39 research outputs found

    Oxygen Radical Scavenger Activity, EPR, NMR, Molecular Mechanics and Extended-Hückel Molecular Orbital Investigation of the Bis(Piroxicam)Copper(II) Complex

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    The oxygen radical scavenger activity (ORSA) of [CuII(Pir)2] (HPir = Piroxicam = 4-hydroxy -2- methyl -N-2- pyridyl -2H- 1,2-benzothiazine -3- carboxamide 1,1-dioxide) was determined by chemiluminescence of samples obtained by mixing human neutrophils (from healthy subjects) and [CuII(Pir)2(DMF)2] (DMF = N,N -dimethylformammide) in DMSO/GLY/PBS (2:1:2, v/v) solution (DMSO = dimethylsulfoxide, GLY = 1,2,3-propantriol, PBS = Dulbecco’s buffer salt solution). The ratio of the residual radicals, for the HPir (1.02·10−4M) and [CuII(Pir)2(DMF)2] (1.08·10−5M)/HPir (8.01·10−−5M) systems was higher than 12 (not stimulated) [excess of piroxicam was added (Cu/Pir molar ratio ≈1:10) in order to have most of the metal complexed as bischelate]. In contrast, the ratio of residual radicals for the CuCl2 (1.00·10−5M) and [CuII(Pir)2(DMF)2] (1.08·10−5M)/Hpir (8.01·10−5M)system was 5. The [CuII(Pir)2] compound is therefore a stronger radical scavenger than either HPir or CuCl2. A molecular mechanics (MM) analysis of the gas phase structures of neutral HPir, its zwitterionic (HPir+-) and anionic (Pir-) forms, and some CuII-piroxicam complexes based on X-ray structures allowed calculation of force constants. The most stable structure for HPir has a ZZZ conformation similar to that found in the CuII (and CdII complexes) in the solid state as well as in the gas phase. The structure is stabilized by a strong H bond which involves the N(amide)-H and O(enolic) groups. The MM simulation for the [CuII(Pir)2(DMF)2] complex showed that two high repulsive intramolecular contacts exist between a pyridyl hydrogen atom of one Pir- molecule with the O donor of the other ligand. These interactions activate a transition toward a pseudo-tetrahedral geometry, in the case the apical ligands are removed. On refluxing a suspension of [CuII(Pir)2(DMF)2] in acetone a brown microcystalline solid with the Cu(Pir)2·0.5DMF stoichiometry was in fact prepared. 13C spin-lattice relaxation rates of neutral, zwitterionic and anionic piroxicam, in DMSO solution are explained by the thermal equilibrium between the three most stable structures of the three forms, thus confirming the high quality of the force field. The EPR spectrum of [CuII(Pir)2(DMF)2] (DMSO/GLY, 2:1, v/v, 298 and 110 K) agrees with a N2O2+O2 pseudo-octahedral coordination geometry. The EPR spectrum of [CuII(Pir)2·0.5DMF agrees with a pseudo-tetrahedral coordination geometry. The parameters extracted from the room temperature spectra of the solution phases are in agreement with the data reported for powder and frozen solutions. The extended-Hückel calculations on minimum energy structures of [CuII(Pir)2(DMF)2] and [CuII(Pir)2] (square planar) revealed that the HOMOs have a relevant character of dx2−y2. On the other hand the HOMO of a computer generated structure for [CuII(Pir)2] (pseudo-tetrahedral) has a relevant character of dxy atomic orbital. A dxy orbital is better suited to allow a dπ-pπ interaction to the O2- anion. Therefore this work shows that the anti-inflammatory activity of piroxicam could be due in part to the formation of [CuII(Pir)2] chelates, which can exert a SOD-like activity

    TRAFAIR: Understanding Traffic Flow to Improve Air Quality

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    Environmental impacts of traffic are of major concern throughout many European metropolitan areas. Air pollution causes 400 000 deaths per year, making it first environmental cause of premature death in Europe. Among the main sources of air pollution in Europe, there are road traffic, domestic heating, and industrial combustion. The TRAFAIR project brings together 9 partners from two European countries (Italy and Spain) to develop innovative and sustainable services combining air quality, weather conditions, and traffic flows data to produce new information for the benefit of citizens and government decision-makers. The project is started in November 2018 and lasts two years. It is motivated by the huge amount of deaths caused by the air pollution. Nowadays, the situation is particularly critical in some member states of Europe. In February 2017, the European Commission warned five countries, among which Spain and Italy, of continued air pollution breaches. In this context, public administrations and citizens suffer from the lack of comprehensive and fast tools to estimate the level of pollution on an urban scale resulting from varying traffic flow conditions that would allow optimizing control strategies and increase air quality awareness. The goals of the project are twofold: monitoring urban air quality by using sensors in 6 European cities and making urban air quality predictions thanks to simulation models. The project is co-financed by the European Commission under the CEF TELECOM call on Open Data

