Condensed tannin reactivity inhibition by internal rearrangements: Detection by CP-MAS 13C NMR

Tannin extracts were prepared from barks of maritime pine (Pinus maritimus), aleppo pine (Pinus halepensis), Norway spruce (Picea abies) and from a mixture of barks of different pine species (Pinus spp., namely 20% black pine (Pinus thunbergii)+ 30% Scots pine (Pinus sylvestris) + 20% maritime pine (Pinus maritimus) + 10% Aleppo Pine (Pinus halepensis) + 5% Douglas fir (Pseudotsuga menziesii) + 15% Norway spruce (Picea abies)) at a paper mill. The 13C-NMR spectra were carried out from these tannins. Blending systems adhesives were prepared with 5% paraformaldehyde to measure the reactivity by gel time, and to determinate the mechanical resistance by thermomechanical analysis (TMA) and the internal bond strength (IB) according to the European Norm EN-312. The CP MAS 13C NMR bands at 163 ppm and the increase number of smaller bands between 20 and 65 ppm clearly indicate that the extraction of procyanidin-type tannins has been incorrect yielded high relative proportions of catechinic acid structures and diarylpropanol-catechinin acid dimer caused by internal flavonoid rearrangement, and causing the blockage of the C6 and C8 reactive sites, rendering unusable the tannin for wood adhesive applications. Thus, the gel times are very long except for the maritime pine tannin with a value of 51 (s). The TMA analysis gave very low MOE values for almost all the tannin extract samples, except for maritime pine. This situation was confirmed by the IB test. Only maritime pine tannin presented a good mechanical resistance with a value of 0.6 (MPa). Only this sample fulfils the standard requested

Oxidative photopolymerization of thiol-terminated polysulfide resins. Application in antibacterial coatings

A UV photoinduced cross-linking of non-modified commercial poly(disulfide) resins (Thioplast) is reported via the air oxidative photocoupling of terminal thiol functions. Catalyzed by a photogenerated guanidine base (TBD), this step-growth photopolymerization is useful to maximize disulfide functions content. The mechanism proceeds through thiol deprotonation into thiolate anions, further oxidized into thiyl radicals, eventually dimerizing into disulfide cross-links. Starting with a detailed structural characterization of the thiol-terminated resin, photooxidative kinetics are studied under exposure to a polychromatic medium-pressure Hg arc using Raman and infrared spectroscopy. The effects of irradiance, film thickness, photobase concentration, resin molar mass, and content of an additional polythiol monomer (reactive diluent) have been investigated. In an effort of upscaling, irradiation under a 365 nm LED panel has enabled the fast preparation of 1.5 μm thick cross-linked poly(disulfide) coatings in a matter of minutes. Capitalizing on the ability of residual thiol groups to react with silver cations, a post-functionalization has been successfully performed, leading to films exhibiting at their surface stable thiolate-silver bonds as proved by X-ray photoelectron spectroscopy. Despite the well-established biocide action of silver ions, no antibacterial action has been evidenced by confocal fluorescence microscopy because of insufficient release

The hidden costs: Identification of indirect costs associated with acute gastrointestinal illness in an Inuit community

Background: Acute gastrointestinal illness (AGI) incidence and per-capita healthcare expenditures are higher in some Inuit communities as compared to elsewhere in Canada. Consequently, there is a demand for strategies that will reduce the individual-level costs of AGI; this will require a comprehensive understanding of the economic costs of AGI. However, given Inuit communities’ unique cultural, economic, and geographic contexts, there is a knowledge gap regarding the context-specific indirect costs of AGI borne by Inuit community members. This study aimed to identify the major indirect costs of AGI, and explore factors associated with these indirect costs, in the Inuit community of Rigolet, Canada, in order to develop a case-based context-specific study framework that can be used to evaluate these costs. Methods: A mixed methods study design and community-based methods were used. Qualitative in-depth, group, and case interviews were analyzed using thematic analysis to identify and describe indirect costs of AGI specific to Rigolet. Data from two quantitative cross-sectional retrospective surveys were analyzed using univariable regression models to examine potential associations between predictor variables and the indirect costs. Results/Significance: The most notable indirect costs of AGI that should be incorporated into cost-of-illness evaluations were the tangible costs related to missing paid employment and subsistence activities, as well as the intangible costs associated with missing community and cultural events. Seasonal cost variations should also be considered. This study was intended to inform cost-of-illness studies conducted in Rigolet and other similar research settings. These results contribute to a better understanding of the economic impacts of AGI on Rigolet residents, which could be used to help identify priority areas and resource allocation for public health policies and programs

Micro- and macroscopic observations of the nucleation process and crystal growth of nanosized Cs-pollucite in an organotemplate-free hydrosol

