Fábrica de Loiça de Sacavém (ca. 1858–1994) was among the first to produce white earthenware in Portugal, becoming one of the country’s leading ceramic manufacturers during the late 19th to early 20th centuries. Research on white earthenware has accompanied the growing interest in post-industrial archaeology but is still poorly explored compared to more ancient ceramic productions. This study focused on the ceramic body, glazes, and colourants of tableware produced by Fábrica de Loiça de Sacavém during the first 50 years of its activity (1859–1910). A multi-analytical approach was selected to investigate the chemical and mineralogical composition of the ceramic body, glaze, and pigments using optical microscopy, variable-pressure scanning electron microscope energy-dispersive X-ray spectroscopy (VP-SEM-EDS), μ-Raman spectroscopy, μ-X-ray Diffraction (μ-XRD), and reflectance spectroscopy (hyperspectral image analysis). The studied tableware was produced with a Ca-poor siliceous–aluminous white earthenware ceramic body covered with transparent alkali lead or lead borosilicate glaze, and most colourants were complex Cr-based pigments. These results are in agreement with the little documental evidence from this period found in the manufacturer’s archives.

Poly(p-xylylene) derivatives, widely known as Parylenes, have been considerably adopted by the scientific community for several applications, ranging from simple passive coatings to active device components. Here, we explore the thermal, structural, and electrical properties of Parylene C, and further present a variety of electronic devices featuring this polymer: transistors, capacitors, and digital microfluidic (DMF) devices. We evaluate transistors produced with Parylene C as a dielectric, substrate, and encapsulation layer, either semitransparent or fully transparent. Such transistors exhibit steep transfer curves and subthreshold slopes of 0.26 V/dec, negligible gate leak currents, and fair mobilities. Furthermore, we characterize MIM (metal–insulator–metal) structures with Parylene C as a dielectric and demonstrate the functionality of the polymer deposited in single and double layers under temperature and AC signal stimuli, mimicking the DMF stimuli. Applying temperature generally leads to a decrease in the capacitance of the dielectric layer, whereas applying an AC signal leads to an increase in said capacitance for double-layered Parylene C only. By applying the two stimuli, the capacitance seems to suffer from a balanced influence of both the separated stimuli. Lastly, we demonstrate that DMF devices with double-layered Parylene C allow for faster droplet motion and enable long nucleic acid amplification reactions.

Many proteins naturally carry metal centers, with a large share of them being in the active sites of several enzymes. Paramagnetic effects are a powerful source of structural information and, therefore, if the native metal is paramagnetic, or it can be functionally substituted with a paramagnetic one, paramagnetic effects can be used to study the metal sites, as well as the overall structure of the protein. One notable example is cobalt(II) substitution for zinc(II) in carbonic anhydrase. In this manuscript we investigate the effects of sodium thiocyanate on the chemical environment of the metal ion of the human carbonic anhydrase II. The electron paramagnetic resonance (EPR) titration of the cobalt(II) protein with thiocyanate shows that the EPR spectrum changes from A-type to C-type on passing from 1:1 to 1:1000-fold ligand excess. This indicates the occurrence of a change in the electronic structure, which may reflect a sizable change in the metal coordination environment in turn caused by a modification of the frozen solvent glass. However, paramagnetic nuclear magnetic resonance (NMR) data indicate that the metal coordination cage remains unperturbed even in 1:1000-fold ligand excess. This result proves that the C-type EPR spectrum observed at large ligand concentration should be ascribed to the low temperature at which EPR measurements are performed, which impacts on the structure of the protein when it is destabilized by a high concentration of a chaotropic agent.

