of view. Using the HI observations, and also by performing a Monte Carlo simulation, we assess the potential of the SSEF technique.

Selecting valuable information to remember: age-related differences and similarities in self-regulated learning

It is often necessary to selectively attend to important information, at the expense of less important information, especially if you know you cannot remember large amounts of information. The present study examined how younger and older adults select valuable information to study, when given unrestricted choices about how to allocate study time. Participants were shown a display of point values ranging from 1–30. Participants could choose which values to study, and the associated word was then shown. Study time, and the choice to restudy words, was under the participant's control during the 2-minute study session. Overall, both age groups selected high value words to study and studied these more than the lower value words. However, older adults allocated a disproportionately greater amount of study time to the higher-value words, and age-differences in recall were reduced or eliminated for the highest value words. In addition, older adults capitalized on recency effects in a strategic manner, by studying high-value items often but also immediately before the test. A multilevel mediation analysis indicated that participants strategically remembered items with higher point value, and older adults showed similar or even stronger strategic process that may help to compensate for poorer memory. These results demonstrate efficient (and different) metacognitive control operations in younger and older adults, which can allow for strategic regulation of study choices and allocation of study time when remembering important information. The findings are interpreted in terms of life span models of agenda-based regulation and discussed in terms of practical applications. (PsycINFO Database Record (c) 2013 APA, all rights reserved)(journal abstract)

Cities’ low carbon plans in an ‘age of austerity’: an analysis of UK local authority actions, attitudes and responses

Background: Cities play a significant role globally in creating carbon emissions but, as centers of major population, innovation and social practice, they also offer important opportunities to tackle climate change. The new challenges faced by cities in an ‘age of austerity’ and decentralist agendas present substantial challenges for coordinated multilevel governance. Results: Based on research carried out in 2011–2012, this paper examines the attitudes and responses of sustainability and climate change officers in UK cities that have prepared low carbon and climate change plans, in the context of these challenges. Using a conceptual framework that analyses ‘awareness’, ‘analysis’ and ‘actions’ (in the context of spending cuts and a new ‘decentralized’ policy agenda) this research suggests that progress on low-carbon futures for cities continues to be fragmented, with increased funding constraints, short-termism and lack of leadership acting as key barriers to progress. Conclusion: Recent UK national policies (including localism, austerity measures and new economic incentives) have not only created further uncertainties, but also scope for cities’ local innovation through policy leverage and self-governing actions.

On the spectra and pseudospectra of a class of non-self-adjoint random matrices and operators

In this paper we develop and apply methods for the spectral analysis of non-selfadjoint tridiagonal infinite and finite random matrices, and for the spectral analysis of analogous deterministic matrices which are pseudo-ergodic in the sense of E. B. Davies (Commun. Math. Phys. 216 (2001), 687–704). As a major application to illustrate our methods we focus on the “hopping sign model” introduced by J. Feinberg and A. Zee (Phys. Rev. E 59 (1999), 6433–6443), in which the main objects of study are random tridiagonal matrices which have zeros on the main diagonal and random ±1’s as the other entries. We explore the relationship between spectral sets in the finite and infinite matrix cases, and between the semi-infinite and bi-infinite matrix cases, for example showing that the numerical range and p-norm ε - pseudospectra (ε > 0, p ∈ [1,∞] ) of the random finite matrices converge almost surely to their infinite matrix counterparts, and that the finite matrix spectra are contained in the infinite matrix spectrum Σ. We also propose a sequence of inclusion sets for Σ which we show is convergent to Σ, with the nth element of the sequence computable by calculating smallest singular values of (large numbers of) n×n matrices. We propose similar convergent approximations for the 2-norm ε -pseudospectra of the infinite random matrices, these approximations sandwiching the infinite matrix pseudospectra from above and below.