    Predictors of Central Compartment Involvement in Patients with Positive Lateral Cervical Lymph Nodes According to Clinical and/or Ultrasound Evaluation

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    Lymph node neck metastases are frequent in papillary thyroid carcinoma (PTC). Current guidelines state, on a weak level of evidence, that level VI dissection is mandatory in the presence of latero-cervical metastases. The aim of our study is to evaluate predictive factors for the absence of level VI involvement despite the presence of metastases to the lateral cervical stations in PTC. Eighty-eight patients operated for PTC with level II-V metastases were retrospectively enrolled in the study. Demographics, thyroid function, autoimmunity, nodule size and site, cancer variant, multifocality, Bethesda and EU-TIRADS, number of central and lateral lymph nodes removed, number of positive lymph nodes and outcome were recorded. At univariate analysis, PTC location and number of positive lateral lymph nodes were risk criteria for failure to cure. ROC curves demonstrated the association of the number of positive lateral lymph nodes and failure to cure. On multivariate analysis, the protective factors were PTC located in lobe center and number of positive lateral lymph nodes < 4. Kaplan-Meier curves confirmed the absence of central lymph nodes as a positive prognostic factor. In the selected cases, Central Neck Dissection (CND) could be avoided even in the presence of positive Lateralcervical Lymph Nodes (LLN+)

    Different Cyberbullying Experiences and Sensemaking Processes about the Sociocultural Context

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    Introduction: Cyberbullying represents one of the main current concerns of parents, educators and clinicians on youth. It consists of aggressive, offensive and injurious behaviors against a person by means of electronic device and sharing abusive content on the web. Previous studies have highlighted that cyberbullying is associated with individual factors, such as personality traits, age, sex and status, often disregarding the value attributed to one's own context of life. According to the Semiotic Dynamic Cultural Psychology Theory (SDPCT), the cultural context can be conceived as a net of interconnected trajectories of meanings, grounding the way of perceiving and experiencing a social environment, and enabling individuals to orient themselves in their material and social world. Aims: The present research aims to explore the relation between directly acted, suffered and indirectly observed behaviors of cyberbullying, the fear to be victim, the awareness of its harmfulness and sensemaking processes of one’s own context. Method: Six hundred twenty-four high school students (Mean AGE = 16.10; SD = 1.60) participated in this study. Participants filled in a questionnaire, consisting of two parts. The former was composed by six scales constructed ad hoc to explore the experience of acted, suffered and observed cyberbullying, the fear of being cyberbullied and the awareness of cyberbullying’s harmfulness. The latter the View of Context (VOC) questionnaire was used to map sensemaking processes through which people interpret their social context. Findings: Results shows significant associations between acted and suffered forms of cyberbullying, between fear of cyberbullying and the awareness of its harmfulness. The acted cyberbullying and suffered cyberbullying are both associated with representation of the context as devaluated (family, schools, social institutions are considered not welcoming, useful or reliable) and deprived of opportunities for the future. Conclusion: On clinical plan, the study suggests the importance of considering the relationships between bullying experienced and acted upon, as well as the role of meaning-making processes in understanding phenomena of social prevarication

    SeaConditions: a web and mobile service for safer professional and recreational activities in the Mediterranean Sea

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    Abstract. Reliable and timely information on the environmental conditions at sea is key to the safety of professional and recreational users as well as to the optimal execution of their activities. The possibility of users obtaining environmental information in due time and with adequate accuracy in the marine and coastal environment is defined as sea situational awareness (SSA). Without adequate information on the environmental meteorological and oceanographic conditions, users have a limited capacity to respond, which has led to loss of lives and to large environmental disasters with enormous consequent damage to the economy, society and ecosystems. Within the framework of the TESSA project, new SSA services for the Mediterranean Sea have been developed. In this paper we present SeaConditions, which is a web and mobile application for the provision of meteorological and oceanographic observation and forecasting products. Model forecasts and satellite products from operational services, such as ECMWF and CMEMS, can be visualized in SeaConditions. In addition, layers of information related to bathymetry, sea level and ocean-colour data (chl a and water transparency) are displayed. Ocean forecasts at high spatial resolutions are included in the version of SeaConditions presented here. SeaConditions provides a user-friendly experience with a fluid zoom capability, facilitating the appropriate display of data with different levels of detail. SeaConditions is a single point of access to interactive maps from different geophysical fields, providing high-quality information based on advanced oceanographic models. The SeaConditions services are available through both web and mobile applications. The web application is available at www.sea-conditions.com and is accessible and compatible with present-day browsers. Interoperability with GIS software is implemented. User feedback has been collected and taken into account in order to improve the service. The SeaConditions iOS and Android apps have been downloaded by more than 105 000 users to date (May 2016), and more than 100 000 users have visited the web version