This paper presents a comprehensive study of the evidence for ancient tin mining at the Ervedosa mine (Vinhais, Portugal). The geological context of the site indicates a rich cassiterite (SnO2) deposit, which was subject to mining in the twentieth century. Some ancient mining and ore processing stone tools were recovered during the twentieth century mining operations, namely one hammer, one pounder, one flat anvil and five small tools used both as pounders and crushing anvils, evidencing prehistoric mining activities. XRF and SEM–EDS chemical analyses were performed on primary and secondary cassiterite samples from the mining site, demonstrating the abundance and chemical heterogeneity of the tin (Sn) ores. The stone tools can be ascribed to Bronze Age or, at the latest, Early Iron Age (2nd millennium to the first half of 1st millennium BCE) by comparison with similar tools from other Iberian and European archaeological contexts. High-resolution photogrammetric 3D models of the tools are made available in this study. The historical descriptions of the findings and the research made on the technical archives about the mine allowed correlating the tools to mining in a primary context, focused on rich quartz veins in granitic or greisen bedrock, rather than mining in a secondary context. XRF and SEM–EDS analyses performed on the stone material and on surface adherences support their identification as specific types of hard rocks, such as granite, amphibolite and quartzite, and allowed the detection of Sn-rich adherent particles, confirming their use for Sn-material processing. The potential relation between the cassiterite resources and the local later prehistoric (Bronze Age to Early Iron Age) settlement pattern is also discussed. The results raise awareness and provide relevant data about the existence of tin mining in primary contexts during later prehistoric times in the NW Iberian Peninsula.

TheBacteroides thetaiotaomicronhas developed a consortium of enzymes capable of overcoming steric constraints and degrading, in a sequential manner, the complex rhamnogalacturonan II (RG-II) polysaccharide. BT0996 protein acts in the initial stages of the RGII depolymerisation, where its two catalytic modules remove the terminal monosaccharides from RG-II side chains A and B. BT0996 is modular and has three putative carbohydrate-binding modules (CBMs) for which the roles in the RG-II degradation are unknown. Here, we present the characterisation of themoduleat the C-terminal domain, which we designated BT0996C. The high-resolution structure obtained by X-ray crystallography reveals that the protein displays a typical β-sandwich fold with structural similarity to CBMs assigned to families 6 and 35. The distinctive features are: 1) the presence of several charged residues at the BT0996-C surface creating a large, broad positive lysine-rich patch that encompasses the putative binding site; and 2) the absence of the highly conserved binding-site signatures observed in CBMs from families 6 and 35, such as region A tryptophan and region C asparagine. These findings hint at a binding mode of BT0996-C not yet observed in its homologues. In line with this, carbohydrate microarrays and microscale thermophoresis show the ability of BT0996-C to bind α1-4-linked polygalacturonic acid, and that electrostatic interactions are essential for the recognition of the anionic polysaccharide. The results support the hypothesis that BT0996-C may have evolved to potentiate the action of BT0996 catalytic modules on the complex structure of RG-II by binding to the polygalacturonic acid backbone sequence.

New dicationic ionic liquids (DcILs) based on carboxylic acid-derived, N-acetyl amino acid-derived or bromide anions, and ammonium cations were synthesized and characterized. DcILs were employed as co-solvents to improve the solubility of ibuprofen and ketoprofen belonging to BCS class II. These DcILs demonstrated to be less cytotoxic towards fibroblasts L929 cells and contributed to an augment in the solubility of both drugs when compared with monocationic ionic liquids (McILs). The cytotoxic profile of some of these ILs was established, and when the linker between two ammonium cations was an ether group or a short alkyl chain an IC50 higher than 200 mM for fibroblasts L929 cells was achieved. The anion structure showed to be a key factor in the solubility of both drugs, being the family of carboxylic acid-derived, the one that presented the most significant effect, followed by N-acetyl amino acid-derived and finally bromide. The two dimensional 1H1H– NOESY NMR spectra showed the interaction between the IL and the two oral drugs, responsible for the improvement of their solubility. The lipophilicity (logP) of ibuprofen and ketoprofen reduced in the presence of these new DcILs.