Reflexive stasis, scale reversal and the myth of modern cinema

This chapter looks at three films whose Portuguese urban settings offer a privileged ground for the re-evaluation of the classical-modern-postmodern categorisation with regard to cinema. They are The State of Things (Wim Wenders, 1982), Foreign Land (Walter Salles and Daniela Thomas, 1995) and Mysteries of Lisbon (Raúl Ruiz, 2010). In them, the city is the place where characters lose their bearings, names, identities, and where vicious circles, mirrors, replicas and mise-en-abyme bring the vertiginous movement that had characterised the modernist city of 1920s cinema to a halt. Curiously, too, it is the place where so-called postmodern aesthetics finally finds an ideal home in self-ironical tales that expose the film medium’s narrative shortcomings. Intermedial devices, whether Polaroid stills or a cardboard cut-out theatre, are then resorted to in order to turn a larger-than-life reality into framed, manageable narrative miniatures. The scaled-down real, however, turns out to be a disappointing simulacrum, a memory ersatz that unveils the illusory character of cosmopolitan teleology. In my approach, I start by examining the intertwined and transnational genesis of these films that resulted in three correlated visions of the end of history and of storytelling, typical of postmodern aesthetics. I move on to consider intermedia miniaturism as an attempt to stop time within movement, an equation that inevitably brings to mind the Deleuzian movement-time binary, which I revisit in an attempt to disentangle it from the classical-modern opposition. I conclude by proposing reflexive stasis and scale reversal as the common denominator across all modern projects, hence, perhaps, a more advantageous model than modernity to signify artistic and political values.

Pensamos que somos historia porque sabemos que somos historia: context, self and self-construction in women's testimonial writing from revolutionary Cuba

This article presents a group of women-authored testimonial texts published between 1959–1989 in revolutionary Cuba. Despite the recent scholarly debates within Latin American Cultural Studies regarding Latin American testimonio, these texts have received little or no critical or theoretical attention within or outside Cuba. The article therefore starts by situating them within the specific context of revolutionary culture, especially with reference to questions of gender, genre and publication. Having established that the texts as a whole privilege the collective revolutionary context and revolutionary experience over gendered or generic aspects, the seven texts are then grouped under a more specific contextual category, as narratives of voluntary work (participation and observation), in order to provide a clearer structure for their description and analysis. Each of the texts is then described within its sub-group, and the article ends by indicating how such texts challenge testimonio paradigms by positing a relational notion of subjectivity.

Supramolecular materials for inkjet printing: self-assembling polymer networks

Electronically complementary, low molecular weight polymers that self-assemble through tuneable π-π stacking interactions to form extended supramolecular polymer networks have been developed for inkjet printing applications and successfully deposited using three different printing techniques. Sequential overprinting of the complementary components results in supramolecular network formation through complexation of π-electron rich pyrenyl or perylenyl chain-ends in one component with π-electron deficient naphthalene diimide residues in a chain-folding polyimide. The complementary π-π stacked polymer blends generate strongly coloured materials as a result of charge-transfer absorptions in the visible spectrum, potentially negating the need for pigments or dyes in the ink formulation. Indeed, the final colour of the deposited material can be tailored by changing varying the end-groups of the π electron rich polymer component. Piezoelectric printing techniques were employed in a proof of concept study to allow characterisation of the materials deposited, and a thermal inkjet printer adapted with imaging software enabled a detailed analysis of the ink-drops as they formed, and of their physical properties. Finally, continuous inkjet printing allowed greater volumes of material to be deposited, on a variety of different substrate surfaces, and demonstrated the utility and versatility of this novel type of ink for industrial applications.

How reliable is internet-based self-reported identity, socio-demographic and obesity measures in European adults?

In e-health intervention studies, there are concerns about the reliability of internet-based, self-reported (SR) data and about the potential for identity fraud. This study introduced and tested a novel procedure for assessing the validity of internet-based, SR identity and validated anthropometric and demographic data via measurements performed face-to-face in a validation study (VS). Participants (n = 140) from seven European countries, participating in the Food4Me intervention study which aimed to test the efficacy of personalised nutrition approaches delivered via the internet, were invited to take part in the VS. Participants visited a research centre in each country within 2 weeks of providing SR data via the internet. Participants received detailed instructions on how to perform each measurement. Individual’s identity was checked visually and by repeated collection and analysis of buccal cell DNA for 33 genetic variants. Validation of identity using genomic information showed perfect concordance between SR and VS. Similar results were found for demographic data (age and sex verification). We observed strong intra-class correlation coefficients between SR and VS for anthropometric data (height 0.990, weight 0.994 and BMI 0.983). However, internet-based SR weight was under-reported (Δ −0.70 kg [−3.6 to 2.1], p < 0.0001) and, therefore, BMI was lower for SR data (Δ −0.29 kg m−2 [−1.5 to 1.0], p < 0.0001). BMI classification was correct in 93 % of cases. We demonstrate the utility of genotype information for detection of possible identity fraud in e-health studies and confirm the reliability of internet-based, SR anthropometric and demographic data collected in the Food4Me study.

