Thermo-compression molding of chitosan with a deep eutectic mixture for biofilms development

Supplementary information available at: http://www.rsc.org/suppdata/c5/gc/c5gc02231b/c5gc02231b1.pdf

On the Hill estimator: a comparison of methods

Extreme value theory (EVT) deals with the occurrence of extreme phenomena. The tail index is a very important parameter appearing in the estimation of the probability of rare events. Under a semiparametric framework, inference requires the choice of a number k of upper order statistics to be considered. This is the crux of the matter and there is no definite formula to do it, since a small k leads to high variance and large values of k tend to increase the bias. Several methodologies have emerged in literature, specially concerning the most popular Hill estimator (Hill, 1975). In this work we compare through simulation well-known procedures presented in Drees and Kaufmann (1998), Matthys and Beirlant (2000), Beirlant et al. (2002) and de Sousa and Michailidis (2004), with a heuristic scheme considered in Frahm et al. (2005) within the estimation of a different tail measure but with a similar context. We will see that the new method may be an interesting alternative.

Family relationship and parenting practices: a pathway to adolesents’ collectivist and individualist values?

Adolescents’ perceptions of parenting and family relationships are important variables for identifying mechanisms involved in how children acquire values and how these values are transmitted through families. In a sample of 515 adolescents, we investigated whether perceptions of the quality of parental practices would predict adolescents’ collectivist and individualist values. We hypothesized that perceived quality of family relations would mediate the relationship between the quality of parental practices and collectivist values but not of individualist values. The results of structural equation modeling suggested that perception of the quality of parental practices predicted adolescents’ both collectivist and individualist values. The predicted mediation effect was found for collectivist values, but not for individualist values. The results point to different functions of parenting and family relations on value acquisition. Implications for practice, such as the development and implementation of interventions to improve the formation of adolescents’ values by enhancing the quality of parenting and family relationships are discussed.

Adolescent parents’ values: the role played by retrospective perceptions of the family-of-origin

Family-of-origin is an important system in individual’s lives, and its influence is extensive over the life cycle. The aim of this study was to investigate, in a sample of adolescents’ parents, whether their retrospective perceptions of parenting and relationship qualities within their families-of-origin during adolescence predicted their current collectivist and individualist values. Participants included 110 Portuguese adults with a mean age of 46.86 years old. The results of structural equation modeling supported that retrospective perceptions of parenting and relationship qualities in the family-of-origin predicted the adults’ collectivist values but not their individualist values. This study highlights the importance of retrospective perceptions of supporting and non-rejecting parenting for value acquisition. The results also suggest that values that preserve and protect family connections and collaborations are more likely to be socialized by families. Implications for practice and for the theories on parenting, values, family-of-origin influences and family intergenerational transmission are discussed.

Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Vanishing spin stiffness in the spin-1/2 Heisenberg chain for any nonzero temperature

Whether at the zero spin density m = 0 and finite temperatures T > 0 the spin stiffness of the spin-1/2 XXX chain is finite or vanishes remains an unsolved and controversial issue, as different approaches yield contradictory results. Here we explicitly compute the stiffness at m = 0 and find strong evidence that it vanishes. In particular, we derive an upper bound on the stiffness within a canonical ensemble at any fixed value of spin density m that is proportional to m2L in the thermodynamic limit of chain length L → ∞, for any finite, nonzero temperature, which implies the absence of ballistic transport for T > 0 for m = 0. Although our method relies in part on the thermodynamic Bethe ansatz (TBA), it does not evaluate the stiffness through the second derivative of the TBA energy eigenvalues relative to a uniform vector potential. Moreover, we provide strong evidence that in the thermodynamic limit the upper bounds on the spin current and stiffness used in our derivation remain valid under string deviations. Our results also provide strong evidence that in the thermodynamic limit the TBA method used by X. Zotos [Phys. Rev. Lett. 82, 1764 (1999)] leads to the exact stiffness values at finite temperature T > 0 for models whose stiffness is finite at T = 0, similar to the spin stiffness of the spin-1/2 Heisenberg chain but unlike the charge stiffness of the half-filled 1D Hubbard model.