Teachers’ knowledge plays a central role in technology integration. In this study we analyze situations, where there is some divergence between the mathematical results and the information offered by the graphing calculator (lack of mathematical fidelity), putting the focus in the teachers and in their approaches. The goal of this study is to analyze, in the light of knowledge for teaching mathematics with technology (KTMT) model, the teachers’ professional knowledge, assuming the situations of lack of mathematical fidelity as having the potential to reveal some characteristics of their knowledge. Specifically, considering the teaching of functions at 10th grade (age 16), we intend to analyze: (1) What knowledge do the teachers have of technology and of its mathematical fidelity? (2) What can the teachers’ options related to situations of lack of mathematical fidelity tell us about their knowledge in other KTMT domains? The study adopts a qualitative and interpretative approach based on the case studies of two teachers. Data were collected by interviews and class observation, being the analysis guided by the KTMT model. The main result points to the relevance of the mathematics and technology knowledge. However, there is evidence of some difficulties to integrate the information provided by the technology with the mathematics, and also of some interference of the teaching and learning and technology knowledge, and specifically of the knowledge related to the students. This suggests that the analysis of the teachers’ actions in relation to situations of lack of mathematical fidelity, can be useful to characterize their KTMT.

Traditional bioactive glass powders are typically composed of irregular particles that can be packed into dense configurations presenting low interconnectivity, which can limit bone ingrowth. The use of novel biocomposite sphere formulations comprising bioactive factors as bone fillers are most advantageous, as it simultaneously allows for packing the particles in a 3-dimensional manner to achieve an adequate interconnected porosity, enhanced biological performance, and ultimately a superior new bone formation. In this work, we develop and characterize novel biocomposite macrospheres of Sr-bioactive glass using sodium alginate, polylactic acid (PLA), and chitosan (CH) as encapsulating materials for finding applications as bone fillers. The biocomposite macrospheres that were obtained using PLA have a larger size distribution and higher porosity and an interconnectivity of 99.7%. Loose apatite particles were observed on the surface of macrospheres prepared with alginate and CH by means of soaking into a simulated body fluid (SBF) for 7 days. A dense apatite layer was formed on the biocomposite macrospheres' surface produced with PLA, which served to protect PLA from degradation. In vitro investigations demonstrated that biocomposite macrospheres had minimal cytotoxic effects on a human osteosarcoma cell line (SaOS-2 cells). However, the accelerated degradation of PLA due to the degradation of bioactive glass may account for the observed decrease in SaOS-2 cells viability. Among the biocomposite macrospheres, those composed of PLA exhibited the most promising characteristics for their potential use as fillers in bone tissue repair applications.

The geochemical signatures of dinosaur eggshells represent well-established proxies in paleoenvironmental and paleobiological research. The variable sampling procedures reported in the literature, however, deserve attention. In order to evaluate the impact of different sampling methodologies on carbon and oxygen isotope and elemental concentrations, grinding was contrasted with drilling to extract powder samples from eggshell fragments collected at several locations. Eggshell data were further contrasted with surface materials, encasing matrix and compared with independent proxies using petrographic and elemental techniques. Iron and manganese elemental concentrations revealed an enrichment sequence depending on the sampling strategy for the same eggshell fragment. This pattern can be mistaken for a variable state of preservation. In contrast, carbon and oxygen isotope values exhibited only subtle differences and lacked clear trends. This suggests that isotope data are less susceptible to different methodological approaches. It is shown that drilling offers a wider range of possibilities compared to grinding (e.g., faster and less destructive). Additionally, drilled powder samples can confidently be used for elemental and isotope analysis, excluding contamination, thus providing a more accurate set of proxy data from eggshell archives.

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This study aims to understand the functional thinking of 10th-grade students while studying functions. Specifically, we intend to answer the following research questions: what are the functional thinking processes used by 10th-grade students when studying functions? What difficulties do students present while learning functions? In view of the nature of this research objective, we adopted a qualitative and interpretative approach. In order to answer these questions, data were collected from the written records produced by the students while solving the proposed tasks, from records of the oral interactions during discussions and from a questionnaire. The results show that functional thinking processes were implicit in the resolution of the tasks proposed to the students. The students expressed an understanding of how the variables were related, presenting evidence of their functional thinking while working on the new concepts represented by the functions addressed in the proposed tasks. Some students expressed difficulties in interpreting the different types of representations associated with the functions, in retaining the necessary information from a graphical representation that would help them to draw conclusions and establish correspondences, in explaining functional relationships, and in interpreting the information provided by algebraic expressions. These difficulties can reduce the recognition of the relationships between variables and their behavior in the different representations, becoming an obstacle to learning for some students.