A rare case of solution and solid state inter-conversion of two copper(II) dimers and a copper(II) chain

Three Cu(II)-azido complexes of formula [Cu2L2(N-3)(2)] (1), [Cu2L2(N-3)(2)]center dot H2O (2) and [CuL(N-3)](n) (3) have been synthesized using the same tridentate Schiff base ligand HL (2-[(3-methylaminopropylimino)-methyl]-phenol), the condensation product of N-methyl-1,3-propanediamine and salicyldehyde). Compounds 1 and 2 are basal-apical mu-1,1 double azido bridged dimers. The dimeric structure of 1 is centro-symmetric but that of 2 is non-centrommetric. Compound 3 is a mu-1,1 single azido bridged 1D chain. The three complexes interconvert in solution and can be obtained in pure form by carefully controlling the synthetic conditions. Compound 2 undergoes an irreversible transformation to 1 upon dehydration in the solid state. The magnetic properties of compounds 1 and 2 show the presence of weak antiferromagnetic exchange interactions mediated by the double 1,1-N-3 azido bridges (J = -2.59(4) and -0.10(1) cm-(1), respectively). The single 1,1-N-3 bridge in compound 3 mediates a negligible exchange interaction.

Inter-comparison of stratospheric mean-meridional circulation and eddy mixing among six reanalysis data sets

The stratospheric mean-meridional circulation (MMC) and eddy mixing are compared among six meteorological reanalysis data sets: NCEP-NCAR, NCEP-CFSR, ERA-40, ERA-Interim, JRA-25, and JRA-55 for the period 1979–2012. The reanalysis data sets produced using advanced systems (i.e., NCEP-CFSR, ERA-Interim, and JRA-55) generally reveal a weaker MMC in the Northern Hemisphere (NH) compared with those produced using older systems (i.e., NCEP/NCAR, ERA-40, and JRA-25). The mean mixing strength differs largely among the data products. In the NH lower stratosphere, the contribution of planetary-scale mixing is larger in the new data sets than in the old data sets, whereas that of small-scale mixing is weaker in the new data sets. Conventional data assimilation techniques introduce analysis increments without maintaining physical balance, which may have caused an overly strong MMC and spurious small-scale eddies in the old data sets. At the NH mid-latitudes, only ERA-Interim reveals a weakening MMC trend in the deep branch of the Brewer–Dobson circulation (BDC). The relative importance of the eddy mixing compared with the mean-meridional transport in the subtropical lower stratosphere shows increasing trends in ERA-Interim and JRA-55; this together with the weakened MMC in the deep branch may imply an increasing age-of-air (AoA) in the NH middle stratosphere in ERA-Interim. Overall, discrepancies between the different variables and trends therein as derived from the different reanalyses are still relatively large, suggesting that more investments in these products are needed in order to obtain a consolidated picture of observed changes in the BDC and the mechanisms that drive them.

An entirely new land? Italy’s post-war culture and its fascist past

Scholarship has for decades emphasised the significant continuities in Italian culture and society after Fascism, calling into question the rhetoric of post-war renewal. This essay proposes a reassessment of that rhetoric through the analysis of five key metaphors with which Italian intellectuals represented national recovery after 1945: parenthesis, disease, flood, childhood, and discovery. While the current critical consensus would lead us to expect a cultural conversation characterised by repression and evasion, an analysis of these five post-war metaphors instead reveals both a penetrating re-assessment of Italian culture after Fascism and an earnest adherence to the cause of national re-vitalisation. Foregrounding the inter-relation of Italy’s prospects for change and its continuities with Fascism, these metaphors suggest that post-war Italian intellectuals conceived of their country’s hopes for renewal, as well as its connections to the recent past, in terms that transcend the binary division favoured in many historical accounts.

