142 research outputs found

    Unexpected differences between thermal and photoinitiated cationic curing of a diglycidyl ether of bisphenol A modified with a multiarm star poly(styrene)-b-poly(ε-caprolactone) polymer

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    The effect of adding a multiarm star poly(styrene)-b-poly(ε-caprolactone) polymer on the cationic thermal and photoinitiated curing of diglycidyl ether of bisphenol A was studied. This star-polymer decelerated the thermal curing of diglycidyl ether of bisphenol A and modified the final structure of the epoxy matrix. The photocuring was influenced significantly by the addition of the multiarm star. When the proportion of this modifier added was 5%, much more time was necessary for complete photocuring (160 min at 40ºC). In the presence of 10% of modifier, the degree of photocuring reached was very low (0.196 at 120°C). A subsequent thermal post-curing was necessary to cure completely the system. During photocuring in presence of poly(styrene)-b-poly(ε-caprolactone), the formation of dormant species, which are reactivated when the temperature increases, takes places. The kinetics of the thermal curing and the photocuring was analyzed using an isoconversional method due to the complexity of the reactive process. Applying this method, it has been confirmed the dependence of activation energy on the degree of conversion. The fracture morphology analyzed by scanning electron microscopy exhibited a second phase originated during photocuring by the presence of the modifier

    Dual-curable stereolithography resins for superior thermomechanical properties

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    Stereolithography (SL) stands out as a relatively fast additive manufacturing method to produce thermoset components with high resolutions. The majority of SL resins consist of acrylate monomers which result in materials with cur-ing-induced shrinkage problems and this, in addition to the incomplete and non-uniform conversions reached in the SL process, results in poor mechanical properties. To address this issue, a dual-curing formulation was developed by mixing an epoxy monomer into a commercial multi-acrylate SL resin: the first curing stage is acrylate free-radical photopolymerization at ambient temperature, and the second curing stage is cationic epoxy homopolymerization at higher temperatures. The fully dual-cured materials are macroscopically homogeneous, with nanoscale domains observed by Atomic Force Mi-croscopy (AFM), and with unimodal tan delta peaks observed in Dynamic Mechanical Analysis (DMA). The uncured material was storage stable at ambient conditions for at least 9 weeks since the epoxy part was virtually unreactive at these temper-atures. With the dual-cured materials, a nearly 10-fold increase in Young’s modulus was achieved over the neat acrylate resin. At the thermal curing stage, the presence of diperoxyketal thermal radical initiator to the liquid formulation facilitated the polymerization of unreacted acrylates that remained from the SL process simultaneously with epoxy homopolymerization and helped the material attain improved properties

    CSF1R blockade slows the progression of amyotrophic lateral sclerosis by reducing microgliosis and invasion of macrophages into peripheral nerves

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    Inflammation is a common neuropathological feature in several neurological disorders, including amyotrophic lateral sclerosis (ALS). We have studied the contribution of CSF1R signalling to inflammation in ALS, as a pathway previously reported to control the expansion and activation of microglial cells. We found that microglial cell proliferation in the spinal cord of SOD1G93A transgenic mice correlates with the expression of CSF1R and its ligand CSF1. Administration of GW2580, a selective CSF1R inhibitor, reduced microglial cell proliferation in SOD1G93A mice, indicating the importance of CSF1-CSF1R signalling in microgliosis in ALS. Moreover, GW2580 treatment slowed disease progression, attenuated motoneuron cell death and extended survival of SOD1G93A mice. Electrophysiological assessment revealed that GW2580 treatment protected skeletal muscle from denervation prior to its effects on microglial cells. We found that macrophages invaded the peripheral nerve of ALS mice before CSF1R-induced microgliosis occurred. Interestingly, treatment with GW2580 attenuated the influx of macrophages into the nerve, which was partly caused by the monocytopenia induced by CSF1R inhibition. Overall, our findings provide evidence that CSF1R signalling regulates inflammation in the central and peripheral nervous system in ALS, supporting therapeutic targeting of CSF1R in this disease

    A Spectral Transfer Function to Harmonize Existing Soil Spectral Libraries Generated by Different Protocols

