pH-mediated interactions between poly(acrylic acid) and methylcellulose in the formation of ultrathin multilayered hydrogels and spherical nanoparticles

Poly(acrylic acid) forms insoluble hydrogen-bonded interpolymer complexes with methylcellulose in aqueous solutions under acidic conditions. In this work the reaction heats and binding constants were determined for the complexation between poly(acrylic acid) and methylcellulose by isothermal titration calorimetry at different pH and findings are correlated with the aggregation processes occurring in this system. The principal contribution to the complexation heat results from primary polycomplex particle aggregation. Transmission electron microscopy of nanoparticles produced at pH 1.4 and 2.4 demonstrated that they are spherical and dense structures. The nanoparticles ranged from 80 to 200 nm, whereas particles formed at pH 3.2 were 20-30 nm and were stabilized against aggregation by a network of uncomplexed macromolecules. For the first time, multilayered materials were developed on the basis of hydrogen-bonded complexes of poly(acrylic acid) and methylcellulose using layer-by-layer deposition on a glass surface. The thickness of these films was a linear function of the number of deposition cycles. The materials were subsequently cross-linked by thermal treatment, resulting in ultrathin hydrogels which detached from the glass substrate upon swelling. The swelling capacity of ultrathin hydrogels differed from the swelling of the thicker films of a similar chemical composition.

Can carbon surface oxidation shift the pore size distribution curve calculated from Ar, N(2) and CO(2) adsorption isotherms? Simulation results for a realistic carbon model

Using the virtual porous carbon model proposed by Harris et al, we study the effect of carbon surface oxidation on the pore size distribution (PSD) curve determined from simulated Ar, N(2) and CO(2) isotherms. It is assumed that surface oxidation is not destructive for the carbon skeleton, and that all pores are accessible for studied molecules (i.e., only the effect of the change of surface chemical composition is studied). The results obtained show two important things, i.e., oxidation of the carbon surface very slightly changes the absolute porosity (calculated from the geometric method of Bhattacharya and Gubbins (BG)); however, PSD curves calculated from simulated isotherms are to a greater or lesser extent affected by the presence of surface oxides. The most reliable results are obtained from Ar adsorption data. Not only is adsorption of this adsorbate practically independent from the presence of surface oxides, but, more importantly, for this molecule one can apply the slit-like model of pores as the first approach to recover the average pore diameter of a real carbon structure. For nitrogen, the effect of carbon surface chemical composition is observed due to the quadrupole moment of this molecule, and this effect shifts the PSD curves compared to Ar. The largest differences are seen for CO2, and it is clearly demonstrated that the PSD curves obtained from adsorption isotherms of this molecule contain artificial peaks and the average pore diameter is strongly influenced by the presence of electrostatic adsorbate-adsorbate as well as adsorbate-adsorbent interactions.

Literature for the very young

This chapter looks at books which will support the very young through their earliest childhood and first few years of schooling. Learning to read can be hard but it is a lot harder if you never encounter the sort of literature that will engage you and motivate you to see the whole learning process as worthwhile. The chapter considers ways to share great texts with young children and how to select good books to share.

Coupling and memory in liquid crystal elastomers

The polymer backbone of a side-chain liquid crystal polymer exhibits an anisotropic shape due to the coupling of the liquid crystal orientational order of the mesogenic side-chains to the backbone. The magnitude and sign of this coupling may be controlled by chemical design. The introduction of chemical cross-links in to such a system provides both a memory of the anisotropic organisation and a mechanism by which the microscopic anisotropy can be realised at a macroscopic level. We show how this anisotropic network structure yields new phenomena when electric or mechanical fields are applied.