Study of the electrical behavior of nanostructured Ti–Ag thin films, prepared by glancing angle deposition

Aiming at biosignal acquisition for bioelectrodes application, Ti-Ag thin films were produced by GLAD, in order to tailor their electromechanical properties. The electrical behaviour of the sculptured Ti-Ag thin films was studied with increasing annealing temperatures. The results revealed a good correlation with the set of morphological features displayed. With the increase of the vapour flux angle, a more defined structure was obtained, as well as a more porous morphology, which increased the electrical resistivity of the coatings. An important point consists in the recrystallization of Ti-Ag intermetallic phases due to the temperature increase (between 558 K and 773 K), which resulted in a sharp decrease of the electrical resistivity values.

Nonlinear behavior of gelatin networks reveals a hierarchical structure

We investigate the strain hardening behavior of various gelatin networks-namely physical gelatin gel, chemically cross-linked gelatin gel, and a hybrid gel made of a combination of the former two-under large shear deformations using the pre-stress, strain ramp, and large amplitude oscillations shear protocols. Further, the internal structures of physical gelatin gels and chemically cross-linked gelatin gels were characterized by small angle neutron scattering (SANS) to enable their internal structures to be correlated with their nonlinear rheology. The Kratky plots of SANS data demonstrate the presence of small cross-linked aggregates within the chemically cross-linked network whereas, in the physical gelatin gels, a relatively homogeneous structure is observed. Through model fitting to the scattering data, we were able to obtain structural parameters, such as the correlation length (ξ), the cross-sectional polymer chain radius (Rc) and the fractal dimension (df) of the gel networks. The fractal dimension df obtained from the SANS data of the physical and chemically cross-linked gels is 1.31 and 1.53, respectively. These values are in excellent agreement with the ones obtained from a generalized nonlinear elastic theory that has been used to fit the stress-strain curves. The chemical cross-linking that generates coils and aggregates hinders the free stretching of the triple helix bundles in the physical gels.

The influence of the Palestinian sociocultural values in shaping the vernacular architecture of Nablus city

Recently, environmental architecture and sustainable construction has been ranked on top of the worldâ s interests. Making use of natural resources helps in reducing energy consumption and costs associated with the operation of buildings. The current architectural approaches and designs in Palestine are far away from environmental concepts, copying and simulating abroad approaches, without taking into account the culture, climate, and inhabitant's needs. On the contrast, vernacular architecture has achieved environmental concepts and has given suitable approaches and samples - without any need to simulate or copy - which come from people and land. This paper discusses how the Palestinian socio-cultural context shaped the residential vernacular architecture in Palestine, taking the old city of Nablus as a case-study. The research concept depends on analysing and trying to understand the effect of the socio-cultural context on vernacular architecture and trying to reach some rules or understandings of how it works in order to reach a modern environmental dwelling that is suitable to this concept. The research method goes through analysing study cases from the traditional architecture models and the Nablus city is selected as a case study. This analytical and qualitative method can lead to deep understanding for how to benefit from vernacular architecture in Palestine in finding the future environmental residential construction. One of the main findings of this research is to set general and special rules for building sustainable buildings in Palestine from the socio-cultural point view, in order to be a reference for designers, stakeholders, ministry of planning, and municipalities.

Preoperative staging of rectal cancer with MRI: correlation with pathologic staging

[INTRODUCTION] An accurate preoperative rectal cancer staging is crucial to the correct management of the disease. Despite great controversy around this issue, pelvic magnetic resonance (RM) is said to be the imagiologic standard modality. This work aimed to evaluate magnetic resonance accuracy in preoperative rectal cancer staging comparing with the anatomopathological results. METHODS We calculated sensibility, specificity, positive (VP positive) and negative (VP negative) predictive values for each T and N. We evaluated the concordance between both methods of staging using the Cohen weighted K (Kw), and through ROC curves, we evaluated magnetic resonance accuracy in rectal cancer staging. RESULTS 41 patients met the inclusion criteria. We achieved an efficacy of 43.9% for T and 61% for N staging. The respective sensibility, specificity, positive and negative predictive values are 33.3%, 94.7%, 33.3% and 94.7% for T1; 62.5%, 32%, 37.0% and 57.1% for T2; 31.8%, 79%, 63.6% and 50% for T3 and 27.8%, 87%, 62.5% and 60.6% for N. We obtained a poor concordance for T and N staging and the anatomopathological results. The ROC curves indicated that magnetic resonance is ineffective in rectal cancer staging. CONCLUSION Magnetic resonance has a moderate efficacy in rectal cancer staging and the major difficulty is in differentiating T2 and T3.