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    Soil spectral libraries (SSLs) are important big-data archives (spectra associated with soil properties) that are analyzed via machine-learning algorithms to estimate soil attributes. Since different spectral measurement protocols are applied when constructing SSLs, it is necessary to examine harmonization techniques to merge the data. In recent years, several techniques for harmonization have been proposed, among which the internal soil standard (ISS) protocol is the most largely applied and has demonstrated its capacity to rectify systematic effects during spectral measurements. Here, we postulate that a spectral transfer function (TF) can be extracted between existing (old) SSLs if a subset of samples from two (or more) different SSLs are remeasured using the ISS protocol. A machine-learning TF strategy was developed, assembling random forest (RF) spectral-based models to predict the ISS spectral condition using soil samples from two existing SSLs. These SSLs had already been measured using different protocols without any ISS treatment the Brazilian (BSSL, generated in 2019) and the European (LUCAS, generated in 2009-2012) SSLs. To verify the TF's ability to improve the spectral assessment of soil attributes after harmonizing the different SSLs' protocols, RF spectral-based models for estimating organic carbon (OC) in soil were developed. The results showed high spectral similarities between the ISS and the ISS-TF spectral observations, indicating that post-ISS rectification is possible. Furthermore, after merging the SSLs with the TFs, the spectral-based assessment of OC was considerably improved, from R2 = 0.61, RMSE (g/kg) = 12.46 to R2 = 0.69, RMSE (g/kg) = 11.13. Given our results, this paper enhances the importance of soil spectroscopy by contributing to analyses in remote sensing, soil surveys, and digital soil mapping

    Structural studies of (rac)-BIPHEN organomagnesiates and intermediates in the halogen-metal exchange of 2-Bromopyridine

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    Four lithium magnesiate complexes (2−5) containing the dianionic (rac)-BIPHEN ligand have been prepared and characterized using X-ray crystallography and NMR spectroscopy. (THF)3·Li2Mg{(rac)-BIPHEN}nBu2, 2, (THF)3·Li2Mg{(rac)-BIPHEN}(CH2SiMe3)2, 3, and (THF)2·Li2Mg{(rac)-BIPHEN}neoPe2, 4, have been prepared by complexation of the appropriate dialkylmagnesium compound with in situ prepared Li(rac)-BIPHEN in a mixture of hydrocarbon/THF. For all structures, the Mg centers are four-coordinate (and retain the alkyl groups); however, in 2 and 3 the two Li centers have different coordination spheres (one binding to one THF molecule, the other to two). The solid-state structures of 2 and 3 are essentially isostructural with that of 4 except that both Li atoms in this molecule have equivalent coordination spheres. The solution behaviors of these three molecules have been studied by 1H, 13C, and DOSY NMR spectroscopy. During the synthesis of 2, it was discovered that a (rac)-BIPHEN-rich (or n-butyl-free) lithium magnesiate, (THF)4Li2Mg{(rac)-BIPHEN}fo2, 2b, could be isolated. The lithium precursor to 2−5, (THF)4·Li4{(rac)-BIPHEN)}2, 1, has also been isolated. Within the molecular structure of this tetranuclear complex, there are three different Li coordination environments. Finally, 2 has already shown promise as a reagent in a halogen−metal exchange reaction with 2-bromopyridine. The structural chemistry at play in this reaction was probed by X-ray crystallography and NMR spectroscopy. The organometallic intermediate pyridyl-magnesiated 5, (THF)2·Li2Mg{(rac)-BIPHEN}(2-pyridyl)2, was isolated in high yield

    CSF1R blockade slows the progression of amyotrophic lateral sclerosis by reducing microgliosis and invasion of macrophages into peripheral nerves

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    Inflammation is a common neuropathological feature in several neurological disorders, including amyotrophic lateral sclerosis (ALS). We have studied the contribution of CSF1R signalling to inflammation in ALS, as a pathway previously reported to control the expansion and activation of microglial cells. We found that microglial cell proliferation in the spinal cord of SOD1G93A transgenic mice correlates with the expression of CSF1R and its ligand CSF1. Administration of GW2580, a selective CSF1R inhibitor, reduced microglial cell proliferation in SOD1G93A mice, indicating the importance of CSF1-CSF1R signalling in microgliosis in ALS. Moreover, GW2580 treatment slowed disease progression, attenuated motoneuron cell death and extended survival of SOD1G93A mice. Electrophysiological assessment revealed that GW2580 treatment protected skeletal muscle from denervation prior to its effects on microglial cells. We found that macrophages invaded the peripheral nerve of ALS mice before CSF1R-induced microgliosis occurred. Interestingly, treatment with GW2580 attenuated the influx of macrophages into the nerve, which was partly caused by the monocytopenia induced by CSF1R inhibition. Overall, our findings provide evidence that CSF1R signalling regulates inflammation in the central and peripheral nervous system in ALS, supporting therapeutic targeting of CSF1R in this disease

    Maresin 1 promotes inflammatory resolution, neuroprotection, and functional neurological recovery after Spinal Cord Injury