The nucleation and crystal growth of nanoscale cesium pollucite aluminosilicate zeolite (ANA topology) from an organotemplate-free precursor suspension are reported. By using a new and reactive synthesis recipe (5.5SiO2:1Al2O3:6Cs2O:140H2O), zeolite nanocrystals with higher Al content (Si/Al ratio = 2.12) are obtained within 120 min under mild condition (180 °C) which is much faster and safer as compared to those previously reported. The solid initially experiences amorphous phase reorganization before nucleation, crystallization and crystal growth take place. The resulting Cs-pollucite nanocrystals (average size 55 nm) display trapezohedron morphology. The nanocrystals are colloidally stabilized in water and they are very active in base-catalyzed cyanoethylation of dipropylamine reaction, giving 89.6% conversion at 180 °C within 50 min. In addition, high solid yield of nanocrystals (ca. 70%) is also achieved, thus offering a green pathway for synthesizing zeolite nanocrystals with high basicity in large scale

Synthesis of Cs-ABW nanozeolite in organotemplate-free system

Cesium-aluminosilicate zeolite nanocrystals with ABW framework structure are synthesized free of organic template using hydrothermal approach. The crystallization process of Cs-ABW zeolite nanocrystals by varying the initial gel molar composition, heating temperature and crystallization time was studied. More detailed investigations of the formation of Cs-ABW nanozeolite using a reactive clear precursor hydrogel (4SiO2:1Al2O3:16Cs2O:160H2O) were then carried out. Fully crystalline Cs-ABW nanozeolites were obtained within 120 min at 180 °C and 22 bar, which is considerably faster and safer in comparison to the currently available method involving treatment at 695 °C, 1000 bar and 46 h. The Cs-ABW nanocrystals have grain shape morphology with a mean size of 32 nm and they do not agglomerate for long durations. The nanosized Cs-ABW zeolite has high alumina content (Si/Al ratio = 1.04). These nanocrystals can be prepared in high solid yield (ca. 82%) thus offering a promising route for large-scale production of highly basic zeolite nanoparticles

Designation processes and semantic substitutions used by european portuguese children in a vocabulary test

This research study focus on the designation processes and semantic substitutions of each word on the vocabulary sub-task from the language test for children – ABFW, standardized in Brazil and adapted to European Portuguese, as well as the comparison of the results obtained in the two countries, to analyze the relevance of their extensibility to the Portuguese population. Methods: The test was applied to 150 children from 5 to 6 years old, of typical development. The test consists of 9 conceptual categories. Each category consists of different words, which were always assessed in the same sequential order. Results: The sample of this study showed a lower performance only in clothes, places and food semantic categories. All the other categories have outperformed the standard. The categories of vocabulary with higher percentage in the right designation of the words were colors and shapes, animals and toys and music instruments. The categories with a higher percentage of substitution processes, from the reference results, were: food and locations. The most recurrent substitution processes were the co-hyponym, words that designate semantic attributes, valorization of the visual stimulus, hypernym and parasynonyms Conclusion: Given the homogeneity of the results of this study with the results obtained with other studies in Brazil, this test reveal potentiality as an instrument for vocabulary assessment in Portugal.Objetivo: Este estudo teve por objetivo a análise e quantificação dos processos de designação e substituição semântica apresentados na prova do vocabulário do Teste de Linguagem Infantil ABFW, padronizado no Brasil e adaptado para Português Europeu (PE), assim como a comparação dos resultados obtidos nos dois países, de forma a analisar a pertinência da sua extensibilidade à população portuguesa. Métodos: A prova foi aplicada a 150 crianças de 5 e 6 anos de idade, de desenvolvimento típico, na Região Norte de Portugal. A prova é constituída por nove categorias conceituais e cada categoria formada por diferentes vocábulos, que foram avaliados sempre pela mesma ordem sequencial. Resultados: A amostra mostrou desempenho inferior, em relação à norma, apenas nas categorias semânticas vestuário, locais e alimentos. Todas as outras categorias revelaram desempenho superior. As categorias do vocabulário que apresentaram maior percentagem de respostas corretas foram: animais, formas e cores e brinquedos e instrumentos musicais. As categorias que apresentaram percentagem superior de processos de substituição, em relação à norma, foram alimentos e locais. Os processos de substituição mais utilizados foram: substituição por co-hipônimo, vocábulos que designam atributos semânticos, valorização do estímulo visual, hiperônimos e parassinônimos. Conclusão: Dada a homogeneidade dos resultados deste estudo com os resultados obtidos em outros estudos no Brasil, esta prova revela potencialidades como instrumento de avaliação do vocabulário em Portugal.This work is funded by CIEd – Research Centre on Education, projects UID/CED/1661/2013 and UID/CED/1661/2016, Institute of Education, University of Minho, through national funds of FCT/MCTESPT.info:eu-repo/semantics/publishedVersio

