A voltametria cíclica e de varrimento linear unidirecional: suas potencialidades na caraterização de processos de corrosão

Artigo licenciado sob uma Licença Creative Commons: https://creativecommons.org/licenses/by-nc/4.0/deed.pt"O artigo apresenta as técnicas da voltametria cíclica e da voltametria de varrimento linear unidirecional, que são métodos eletroquímicos extremamente úteis e versáteis no estudo do comportamento de um metal ou liga, face a ambientes mais ou menos agressivos. As potencialidades das técnicas são realçadas, assim como as vantagens introduzidas pela instrumentação digital. Trata-se de um artigo de divulgação, tendo por objetivo ser acessível a engenheiros, técnicos e outros, a trabalhar na área da corrosão. Para exemplificar o tipo de informação que pode ser obtida são apresentados resultados de vários estudos realizados pelos autores.

Enhancing the teaching-research nexus in the undergraduate curriculum through assessment

Successful linkages between teaching and research in the undergraduate curriculum are strongly dependent on academics’ ability to encourage and facilitate an inquiry based approach to learning. An assessment strategy in which students become active participants in the assessment process is crucial to facilitate the development of this inquiry based approach. Developing this so-called research-mindedness is central to helping students' to become independent learners and to be more effective professionals in their future careers. This paper describes a distributed systems approach to assessment implemented in the undergraduate module Molecular Biology. The assessment comprised a series of sequence identification, database use and analysis steps, with each student being given a different starting gene. In combination, the students analysed an entire genetic pathway. This approach allows the assignments generated to be combined and used to address a single larger question, which can be either teaching or research based. This is then fed back into the teaching. This direct link between the assessment outcomes and the learning process increases student engagement with the subject and sense of ownership of the work carried out. This approach to assessment, in which students undertake a small part of a larger task, is ideal for various technical, skills-based, assignments, such as those central to the many types of bioinformatics analyses. However, it can be adapted to various types of meta-review. The paper discusses the details for the implementation, as well as the benefits and potential pitfalls of the approach

Galvanic corrosion of two non noble dental alloys

Artigo licenciado sob uma Licença Creative Commons: https://creativecommons.org/licenses/by/4.0/"This study aims to evaluate the corrosion resistance of two nonnoble dental alloys, namely, the Wiron®88 (Ni–Cr–Mo) and the Remanium 2000+ (Co–Cr–Mo–W). A noble alloy, the V-Gnathos® Plus (AuPt) previously studied was also considered for the purpose of comparison. The study was conducted in artificial saliva, pH 7.1, at 37 °C, by cyclic and linear sweep voltammetry, electrochemical impedance spectroscopy and chronoamperometry. The Rp value of the alloy of high contents of Ni, the Wiron®88, was 26.2±0.2 kΩ cm2 and of the one with high contents of Co, the Remanium 2000+, was 22.5±0.6 kΩ cm2. Data from linear polarization resistance and electrochemical impedance spectroscopy lead to the same order for the resistance against corrosion. The order from the less to the more reactive alloy is: Wiron®88 → Remanium 2000+. The galvanic cell obtained by coupling the two nonnoble alloys presents very low cell potential (a few mV, -18 mV), while the galvanic cell between one noble alloy (the V-Gnathos® Plus) and the Wiron®88 showed a higher cell potential (-104 mV). Both galvanic couples, under short circuit, have lead to the release of cations, namely, Co2+, in the case of the Wiron®88|Remanium 2000+ and Ni2+ for the Wiron®88|V-Gnathos® Plus, galvanic couples, respectively, with the ionic concentrations reaching values of 12.15 and 7.30 μg L-1 (7.30 ppb), respectively. SEM micrographs obtained after 25 days immersion in artificial saliva, at 37 °C, showed the formation of well-defined pits on the surface of the two non-noble alloys.

Specification of osteoblast cell fate by canonical Wnt signaling requires Bmp2

Enhanced BMP or canonical Wnt (cWnt) signaling are therapeutic strategies employed to enhance bone formation and fracture repair, but the mechanisms each pathway utilizes to specify cell fate of bone-forming osteoblasts remain poorly understood. Among all BMPs expressed in bone, we find that singular deficiency of Bmp2 blocks the ability of cWnt signaling to specify osteoblasts from limb bud or bone marrow progenitors. When exposed to cWnts, Bmp2-deficient cells fail to progress through the Runx2/Osx1 checkpoint and thus do not upregulate multiple genes controlling mineral metabolism in osteoblasts. Cells lacking Bmp2 after induction of Osx1 differentiate normally in response to cWnts, suggesting that pre-Osx1(+) osteoprogenitors are an essential source and a target of BMP2. Our analysis furthermore reveals Grainyhead-like 3 (Grhl3) as a transcription factor in the osteoblast gene regulatory network induced during bone development and bone repair, which acts upstream of Osx1 in a BMP2-dependent manner. The Runx2/Osx1 transition therefore receives crucial regulatory inputs from BMP2 that are not compensated for by cWnt signaling, and this is mediated at least in part by induction and activation of Grhl3.National Institute of Arthritis and Musculoskeletal and Skin Diseases (NIH-NIAMS)Harvard Sch Dent Med, Dept Dev Biol, 188 Longwood Ave, Boston, MA 02115 USASaitama Med Univ, Res Ctr Genom Med, Div Pathophysiol, 1397-1 Yamane, Hidaka, Saitama 3501241, JapanUniv Fed Sao Paulo, Inst Ciencia & Tecnol, Rua Talim 330, BR-12231280 Sao Jose Dos Campos, SP, BrazilUniversidade Federal de São Paulo, Rua Talim, 330, São José dos Campos, São Paulo, CEP 12231-280, BrazilNIH-NIAMS: R01 AR055904Web of Scienc