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    Resolution of inflammation is defective after spinal cord injury (SCI), which impairs tissue integrity and remodeling and leads to functional deficits. Effective pharmacological treatments for SCI are not currently available. Maresin 1 (MaR1) is a highly conserved specialized proresolving mediator (SPM) hosting potent anti-inflammatory and proresolving properties with potent tissue regenerative actions. Here, we provide evidence that the inappropriate biosynthesis of SPM in the lesioned spinal cord hampers the resolution of inflammation and leads to deleterious consequences on neurological outcome in adult female mice. We report that, after spinal cord contusion injury in adult female mice, the biosynthesis of SPM is not induced in the lesion site up to 2 weeks after injury. Exogenous administration of MaR1, a highly conserved SPM, propagated inflammatory resolution after SCI, as revealed by accelerated clearance of neutrophils and a reduction in macrophage accumulation at the lesion site. In the search of mechanisms underlying the proresolving actions of MaR1 in SCI, we found that this SPM facilitated several hallmarks of resolution of inflammation, including reduction of proinflammatory cytokines (CXCL1, CXCL2, CCL3, CCL4, IL6, and CSF3), silencing of major inflammatory intracellular signaling cascades (STAT1, STAT3, STAT5, p38, and ERK1/2), redirection of macrophage activation toward a prorepair phenotype, and increase of the phagocytic engulfment of neutrophils by macrophages. Interestingly, MaR1 administration improved locomotor recovery significantly and mitigated secondary injury progression in a clinical relevant model of SCI. These findings suggest that proresolution, immunoresolvent therapies constitute a novel approach to improving neurological recovery after acute SCI.SIGNIFICANCE STATEMENT Inflammation is a protective response to injury or infection. To result in tissue homeostasis, inflammation has to resolve over time. Incomplete or delayed resolution leads to detrimental effects, including propagated tissue damage and impaired wound healing, as occurs after spinal cord injury (SCI). We report that inflammation after SCI is dysregulated in part due to inappropriate synthesis of proresolving lipid mediators. We demonstrate that the administration of the resolution agonist referred to as maresin 1 (MaR1) after SCI actively propagates resolution processes at the lesion site and improves neurological outcome. MaR1 is identified as an interventional candidate to attenuate dysregulated lesional inflammation and to restore functional recovery after SCI

    The Brazilian Soil Spectral Service (BraSpecS): A User-Friendly System for Global Soil Spectra Communication

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    Although many Soil Spectral Libraries (SSLs) have been created globally, these libraries still have not been operationalized for end-users. To address this limitation, this study created an online Brazilian Soil Spectral Service (BraSpecS). The system was based on the Brazilian Soil Spectral Library (BSSL) with samples collected in the Visible–Near–Short-wave infrared (vis–NIR–SWIR) and Midinfrared (MIR) ranges. The interactive platform allows users to find spectra, act as custodians of the data, and estimate several soil properties and classification. The system was tested by 500 Brazilian and 65 international users. Users accessed the platform (besbbr.com.br), uploaded their spectra, and received soil organic carbon (SOC) and clay content prediction results via email. The BraSpecS prediction provided good results for Brazilian data, but performed variably for other countries. Prediction for countries outside of Brazil using local spectra (External Country Soil Spectral Libraries, ExCSSL) mostly showed greater performance than BraSpecS. Clay R2 ranged from 0.5 (BraSpecS) to 0.8 (ExCSSL) in vis–NIR–SWIR, but BraSpecS MIR models were more accurate in most situations. The development of external models based on the fusion of local samples with BSSL formed the Global Soil Spectral Library (GSSL). The GSSL models improved soil properties prediction for different countries. Nevertheless, the proposed system needs to be continually updated with new spectra so they can be applied broadly. Accordingly, the online system is dynamic, users can contribute their data and the models will adapt to local information. Our community-driven web platform allows users to predict soil attributes without learning soil spectral modeling, which will invite end-users to utilize this powerful technique

    Artificial Intelligence for the Advancement of Lunar and Planetary Science and Exploration

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    AI-driven methods have potential to minimise manual labour during planetary data processing and aid ongoing missions with real-time data analysis. This white paper focuses on key areas of AI-driven research, the need for open source training data, and the importance of collaboration between academia and industries to advance AI-driven research

    Cystic Echinococcosis in Spain: Current Situation and Relevance for Other Endemic Areas in Europe

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    Cystic echinococcosis (CE) remains an important health problem in many regions of the world, both where no control measures have been implemented, and where control programs have been incompletely successful with ensuing re-emergence of the disease. In Spain, official data on CE show an increase in the proportion of intermediate hosts with CE during the last few years, and autochthonous pediatric patients have been reported, a sign of active local transmission of disease. A similar picture emerges from data reported to the European Food Safety Authority by other European countries. Nevertheless, several crucial aspects related to CE that would help better understand and control the disease have not been tackled appropriately, in particular the emergence of infection in specific geographical areas. In this respect, while some data are missing, other data are conflicting because they come from different databases. We review the current situation of CE in Spain compared with areas in which similar problems in the CE field exist, and offer recommendations on how to overcome those limitations. Specifically, we believe that the introduction of national registries for CE with online data entry, following the example set by the European Registry for Alveolar Echinococcosis, would help streamline data collection on CE by eliminating the need for evaluating and integrating data from multiple regions, by avoiding duplication of data from patients who access several different health facilities over time, and by providing much needed clinical and epidemiological data that are currently accessible only to clinicians
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