Relation between the fatty acid composition of peripheral blood mononuclear cells and measures of immune cell function in health free-living subjects aged 25-72 y

Background: There is little information about the relation between the fatty acid composition of human immune cells and the function of those cells over the habitual range of fatty acid intakes. Objective: The objective of the study was to determine the relation between the fatty acid composition of human peripheral blood mononuclear cell (PBMC) phospholipids and the functions of human immune cells. Design: One hundred fifty healthy adult subjects provided a fasting blood sample. The phagocytic and oxidative burst activities of monocytes and neutrophils were measured in whole blood. PBMCs were isolated and used to measure lymphocyte proliferation in response to the T cell mitogen concanavalin A and the production of cytokines in response to concanavalin A or bacterial lipopolysaccharide. The fatty acid composition of plasma and PBMC phospholipids was determined. Results: Wide variations in fatty acid composition of PBMC phospholipids and immune cell functions were identified among the subjects. The proportions of total Polyunsaturated fatty acids (PUFAs), of total n-6 and n-3 PUFAs, and of several individual PUFAs in PBMC phospholipids were positively correlated with phagocytosis by neutrophils and monocytes, neutrophil oxidative burst, lymphocyte proliferation, and interferon gamma production. The ratios of saturated fatty acids to PUFAs and of n-6 to n-3 PUFAs were negatively correlated with these same immune functions. The relation of PBMC fatty acid composition to monocyte oxidative burst was the reverse of its relation to monocyte phagocytosis and neutrophil oxidative burst. Conclusion: Variations in the fatty acid composition of PBMC phospholipids account for some of the variability in immune cell functions among healthy adults.

Innovation in construction: a sociology of technology approach

An alternative approach to understanding innovation is made using two intersecting ideas. The first is that successful innovation requires consideration of the social and organizational contexts in which it is located. The complex context of construction work is characterized by inter-organizational collaboration, a project-based approach and power distributed amongst collaborating organizations. The second is that innovations can be divided into two modes: ‘bounded’, where the implications of innovation are restricted within a single, coherent sphere of influence, and ‘unbounded’, where the effects of implementation spill over beyond this. Bounded innovations are adequately explained within the construction literature. However, less discussed are unbounded innovations, where many firms' collaboration is required for successful implementation, even though many innovations can be considered unbounded within construction's inter-organizational context. It is argued that unbounded innovations require an approach to understand and facilitate the interactions both within a range of actors and between the actors and technological artefacts. The insights from a sociology of technology approach can be applied to the multiplicity of negotiations and alignments that constitute the implementation of unbounded innovation. The utility of concepts from the sociology of technology, including ‘system building’ and ‘heterogeneous engineering’, is demonstrated by applying them to an empirical study of an unbounded innovation on a major construction project (the new terminal at Heathrow Airport, London, UK). This study suggests that ‘system building’ contains outcomes that are not only transformations of practices, processes and systems, but also the potential transformation of technologies themselves.

Present state of global wetland extent and wetland methane modelling: conclusions from a model inter-comparison project (WETCHIMP)

Global wetlands are believed to be climate sensitive, and are the largest natural emitters of methane (CH4). Increased wetland CH4 emissions could act as a positive feedback to future warming. The Wetland and Wetland CH4 Inter-comparison of Models Project (WETCHIMP) investigated our present ability to simulate large-scale wetland characteristics and corresponding CH4 emissions. To ensure inter-comparability, we used a common experimental protocol driving all models with the same climate and carbon dioxide (CO2) forcing datasets. The WETCHIMP experiments were conducted for model equilibrium states as well as transient simulations covering the last century. Sensitivity experiments investigated model response to changes in selected forcing inputs (precipitation, temperature, and atmospheric CO2 concentration). Ten models participated, covering the spectrum from simple to relatively complex, including models tailored either for regional or global simulations. The models also varied in methods to calculate wetland size and location, with some models simulating wetland area prognostically, while other models relied on remotely sensed inundation datasets, or an approach intermediate between the two. Four major conclusions emerged from the project. First, the suite of models demonstrate extensive disagreement in their simulations of wetland areal extent and CH4 emissions, in both space and time. Simple metrics of wetland area, such as the latitudinal gradient, show large variability, principally between models that use inundation dataset information and those that independently determine wetland area. Agreement between the models improves for zonally summed CH4 emissions, but large variation between the models remains. For annual global CH4 emissions, the models vary by ±40% of the all-model mean (190 Tg CH4 yr−1). Second, all models show a strong positive response to increased atmospheric CO2 concentrations (857 ppm) in both CH4 emissions and wetland area. In response to increasing global temperatures (+3.4 °C globally spatially uniform), on average, the models decreased wetland area and CH4 fluxes, primarily in the tropics, but the magnitude and sign of the response varied greatly. Models were least sensitive to increased global precipitation (+3.9 % globally spatially uniform) with a consistent small positive response in CH4 fluxes and wetland area. Results from the 20th century transient simulation show that interactions between climate forcings could have strong non-linear effects. Third, we presently do not have sufficient wetland methane observation datasets adequate to evaluate model fluxes at a spatial scale comparable to model grid cells (commonly 0.5°). This limitation severely restricts our ability to model global wetland CH4 emissions with confidence. Our simulated wetland extents are also difficult to evaluate due to extensive disagreements between wetland mapping and remotely sensed inundation datasets. Fourth, the large range in predicted CH4 emission rates leads to the conclusion that there is both substantial parameter and structural uncertainty in large-scale CH4 emission models, even after uncertainties in wetland areas are accounted for.