Examining reliability of seasonal to decadal sea surface temperature forecasts: the role of ensemble dispersion

Useful probabilistic climate forecasts on decadal timescales should be reliable (i.e. forecast probabilities match the observed relative frequencies) but this is seldom examined. This paper assesses a necessary condition for reliability, that the ratio of ensemble spread to forecast error being close to one, for seasonal to decadal sea surface temperature retrospective forecasts from the Met Office Decadal Prediction System (DePreSys). Factors which may affect reliability are diagnosed by comparing this spread-error ratio for an initial condition ensemble and two perturbed physics ensembles for initialized and uninitialized predictions. At lead times less than 2 years, the initialized ensembles tend to be under-dispersed, and hence produce overconfident and hence unreliable forecasts. For longer lead times, all three ensembles are predominantly over-dispersed. Such over-dispersion is primarily related to excessive inter-annual variability in the climate model. These findings highlight the need to carefully evaluate simulated variability in seasonal and decadal prediction systems.Useful probabilistic climate forecasts on decadal timescales should be reliable (i.e. forecast probabilities match the observed relative frequencies) but this is seldom examined. This paper assesses a necessary condition for reliability, that the ratio of ensemble spread to forecast error being close to one, for seasonal to decadal sea surface temperature retrospective forecasts from the Met Office Decadal Prediction System (DePreSys). Factors which may affect reliability are diagnosed by comparing this spread-error ratio for an initial condition ensemble and two perturbed physics ensembles for initialized and uninitialized predictions. At lead times less than 2 years, the initialized ensembles tend to be under-dispersed, and hence produce overconfident and hence unreliable forecasts. For longer lead times, all three ensembles are predominantly over-dispersed. Such over-dispersion is primarily related to excessive inter-annual variability in the climate model. These findings highlight the need to carefully evaluate simulated variability in seasonal and decadal prediction systems.

Palaeobiology of the medieval population of Albano (Rome, Italy): a combined morphological and biomolecular approach

Recent years have seen increased interest in skeletal populations from the Imperial Roman Age in Italy, but much less is known about diet and standards of living in the subsequent medieval period. To fill this gap, we conducted a morphological analysis of human remains from Albano, an Italian town near Rome, as well as a stable isotope analysis of bone collagen to reconstruct diet. The sample was recovered from a Medieval cemetery (1040–1220 cal. yr. BP) located in the gardens of the historical Palazzo Doria Pamphili in Albano. A minimum number of 40 individuals (31 adults and 9 sub-adults) were examined using standard methods. Though the general health status of the population was good, signs of cribra orbitalia and diffuse enthesopathies were noted during the morphological examination. Stable carbon and nitrogen isotope analyses of the bone collagen from 24 adult humans and three faunal bones indicate that the diet of the population may be described as predominantly terrestrial and C3-plant based although the data for some of the individuals suggest a modest consumption of C4-(millet) based or aquatic proteins. No evidence of significant dietary differences between the sexes was found. The comparison of the isotope data from Albano with those from populations recovered in the same region is consistent with a shift from a terrestrial, possibly plant foods-dominated subsistence in the Early Middle Ages to a diet with a higher contribution from animal proteins, both terrestrial and aquatic, in the Later Middle Ages.

Nationalised large-scale mining, trade unions and community representation: perspectives from Northern Madagascar

This article critically explores the nature and purpose of relationships and inter-dependencies between stakeholders in the context of a parastatal chromite mining company in the Betsiboka Region of Northern Madagascar. An examination of the institutional arrangements at the interface between the mining company and local communities identified power hierarchies and dependencies in the context of a dominant paternalistic environment. The interactions, inter alia, limited social cohesion and intensified the fragility and weakness of community representation, which was further influenced by ethnic hierarchies between the varied community groups; namely, indigenous communities and migrants to the area from different ethnic groups. Moreover, dependencies and nepotism, which may exist at all institutional levels, can create civil society stakeholder representatives who are unrepresentative of the society they are intended to represent. Similarly, a lack of horizontal and vertical trust and reciprocity inherent in Malagasy society engenders a culture of low expectations regarding transparency and accountability, which further catalyses a cycle of nepotism and elite rent-seeking behaviour. On the other hand, leaders retain power with minimal vertical delegation or decentralisation of authority among levels of government and limit opportunities to benefit the elite, perpetuating rent-seeking behaviour within the privileged minority. Within the union movement, pluralism and the associated politicisation of individual unions restricts solidarity, which impacts on the movement’s capacity to act as a cohesive body of opinion and opposition. Nevertheless, the unions’ drive to improve their social capital has increased expectations of transparency and accountability, resulting in demands for greater engagement in decision-making processes.