    The evolving SARS-CoV-2 epidemic in Africa: Insights from rapidly expanding genomic surveillance

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    INTRODUCTION Investment in Africa over the past year with regard to severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) sequencing has led to a massive increase in the number of sequences, which, to date, exceeds 100,000 sequences generated to track the pandemic on the continent. These sequences have profoundly affected how public health officials in Africa have navigated the COVID-19 pandemic. RATIONALE We demonstrate how the first 100,000 SARS-CoV-2 sequences from Africa have helped monitor the epidemic on the continent, how genomic surveillance expanded over the course of the pandemic, and how we adapted our sequencing methods to deal with an evolving virus. Finally, we also examine how viral lineages have spread across the continent in a phylogeographic framework to gain insights into the underlying temporal and spatial transmission dynamics for several variants of concern (VOCs). RESULTS Our results indicate that the number of countries in Africa that can sequence the virus within their own borders is growing and that this is coupled with a shorter turnaround time from the time of sampling to sequence submission. Ongoing evolution necessitated the continual updating of primer sets, and, as a result, eight primer sets were designed in tandem with viral evolution and used to ensure effective sequencing of the virus. The pandemic unfolded through multiple waves of infection that were each driven by distinct genetic lineages, with B.1-like ancestral strains associated with the first pandemic wave of infections in 2020. Successive waves on the continent were fueled by different VOCs, with Alpha and Beta cocirculating in distinct spatial patterns during the second wave and Delta and Omicron affecting the whole continent during the third and fourth waves, respectively. Phylogeographic reconstruction points toward distinct differences in viral importation and exportation patterns associated with the Alpha, Beta, Delta, and Omicron variants and subvariants, when considering both Africa versus the rest of the world and viral dissemination within the continent. Our epidemiological and phylogenetic inferences therefore underscore the heterogeneous nature of the pandemic on the continent and highlight key insights and challenges, for instance, recognizing the limitations of low testing proportions. We also highlight the early warning capacity that genomic surveillance in Africa has had for the rest of the world with the detection of new lineages and variants, the most recent being the characterization of various Omicron subvariants. CONCLUSION Sustained investment for diagnostics and genomic surveillance in Africa is needed as the virus continues to evolve. This is important not only to help combat SARS-CoV-2 on the continent but also because it can be used as a platform to help address the many emerging and reemerging infectious disease threats in Africa. In particular, capacity building for local sequencing within countries or within the continent should be prioritized because this is generally associated with shorter turnaround times, providing the most benefit to local public health authorities tasked with pandemic response and mitigation and allowing for the fastest reaction to localized outbreaks. These investments are crucial for pandemic preparedness and response and will serve the health of the continent well into the 21st century

    Effect of trochleocapitellar index on adult patient-reported outcomes after noncomminuted intra-articular distal humeral fractures

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    Background: Anatomic surgical reduction of intra-articular fractures of the distal humerus is important to achieve the best long-term outcomes and prevent post-traumatic arthritis. In this study we compared the radiographic reduction using the trochleocapitellar index. We also correlated the trochleocapitellar index to the functional outcomes next to the comparison of the triceps brachii lifting approach and olecranon osteotomy approach, 2 common approaches for distal humeral fractures. Methods: From January 2006 to June 2016, patients with elbow fractures were registered in 4 centers. The trochleocapitellar index, a ratio between the angle of the capitellum and the trochlea to the midline of the distal humerus on anterior-posterior radiographs, was calculated for included patients. Functional outcomes were measured using the Oxford Elbow Score and the Mayo Elbow Performance Score. Bone healing was measured using radiographic union scoring. Results: There were 86 patients enrolled: 46 in the olecranon osteotomy group and 40 in the triceps lifting group. Functional outcomes and bone healing did not differ between the approaches. Functional results had a medium correlation with the trochleocapitellar index, which did not differ between the 2 approaches (olecranon osteotomy group, κ = 0.56; triceps lifting group, κ = 0.57; P =.7932). Conclusions: The trochleocapitellar index has a moderate predictive value on the functional results after 12 months after open reduction and internal fixation of intra-articular distal humeral factures. There is no difference in reduction, as measured by trochlear index and functional outcome scores, between the olecranon osteotomy approach and the triceps brachii lifting approach groups
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