A singular vector perspective of 4D-Var: Filtering and interpolation

Four-dimensional variational data assimilation (4D-Var) combines the information from a time sequence of observations with the model dynamics and a background state to produce an analysis. In this paper, a new mathematical insight into the behaviour of 4D-Var is gained from an extension of concepts that are used to assess the qualitative information content of observations in satellite retrievals. It is shown that the 4D-Var analysis increments can be written as a linear combination of the singular vectors of a matrix which is a function of both the observational and the forecast model systems. This formulation is used to consider the filtering and interpolating aspects of 4D-Var using idealized case-studies based on a simple model of baroclinic instability. The results of the 4D-Var case-studies exhibit the reconstruction of the state in unobserved regions as a consequence of the interpolation of observations through time. The results also exhibit the filtering of components with small spatial scales that correspond to noise, and the filtering of structures in unobserved regions. The singular vector perspective gives a very clear view of this filtering and interpolating by the 4D-Var algorithm and shows that the appropriate specification of the a priori statistics is vital to extract the largest possible amount of useful information from the observations. Copyright © 2005 Royal Meteorological Society

Quantitative model for the kinetics of lyotropic phase transitions involving changes in monolayer curvature

We present a kinetic model for transformations between different self-assembled lipid structures. The model shows how data on the rates of phase transitions between mesophases of different geometries can be used to provide information on the mechanisms of the transformations and the transition states involved. This can be used, for example, to gain an insight into intermediate structures in cell membrane fission or fusion. In cases where the monolayer curvature changes on going from the initial to the final mesophase, we consider the phase transition to be driven primarily by the change in the relaxed curvature with pressure or temperature, which alters the relative curvature elastic energies of the two mesophase structures. Using this model, we have analyzed previously published kinetic data on the inter-conversion of inverse bicontinuous cubic phases in the 1-monoolein-30 wt% water system. The data are for a transition between QII(G) and QII(D) phases, and our analysis indicates that the transition state more closely resembles the QII(D) than the QII(G) phase. Using estimated values for the monolayer mean curvatures of the QII(G) and QII(D) phases of -0.123 nm(-1) and -0.133 nm(-1), respectively, gives values for the monolayer mean curvature of the transition state of between -0.131 nm(-1) and -0.132 nm(-1). Furthermore, we estimate that several thousand molecules undergo the phase transition cooperatively within one "cooperative unit", equivalent to 1-2 unit cells of QII(G) or 4-10 unit cells of QII(D).