MicroRNA and mRNA profiling in the idiopathic inflammatory myopathies

Background The idiopathic inflammatory myopathies (IIMs) are heterogeneous autoimmune conditions of skeletal muscle inflammation and weakness. MicroRNAs (miRNAs) are short, non-coding RNA which regulate gene expression of target mRNAs. The aim of this study was to profile miRNA and mRNA in IIM and identify miRNA-mRNA relationships which may be relevant to disease. Methods mRNA and miRNA in whole blood samples from 7 polymyositis (PM), 7 dermatomyositis (DM), 5 inclusion body myositis and 5 non-myositis controls was profiled using next generation RNA sequencing. Gene ontology and pathway analyses were performed using GOseq and Ingenuity Pathway Analysis. Dysregulation of miRNAs and opposite dysregulation of predicted target mRNAs in IIM subgroups was validated using RTqPCR and investigated by transfecting human skeletal muscle cells with miRNA mimic. Results Analysis of differentially expressed genes showed that interferon signalling, and anti-viral response pathways were upregulated in PM and DM compared to controls. An anti-Jo1 autoantibody positive subset of PM and DM (n = 5) had more significant upregulation and predicted activation of interferon signalling and highlighted T-helper (Th1 and Th2) cell pathways. In miRNA profiling miR-96-5p was significantly upregulated in PM, DM and the anti-Jo1 positive subset. RTqPCR replicated miR-96-5p upregulation and predicted mRNA target (ADK, CD28 and SLC4A10) downregulation. Transfection of a human skeletal muscle cell line with miR-96-5p mimic resulted in significant downregulation of ADK. Conclusion MiRNA and mRNA profiling identified dysregulation of interferon signalling, anti-viral response and T-helper cell pathways, and indicates a possible role for miR-96-5p regulation of ADK in pathogenesis of IIM

Condensed tannin reactivity inhibition by internal rearregements: detection by CP-Mas 13C NMR

Tannin extracts were prepared from barks of maritime pine (Pinus maritimus), aleppo pine (Pinushalepensis), Norway spruce (Picea abies) and from a mixture of barks of different pine species (Pinusspp., namely 20% black pine (Pinus thunbergii)+ 30% Scots pine (Pinus sylvestris) + 20% maritime pine(Pinus maritimus) + 10% Aleppo Pine (Pinus halepensis) + 5% Douglas fir (Pseudotsuga menziesii) +15% Norway spruce (Picea abies)) at a paper mill. The 13C-NMR spectra were carried out from thesetannins. Blending systems adhesives were prepared with 5% paraformaldehyde to measure the reactivityby gel time, and to determinate the mechanical resistance by thermomechanical analysis (TMA) andthe internal bond strength (IB) according to the European Norm EN-312. The CP MAS 13C NMR bandsat 163 ppm and the increase number of smaller bands between 20 and 65 ppm clearly indicate that theextraction of procyanidin-type tannins has been incorrect yielded high relative proportions of catechinicacid structures and diarylpropanol-catechinin acid dimer caused by internal flavonoid rearrangement, andcausing the blockage of the C6 and C8 reactive sites, rendering unusable the tannin for wood adhesiveapplications. Thus, the gel times are very long except for the maritime pine tannin with a value of 51(s). The TMA analysis gave very low MOE values for almost all the tannin extract samples, except formaritime pine. This situation was confirmed by the IB test. Only maritime pine tannin presented a goodmechanical resistance with a value of 0.6 (MPa). Only this sample fulfils the standard requested

Condensed tannin reactivity inhibition by internal rearrangements: Detection by CP-MAS 13C NMR

Tannin extracts were prepared from barks of maritime pine (Pinus maritimus), aleppo pine (Pinus halepensis), Norway spruce (Picea abies) and from a mixture of barks of different pine species (Pinus spp., namely 20% black pine (Pinus thunbergii)+ 30% Scots pine (Pinus sylvestris) + 20% maritime pine (Pinus maritimus) + 10% Aleppo Pine (Pinus halepensis) + 5% Douglas fir (Pseudotsuga menziesii) + 15% Norway spruce (Picea abies)) at a paper mill. The 13C-NMR spectra were carried out from these tannins. Blending systems adhesives were prephe increase number of smaller bands between 20 and 65 ppm clearly indicate that the extraction of procyanidin-type tannins has been incorrect yielded high relative proportions of catechinic acid structures and diarylpropanol-catechinin acid dimer caused by internal flavonoid rearrangement, and causing the blockage of the C6 and C8 reactive sites, rendering unusable the tannin for wood adhesive applications. Thus, the gel times are very long except for the maritime pine tannin with a value of 51 (s). The TMA analysis gave very low MOE values for almost all the tannin extract samples, except for maritime pine. This situation was confirmed by the IB test. Only maritime pine tannin presented a good mechanical resistance with a value of 0.6 (MPa). Only this sample fulfils the standard requested