Nickel(II) complexes of bidentate N-N′ ligands containing mixed pyrazole, pyrimidine and pyridine aromatic rings as catalysts for ethylene polymerisation

This work describes the synthesis and characterisation of Ni(II) complexes of the following neutral bidentate nitrogen ligands containing pyrazole (pz), pyrimidine (pm) and pyridine (py) aromatic rings: 2-pyrazol-1-yl-pyrimidine (pzpm), 2-(4-methyl-pyrazol-1-yl)-pyrimidine (4-Mepzpm), 2-(4-bromo-pyrazol-1-yl)-pyrimidine (4-Brpzpm), 2-(3,5-dimethyl-pyrazol-1-yl)-pyrimidine (pz*pm), 2-pyrazol-1-yl-pyridine (pzpy) and bis(3,5-dimethylpyrazol-1-yl)phenylmethane (bpz*mph). The complexes [NiBr2(pzpm)] (1), [NiBr2(4-Mepzpm)] (2), [NiBr2(4-Brpzpm)] (3), [NiBr2(pz*pm)] (4), [NiBr2(pzpy)] (5) and [NiBr2(bpz*mph)] (6) were tested as catalysts for ethylene polymerisation, in the presence of the cocatalysts methylaluminoxane (MAO) or diethylaluminium chloride (AlEt2Cl), the catalyst systems 1-3/MAO showing moderate to high activities up to the temperature of 20 °C only in the presence of MAO, whereas 4-6/MAO revealed to be inactive. Other related Pd(II) complexes, already reported in previous works, such as [PdClMe(pzpm)], [PdClMe(pz*pm)], [PdClMe(pzpy)] and [PdClMe(bpz*mph)], also showed to be inactive in the polymerisation of ethylene, when activated by MAO or AlEt2Cl. Selected samples of polyethylene products were characterised by GPC/SEC, 1H and 13C NMR and DSC, showing to be low molecular weight polymers with Mn values ranging from ca. 550 to 1500 g mol−1 and unusually low dispersities of 1.2–1.7, with total branching degrees generally varying between 2 and 12%, melting temperatures from 40 to 120 °C and crystallinities from 40 to 70%.

Cultural circuits of climate change in U.K. broadsheet newspapers, 1985–2003

This article argues for a cultural perspective to be brought to bear on studies of climate change risk perception. Developing the “circuit of culture” model, the article maintains that the producers and consumers of media texts are jointly engaged in dynamic, meaning-making activities that are context-specific and that change over time. A critical discourse analysis of climate change based on a database of newspaper reports from three U.K. broadsheet papers over the period 1985–2003 is presented. This empirical study identifies three distinct circuits of climate change—1985–1990, 1991–1996, 1997–2003—which are characterized by different framings of risks associated with climate change. The article concludes that there is evidence of social learning as actors build on their experiences in relation to climate change science and policy making. Two important factors in shaping the U.K.’s broadsheet newspapers’ discourse on “dangerous” climate change emerge as the agency of top political figures and the dominant ideological standpoints in different newspapers.

O uso de Charges como instrumento para identificação de concepções individuais e representações sociais sobre a Dengue

A dengue é hoje uma das doenças com maior incidência no Brasil, com especial frequência no município de Fênix –Paraná. No presente estudo pretendeu-se analisar as concepções que as crianças têm sobre a dengue, identificando os componentes do modelo KVP, bem como conhecer as representações sociais deste grupo. Para o efeito optou-se pela utilização de charges com alunos do 5º ano do ensino fundamental de uma escola localizada no município de Fênix, cujos textos foram analisados para identificação de categorias e dos componentes do modelo KVP (conhecimentos, valores e práticas) a elas associadas. Foram identificadas quatro categorias de respostas sobre a interpretação da charge relativa à dengue: (i) prevenção da dengue, (ii) perigoso que pode levar à morte, (iii) problema de saúde pública e (iv) combater a dengue. Verificou-se que a “prevenção da dengue” foi a categoria em que se identificaram os três domínios K, V e P implicados na construção das concepções, enquanto as duas categorias “perigoso que pode levar à morte” e “problema de saúde pública” apresentaram apenas os domínios K e V, e a categoria “combater a dengue” apenas evidenciou o domínio V. Os resultados do estudo mostraram que os alunos já veem a dengue como um problema com consequências sérias e que todos têm sua responsabilidade no controle da doença. Percebe-se, portanto, que todo o trabalho que vem sendo realizado pela secretaria de saúde, pelas escolas ou campanhas publicitárias esta surtindo efeito, uma vez que no ano de 2014 houve uma redução do número de casos no município foco da pesquisa.