The role of drama in the teaching of speaking and listening as the basis for social capital

This paper explores how the concept of 'social capital' relates to the teaching of speaking and listening. The argument draws on Bourdieu's notion that a common language is an illusion but posits that an understanding of the grammar of speech can be productive in the development of both an understanding of what constitutes effective speech and the development of competence in speaking. It is argued that applying structuralist notions of written grammar is an inadequate approach to understanding speech acts or enhancing the creative use of speech. An analysis is made of how typical features of speech relate to dramatic dialogue and how the meaning of what is said is contingent upon aural and visual signifiers. On this basis a competent speaker is seen as being one who produces expressions appropriate for a range of situations by intentionally employing such signifiers. The paper draws on research into the way drama teachers make explicit reference to and use of semiotics and dramatic effectiveness in order to improve students' performance and by so doing empower them to increase their social capital. Ultimately, it is concluded that helping students identify, analyse and employ the aural, visual and verbal grammar of spoken English is not an adjunct to the subject of drama, but an intrinsic part of understanding the art form. What is called for is a re-appraisal by drama teachers of their own understanding of concepts relating to speech acts in order to enhance this area of their work.

Expression of four beta-galactosidases from Bifidobacterium bifidum NCIMB41171 and their contribution on the hydrolysis and synthesis of galactooligosaccharides

This paper deals with two aspects tightly related to the enzymatic characteristics and expression of four beta-galactosidases (BbgI, BbgII, BbgIII and BbgIV) from Bifidobacterium bifidum NCIMB41171. The growth patterns of this strain indicated a preference towards complex (i.e. lactose, galactooligosaccharides (GOSs)) rather than simple carbohydrates (i.e. glucose and galactose) and a collaborative action and synergistic relation of more than one beta-galactosidase isoenzyme for either lactose or GOS hydrolysis and subsequent assimilation. Native polyacrylamide gel electrophoresis analysis of protein extracts from cells growing on different carbohydrates (i.e. glucose, lactose or GOS) indicated that two lactose hydrolysing enzymes (BbgI and BbgIII) and one GOS hydrolysing enzyme (BbgII) were constitutively expressed, whereas a fourth lactose hydrolysing enzyme (BbgIV) was induced in the presence of lactose or different GOS fractions. Furthermore, the beta-galactosidase expression profiles of B. bifidum cells and the transgalactosylating properties of each individual isoenzyme, with lactose as substrate, clearly indicated that mainly three isoenzymes (BbgI, BbgIII and BbgIV) are implicated in GOS synthesis when whole B. bifidum cells are utilised. Two of the isoenzymes (BbgI and BbgIV) proved to have better transgalactosylating properties giving yields ranging from 42% to 47% whereas the rest (BbgI and BbgIII) showed lower yields (15% and 29%, respectively).

Intonation abilities of children with Williams syndrome: a preliminary investigation

Purpose: The authors investigated expressive and receptive intonation abilities in children with Williams syndrome (WS) and the relation of these abilities to other linguistic abilities. Method: Fourteen children with WS, 14 typically developing children matched to the WS group for receptive language (LA), and 15 typically developing children matched to the WS group for chronological age (CA) were compared on a range of receptive and expressive intonation tasks from the Profiling Elements of Prosodic Systems-Child version (PEPS-C) battery. Results: The WS group performed similarly to the LA group on all intonation tasks apart from the long-item imitation task, on which the WS group scored significantly lower than the LA group. When compared with the CA group, the WS group was significantly poorer on all aspects of intonation. Whereas there were a number of significant correlations between the intonation and language measures in the control groups, in the WS group, there was only 1 significant correlation between a PEPS-C task and one of the language measures. Conclusion: As a result of this study, the authors concluded that children with WS have expressive and receptive intonation abilities as expected for their level of language comprehension and that intonation and other linguistic abilities in WS are not strongly related.

Smoothness of scale functions for spectrally negative Lévy processes

Scale functions play a central role in the fluctuation theory of spectrally negative Lévy processes and often appear in the context of martingale relations. These relations are often require excursion theory rather than Itô calculus. The reason for the latter is that standard Itô calculus is only applicable to functions with a sufficient degree of smoothness and knowledge of the precise degree of smoothness of scale functions is seemingly incomplete. The aim of this article is to offer new results concerning properties of scale functions in relation to the smoothness of the underlying Lévy measure. We place particular emphasis on spectrally negative Lévy processes with a Gaussian component and processes of bounded variation. An additional motivation is the very intimate relation of scale functions to renewal functions of subordinators. The results obtained for scale functions have direct implications offering new results concerning the smoothness of such renewal functions for which there seems to be very little existing literature on this topic.