Synthesis of gold functionalised nanoparticles with the eranthis hyemalis lectin and preliminary toxicological studies on caenorhabditis elegans

The lectin found in the tubers of the Winter Aconite (Eranthis hyemalis) plant (EHL) is a Type II Ribosome Inactivating Protein (RIP). Type II RIPs have shown anti-cancer properties and have great potential as therapeutic agents. Similarly, colloidal gold nanoparticles are successfully used in biomedical applications as they can be functionalised with ligands with high affinity and specificity for target cells to create therapeutic and imaging agents. Here we present the synthesis and characterization of gold nanoparticles conjugated with EHL and the results of a set of initial assays to establish whether the biological effect of EHL is altered by the conjugation. Gold nanoparticles functionalised with EHL (AuNPs@EHL) were successfully synthesised by bioconjugation with citrate gold nanoparticles (AuNPs@Citrate). The conjugates were analysed by UV-Vis spectroscopy, Dynamic Light Scattering (DLS), Zeta Potential analysis, and Transmission Electron Microscopy (TEM). Results indicate that an optimal functionalisation was achieved with the addition of 100 µL of EHL (concentration 1090 ± 40 µg/mL) over 5 mL of AuNPs (concentration [Au0] = 0.8 mM). Biological assays on the effect of AuNPs@EHL were undertaken on Caenorhabditis elegans, a free-living nematode commonly used for toxicological studies, that has previously been shown to be strongly affected by EHL. Citrate gold nanoparticles did not have any obvious effect on the nematodes. For first larval stage (L1) nematodes, AuNPs@EHL showed a lower biological effect than EHL. For L4 stage, pre-adult nematodes, both EHL alone and AuNPs@EHL delayed the onset of reproduction and reduced fecundity. These assays indicate that EHL can be conjugated to gold nanoparticles and retain elements of biocidal activity

Light, medium-weight or heavy? The nature of the first supermassive black hole seeds

Observations of hyper-luminous quasars at $z>6$ reveal the rapid growth of supermassive black holes (SMBHs $>10^9 \rm M_{\odot}$) whose origin is still difficult to explain. Their progenitors may have formed as remnants of massive, metal free stars (light seeds), via stellar collisions (medium-weight seeds) and/or massive gas clouds direct collapse (heavy seeds). In this work we investigate for the first time the relative role of these three seed populations in the formation of $z>6$ SMBHs within an Eddington-limited gas accretion scenario. To this aim, we implement in our semi-analytical data-constrained model a statistical description of the spatial fluctuations of Lyman-Werner (LW) photo-dissociating radiation and of metal/dust enrichment. This allows us to set the physical conditions for BH seeds formation, exploring their relative birth rate in a highly biased region of the Universe at $z>6$. We find that the inclusion of medium-weight seeds does not qualitatively change the growth history of the first SMBHs: although less massive seeds ($<10^3 \rm M_\odot$) form at a higher rate, the mass growth of a $\sim 10^9 \rm M_\odot$ SMBH at $z<15$ is driven by efficient gas accretion (at a sub-Eddington rate) onto its heavy progenitors ($10^5 \rm M_\odot$). This conclusion holds independently of the critical level of LW radiation and even when medium-weight seeds are allowed to form in higher metallicity galaxies, via the so-called super-competitive accretion scenario. Our study suggests that the genealogy of $z \sim 6$ SMBHs is characterized by a rich variety of BH progenitors, which represent only a small fraction ($< 10 - 20\%$) of all the BHs that seed galaxies at $z > 15$.Comment: (21 pages, 18 figures, 2 tables. Accepted for publication in MNRAS

Identification of genomic loci associated with genotypic and phenotypic variation among Pseudomonas aeruginosa clinical isolates from pneumonia