Examining reliability of seasonal to decadal sea surface temperature forecasts: the role of ensemble dispersion

Useful probabilistic climate forecasts on decadal timescales should be reliable (i.e. forecast probabilities match the observed relative frequencies) but this is seldom examined. This paper assesses a necessary condition for reliability, that the ratio of ensemble spread to forecast error being close to one, for seasonal to decadal sea surface temperature retrospective forecasts from the Met Office Decadal Prediction System (DePreSys). Factors which may affect reliability are diagnosed by comparing this spread-error ratio for an initial condition ensemble and two perturbed physics ensembles for initialized and uninitialized predictions. At lead times less than 2 years, the initialized ensembles tend to be under-dispersed, and hence produce overconfident and hence unreliable forecasts. For longer lead times, all three ensembles are predominantly over-dispersed. Such over-dispersion is primarily related to excessive inter-annual variability in the climate model. These findings highlight the need to carefully evaluate simulated variability in seasonal and decadal prediction systems.Useful probabilistic climate forecasts on decadal timescales should be reliable (i.e. forecast probabilities match the observed relative frequencies) but this is seldom examined. This paper assesses a necessary condition for reliability, that the ratio of ensemble spread to forecast error being close to one, for seasonal to decadal sea surface temperature retrospective forecasts from the Met Office Decadal Prediction System (DePreSys). Factors which may affect reliability are diagnosed by comparing this spread-error ratio for an initial condition ensemble and two perturbed physics ensembles for initialized and uninitialized predictions. At lead times less than 2 years, the initialized ensembles tend to be under-dispersed, and hence produce overconfident and hence unreliable forecasts. For longer lead times, all three ensembles are predominantly over-dispersed. Such over-dispersion is primarily related to excessive inter-annual variability in the climate model. These findings highlight the need to carefully evaluate simulated variability in seasonal and decadal prediction systems.

La adquisición de las cláusulas interrogativas parciales en el Español infantil: ¿Reglas innatas o fórmulas aprendidas?

Abstract According to Usage-based Theory (Tomasello 2006), children acquire wh- questions by initially producing concrete formula structures that happen to be very frequent in the input. In this research we analyze the wh-questions produced by three Spanish-speaking children (age range: 0;11-3;11) in longitudinal samples of spontaneous speech to determine whether the Usage-based Theory can explain the wh-question acquisition in Spanish. Results show that: i) the first wh-questions are formula, that appeared with few interrogative particles, and that are highly frequent in the input; ii) as the child develops, wh-questions become more complex, in which this structures are produced with more varied interrogative particles and different verbs; iii) the input seems to play a relevant role in the acquisition of wh-questions. Results seem to validate the Usage-based Theory.

Decentralising natural resource governance in Ghana: critical reflections on the artisanal and small-scale mining sector

This paper critically examines the impact of decentralization on contemporary and future governance arrangements in Ghana’s artisanal and small-scale mining (ASM) sector. The sector, while providing valuable employment in rural areas, is beleaguered by environmental and social issues. Proponents of decentralization argue that re-distributing decision-making authority leads to more responsive, transparent and efficient natural resource management. The analysis presented here, however, demonstrates how weak decentralization has exacerbated the complex, conflictual and clandestine nature of local resource politics surrounding ASM. If future decentralization reforms are going to reverse this trend and improve the governance of ASM in Ghana, then facilitating the participation of traditional authorities is imperative. It is argued that doing so requires addressing the reticence regarding the role of chiefs in resource governance; simply ironing out existing technical issues with decentralization reforms is unlikely to improve the social and environmental performance of ASM in the country. In light of the chronic resource management deficiencies in Ghana, epitomized in the ASM sector, fostering frank political debates on resource governance is becoming urgent.

Los historiadores y los financieros de la Francia del Antiguo Régimen

This article proposes a brief historiographical survey of works on the financiers of Ancien Regime France. It argues that the historians’ main conclusions vary according to the period they study and their main research issue (e.g. the building of the Absolute monarchy, financial crises, economic growth). It suggests that the new consensus about the social origins of the financiers does not fully clarify the question of their perception by the public and their role in the monarchy. It notes that the activities of the financiers were varied and evolved over time, and that the technical aspects of their activities remain poorly known, making it difficult to offer a simple answer to the broad question of their worth and their cost for the monarchy.