Northern winter stratospheric temperature and ozone responses to ENSO inferred from an ensemble of Chemistry Climate Models

The connection between the El Ni˜no Southern Oscillation (ENSO) and the Northern polar stratosphere has been established from observations and atmospheric modeling. Here a systematic inter-comparison of the sensitivity of the modeled stratosphere to ENSO in Chemistry Climate Models (CCMs) is reported. This work uses results from a number of the CCMs included in the 2006 ozone assessment. In the lower stratosphere, the mean of all model simulations reports a warming of the polar vortex during strong ENSO events in February–March, consistent with but smaller than the estimate from satellite observations and ERA40 reanalysis. The anomalous warming is associated with an anomalous dynamical increase of column ozone north of 70� N that is accompanied by coherent column ozone decrease in the Tropics, in agreement with that deduced from the NIWA column ozone database, implying an increased residual circulation in the mean of all model simulations during ENSO. The spread in the model responses is partly due to the large internal stratospheric variability and it is shown that it crucially depends on the representation of the tropospheric ENSO teleconnection in the models.

Association of low adiponectin levels with the metabolic syndrome--the Chennai Urban Rural Epidemiology Study (CURES-4)

The aim of the study was to assess the relation of adiponectin levels with the metabolic syndrome in Asian Indians, a high-risk group for diabetes and premature coronary artery disease. The study was conducted on 100 (50 men and 50 women) type 2 diabetic subjects and 100 age and sex matched subjects with normal glucose tolerance selected from the Chennai Urban Rural Epidemiology Study, an ongoing population study in Chennai in southern India. Metabolic syndrome was defined using modified Adult Treatment Panel III (ATPIII) guidelines. Adiponectin values were significantly lower in diabetic subjects (men: 5.2 vs 8.3 microg/mL, P=.00l; women: 7.6 vs 11.1 microg/mL, P<.00l) and those with the metabolic syndrome (men: 5.0 vs 6.8 microg/mL, P=.01; women: 6.5 vs 9.9 microg/mL, P=.001) compared with those without. Linear regression analysis revealed adiponectin to be associated with body mass index (P<.05), waist circumference (P<.01), fasting plasma glucose (P=.001), glycated hemoglobin (P<.001), triglycerides (P<.00l), high-density lipoprotein (HDL) cholesterol (P<.001), cholesterol/HDL ratio (P<.00l), and insulin resistance measured by homeostasis assessment model (P<.00l). Factor analysis identified 2 factors: factor 1, negatively loaded with adiponectin and HDL cholesterol and positively loaded with triglycerides, waist circumference, and insulin resistance measured by homeostasis assessment model; and factor 2, with a positive loading of waist circumference and systolic and diastolic blood pressure. Logistic regression analysis revealed adiponectin to be negatively associated with metabolic syndrome (odds ratio [OR], 0.365; P<.001) even after adjusting for age (OR, 0.344; P<.00l), sex (OR, 0.293; P<.001), and body mass index (OR, 0.292; P<.00l). Lower adiponectin levels are associated with the metabolic syndrome per se and several of its components, particularly, diabetes, insulin resistance, and dyslipidemia in this urban south Indian population.

Max Weber in the thought of Edward Shils (1910–1995) and Ernest Gellner (1925–1995): the paradox of two Weberian approaches to the understanding of nations and nationalism?

This article traces the paradoxical impact of Weber's oeuvre on two major scholars of nationalism, Ernest Gellner and Edward Shils. Both these scholars died in 1995, leaving behind a rich corpus of writings on the nation and nationalism, much of which was inspired by Max Weber. The paradox is that although neither scholar accepted Weber's sceptical attitude to the concept of ‘nation’, they both used his other major concepts, such as ‘rationality’, ‘disenchantment’, ‘unintended consequences’, the ‘ethic of responsibility’ and ‘charisma’, in their very analyses of the nation and nationalism. And they both saw, each in his own way, the nation and nationalism as constitutive elements of modern societies. However, the paradox ceases being a paradox if one sees the integration, by Shils and Gellner, of concepts of the nation and of nationalism in the analysis of modernity, as a development of Weber's ideas.