In this work, a genotype-phenotype survey of a highly diversified Pseudomonas aeruginosa collection was conducted, aiming to detail pathogen-associated scenarios that clinicians face nowadays. Genetic relation based on RAPD-PCR of 705 isolates, retrieved from 424 patients and several clinical contexts, reported an almost isolate-specific molecular-pattern. Pneumonia-associated isolates HB13 and HB15, clustered in the same RAPD-PCR group, were selected to evaluate the genomic background underlying their contrasting antibiotic resistance and virulence. The HB13 genome harbors antibiotic-inactivating enzymes-coding genes (e.g. aac(3)-Ia, arr, blaVIM-2) and single-nucleotide variations (SNVs) in antibiotic targets, likely accounting for its pan-resistance, whereas HB15 susceptibility correlated to predicted dysfunctional alleles. Isolate HB13 showed the unprecedented rhl-cluster absence and variations in other pathogen competitiveness contributors. Conversely, HB15 genome comprises exoenzyme-coding genes and SNVs linked to increased virulence. Secretome analysis identified signatures features with unknown function as potential novel pathogenic (e.g. a MATE-protein in HB13, a protease in HB15) and antibiotic resistance (a HlyD-like secretion protein in HB13) determinants. Detection of active prophages, proteases (including protease IV and alkaline metalloproteinase), a porin and a peptidase in HB15 highlights the secreted arsenal likely essential for its virulent behavior. The presented phenotype-genome association will contribute to the current knowledge on Pseudomonas aeruginosa pathogenomics.This work was supported by the strategic programme UID/BIA/0050/2013 (POCI-01-0145-FEDER-007569) funded by national funds through FCT I.P., by ERDF through the COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI) and through a PhD grant (SFRH/BD/98558/2013) attributed to C.S.M. The facility for Biological Mass Spectrometry Isabel Moura was funded by Proteomass Scientific Society. H.M.S. is funded by the FCT 2015 Investigator Program (IF/00007/2015)

The polytropic approximation and X-ray scaling relations: constraints on gas and dark matter profiles for galaxy groups and clusters

We constrain gas and dark matter (DM) parameters of galaxy groups and clusters, by comparing X-ray scaling relations to theoretical expectations, obtained assuming that the gas is in hydrostatic equilibrium with the DM and follows a polytropic relation. We vary four parameters: the gas polytropic index Gamma, its temperature at large radii T_xi, the DM logarithmic slope at large radii zeta and its concentration c_vir. When comparing the model to the observed mass-temperature (M-T) relation of local clusters, our results are independent of both T_xi and c_vir. We thus obtain constraints on Gamma, by fixing the DM profile, and on zeta, by fixing the gas profile. For an NFW DM profile, we find that 6/5<Gamma<13/10, which is consistent with numerical simulations and observations of individual clusters. Taking 6/5<Gamma<13/10 allows the DM profile to be slightly steeper than the NFW profile at large radii. Upon including local groups, we constrain the mass-dependence of Gamma and the value of T_xi. Interestingly, with Gamma=6/5 and zeta=-3, we reproduce the observed steepening/breaking of the M-T relation at low M, if 10^6 K<T_xi<10^7 K, consistent with simulations and observations of the warm-hot intergalactic medium. When extrapolated to high redshift z, the model with a constant Gamma reproduces the expected self-similar behaviour. We also account for the observed, non-self-similar relations provided by some high-z clusters, as they provide constraints on the evolution of Gamma. Comparing our model to the observed luminosity-temperature relation, we discriminate between different M-c_vir relations: a weak dependence of c_vir on M is currently preferred by data. This simple theoretical model accounts for much of the complexity of recent, improved X-ray scaling relations, provided that we allow for a mild dependence of Gamma on M or for T_xi consistent with intercluster values. [abridged]Comment: 20 pages, 18 figures, 2 tables. Accepted for publication in MNRAS, with minor changes. Accepted version plus two typos corrected. Abstract abridged for astro-ph submissio

Intramolecular excimer formation and sensing behavior of new fluorimetric probes and their interactions with metal cations and barbituric acids

A new family of compounds able to promote host-guest interactions with specific molecules (e.g., cyanuric and parabanic acids) and to coordinate metal ions, namely Zn(II) and Cu(II), has been synthesized and fully characterized. The new probes derive from the attachment of two methylaminopyrene units to the carbonyl precursor 2,6-bis(2-formylphenoxymethyl)pyridine.http://www.sciencedirect.com/science/article/B6THH-4HF5KD3-1/1/ef66847d1e019d05e2068bef93cfbd9

Synthesis and Structural Characterization of Branched Bimetallic AuPd Nanoparticles with a Highly Tunable Optical Response

Bimetallic nanostructures composed of gold (Au) and palladium (Pd) have garnered increased interest for their applications in heterogeneous catalysis. This study reports a simple strategy for manufacturing Au@Pd bimetallic branched nanoparticles (NPs), which offer a tunable optical response, using polyallylamine-stabilized branched AuNPs as template cores for Pd overgrowth. The palladium content can be altered by manipulating the concentration of PdCl4 2− and ascorbic acid (AA) that are injected, which permit an overgrowth of the Pd shell up to ca. 2 nm thick. The homogeneous distribution of Pd at the surfaces of Au NPs can be carried out regardless of their size or branching degree, which allows for an adjustment of the plasmon response in the near-infrared (NIR) spectral range. As a proof of concept, the nanoenzymatic activity of pure gold and gold−palladium NPs was compared, exploring their peroxidase-like activity in the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). The bimetallic AuPd NPs demonstrate an increase in the catalytic properties attributed to the presence of palladium at the surface of gold