The neoliberal way of war: a critical analysis of contemporary British security in policy and practice.

Dominant paradigms of causal explanation for why and how Western liberal-democracies go to war in the post-Cold War era remain versions of the 'liberal peace' or 'democratic peace' thesis. Yet such explanations have been shown to rest upon deeply problematic epistemological and methodological assumptions. Of equal importance, however, is the failure of these dominant paradigms to account for the 'neoliberal revolution' that has gripped Western liberal-democracies since the 1970s. The transition from liberalism to neoliberalism remains neglected in analyses of the contemporary Western security constellation. Arguing that neoliberalism can be understood simultaneously through the Marxian concept of ideology and the Foucauldian concept of governmentality – that is, as a complementary set of 'ways of seeing' and 'ways of being' – the thesis goes on to analyse British security in policy and practice, considering it as an instantiation of a wider neoliberal way of war. In so doing, the thesis draws upon, but also challenges and develops, established critical discourse analytic methods, incorporating within its purview not only the textual data that is usually considered by discourse analysts, but also material practices of security. This analysis finds that contemporary British security policy is predicated on a neoliberal social ontology, morphology and morality – an ideology or 'way of seeing' – focused on the notion of a globalised 'network-market', and is aimed at rendering circulations through this network-market amenable to neoliberal techniques of government. It is further argued that security practices shaped by this ideology imperfectly and unevenly achieve the realisation of neoliberal 'ways of being' – especially modes of governing self and other or the 'conduct of conduct' – and the re-articulation of subjectivities in line with neoliberal principles of individualism, risk, responsibility and flexibility. The policy and practice of contemporary British 'security' is thus recontextualised as a component of a broader 'neoliberal way of war'.

Bio-fabrication and physiological self-release of tissue equivalents using smart peptide amphiphile templates

In this study we applied a smart biomaterial formed from a self-assembling, multi-functional synthetic peptide amphiphile (PA) to coat substrates with various surface chemistries. The combination of PA coating and alignment-inducing functionalised substrates provided a template to instruct human corneal stromal fibroblasts to adhere, become aligned and then bio-fabricate a highlyordered, multi-layered, three-dimensional tissue by depositing an aligned, native-like extracellular matrix. The newly-formed corneal tissue equivalent was subsequently able to eliminate the adhesive properties of the template and govern its own complete release via the action of endogenous proteases. Tissues recovered through this method were structurally stable, easily handled, and carrier-free. Furthermore, topographical and mechanical analysis by atomic force microscopy showed that tissue equivalents formed on the alignment-inducing PA template had highly-ordered, compact collagen deposition, with a two-fold higher elastic modulus compared to the less compact tissues produced on the non-alignment template, the PA-coated glass. We suggest that this technology represents a new paradigm in tissue engineering and regenerative medicine, whereby all processes for the biofabrication and subsequent self-release of natural, bioprosthetic human tissues depend solely on simple templatetissue feedback interactions.

Spectral analysis and the Aharonov-Bohm\~ effect on certain almost-Riemannian manifold

We study spectral properties of the Laplace-Beltrami operator on two relevant almost-Riemannian manifolds, namely the Grushin structures on the cylinder and on the sphere. This operator contains first order diverging terms caused by the divergence of the volume. We get explicit descriptions of the spectrum and the eigenfunctions. In particular in both cases we get a Weyl's law with leading term Elog E. We then study the drastic effect of Aharonov-Bohm magnetic potentials on the spectral properties. Other generalised Riemannian structures including conic and anti-conic type manifolds are also studied. In this case, the Aharonov-Bohm magnetic potential may affect the self-adjointness of the Laplace-Beltrami operator.

Self-congruence, functional congruence, and destination choice

This study's purpose is to investigate the effects of self-congruence and functional congruence on tourists' destination choice. The present research contributes to the gap in the consumer behavior literature by examining the relationships among self-congruence, functional congruence, and destination choice. Based on a sample of 367 British residents, the three research hypotheses are tested using multinomial logistic regression analysis. The study results suggest that a tourist's destination choice is influenced strongly by functional congruence, but not by self-congruence. The article closes with theoretical and managerial implications as well as future research directions.