970 resultados para ORR


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Characterising catchment scale biogeochemical processes controlling nitrate fate in groundwater constitutes a fundamental consideration when applying programmes of measures to reduce risks posed by diffuse agricultural pollutants to water quality. Combining hydrochemical analyses with nitrate isotopic data and physical hydrogeological measurements permitted characterisation of biogeochemical processes influencing nitrogen fate and transport in the groundwater in two fractured bedrock aquifers with contrasting hydrogeology but comparable nutrient loads. Hydrochemical and isotopic analyses of groundwater samples collected from moderately fractured, diffusely karstified limestone indicated nitrification controlled dissolved nitrogen fate and delivery to aquatic receptors. By contrast nitrate concentrations in groundwater were considerably lower in a low transmissivity highly lithified sandstone and pyrite-bearing shale unit with patchy subsoil cover. Geophysical and hydrochemical investigations showed shallower intervals contained hydraulically active fractures where denitrification was reflected through lower nitrogen levels and an isotopic enrichment ratio of 1.7 between δ15N and δ18O. Study findings highlight the influence of bedrock hydrogeological conditions on aqueous nitrogen mobility. Investigation results demonstrate that bedrock conditions need to be considered when implementing catchment management plans to reduce the impact of agricultural practices on the quality of groundwater and baseflow in receiving rivers.

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Triple Negative Breast Cancer (TNBC) is defined by the lack of ERα, PR expression and HER2 overexpression and is the breast cancer subtype with the poorest clinical outcomes. Our aim was to identify genes driving TNBC proliferation and/or survival which could represent novel therapeutic targets. We performed microarray profiling of primary TNBCs and generated differential genelists based on clinical outcomes following the chemotherapy regimen FEC (5-Fluorouracil/Epirubicin/Cyclophosphamide -‘good’ outcome no relapse > 3 years; ‘poor’ outcome relapse < 3 years). Elevated expression of thromboxane A2 receptor (TBXA2R) was observed in ‘good’ outcome TNBCs. TBXA2R expression was higher specifically in TNBC cell lines and TBXA2R knockdowns consistently showed dramatic cell killing in TNBC cells. TBXA2R mRNA and promoter activities were up-regulated following BRCA1 knockdown, with c-Myc being required for BRCA1-mediated transcriptional repression. We demonstrated that TBXA2R enhanced TNBC cell migration, invasion and activated Rho signalling, phenotypes which could be reversed using Rho-associated Kinase (ROCK) inhibitors. TBXA2R also protected TNBC cells from DNA damage by negatively regulating reactive oxygen species levels. In summary, TBXA2R is a novel breast cancer-associated gene required for the survival and migratory behaviour of a subset of TNBCs and could provide opportunities to develop novel, more effective treatments.

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High-performance and low-cost bifunctional electrocatalysts play crucial roles in oxygen reduction and evolution reactions. Herein, a novel three-dimensional (3D) bifunctional electrocatalyst was prepared by embedding CoO nanoparticles into nitrogen and sulfur co-doped carbon nanofiber networks (denoted as CoO@N/S-CNF) through a facile approach. The carbon nanofiber networks were derived from a nanostructured biological material which provided abundant functional groups to nucleate and anchor nanoparticles while retaining its interconnected 3D porous structure. The composite possesses a high specific surface area and graphitization degree, which favors both mass transport and charge transfer for electrochemical reaction. The CoO@N/S-CNF not only exhibits highly efficient catalytic activity towards oxygen reduction reaction (ORR) in alkaline media with an onset potential of about 0.84 V, but also shows better stability and stronger resistance to methanol than Pt/C. Furthermore, it only needs an overpotential of 1.55 V to achieve a current density of 10 mA cm-2, suggesting that it is an efficient electrocatalyst for oxygen evolution reaction (OER). The ΔE value (oxygen electrode activity parameter) of CoO@N/S-CNF is calculated to be 0.828 V, which demonstrates that the composite could be a promising bifunctional electrocatalyst for both ORR and OER.

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Three-dimensional ordered mesoporous (3DOM) CuCo2O4 materials have been synthesized via a hard template and used as bifunctional electrocatalysts for rechargeable Li-O2 batteries. The characterization of the catalyst by X-ray diffractometry and transmission electron microscopy confirms the formation of a single-phase, 3-dimensional, ordered mesoporous CuCo2O4 structure. The as-prepared CuCo2O4 nanoparticles possess a high specific surface area of 97.1 m2 g- 1 and a spinel crystalline structure. Cyclic voltammetry demonstrates that mesoporous CuCo2O4 catalyst enhances the kinetics for either oxygen reduction reaction (ORR) or oxygen evolution reaction (OER). The Li-O2 battery utilizing 3DOM CuCo2O4 shows a higher specific capacity of 7456 mAh g- 1 than that with pure Ketjen black (KB). Moreover, the CuCo2O4-based electrode enables much enhanced cyclability with a 610 mV smaller discharge-recharge voltage gap than that of the carbon-only cathode at a current rate of 100 mA g- 1. Such excellent catalytic performance of CuCo2O4 could be associated with its larger surface area and 3D ordered mesoporous structure. The excellent electrochemical performances coupled with its facile and cost-effective way will render the 3D mesoporous CuCo2O4 nanostructures as attractive electrode materials for promising application in Li-O2 batteries.

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In this paper, Sr2Fe1.5Mo0.4Nb0.1O6-δ (SFMNb)-xSm0.2Ce0.8O2-δ (SDC) (x = 0, 20, 30, 40, 50 wt%) composite cathode materials were synthesized by a one-pot combustion method to improve the electrochemical performance of SFMNb cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The fabrication of composite cathodes by adding SDC to SFMNb is conducive to providing extended electrochemical reaction zones for oxygen reduction reactions (ORR). X-ray diffraction (XRD) demonstrates that SFMNb is chemically compatible with SDC electrolytes at temperature up to 1100 °C. Scanning electron microscope (SEM) indicates that the SFMNb-SDC composite cathodes have a porous network nanostructure as well as the single phase SFMNb. The conductivity and thermal expansion coefficient of the composite cathodes decrease with the increased content of SDC, while the electrochemical impedance spectra (EIS) exhibits that SFMNb-40SDC composite cathode has optimal electrochemical performance with low polarization resistance (Rp) on the La0.9Sr0.1Ga0.8Mg0.2O3 electrolyte. The Rp of the SFMNb-40SDC composite cathode is about 0.047 Ω cm2 at 800 °C in air. A single cell with SFMNb-40SDC cathode also displays favorable discharge performance, whose maximum power density is 1.22 W cm-2 at 800 °C. All results indicate that SFMNb-40SDC composite material is a promising cathode candidate for IT-SOFCs.

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Abstract: The first metatarsal sesamoid bones are not always taken into consideration when making a diagnosis, in pathologies that affect the region of the first metatarsal head. This is due to the insufficient knowledge of all the pathologies that can affect the sesamoids and the relative little incidence that they have. With the increment of sports activities, in particular the running, increasingly affects of the symptoms concerning this region are observed. Methods: A literature search was performed in 5 databases (Medline, PubMed, Scopus, Cochrane Library and BUCEA). The terms included in the search were: sesamoids, anatomy, biomechanics, sesamoids review and sesamoids pathology. In the initial search articles with no more than 10 years, only humans and revision texts are considered. Results: 24 articles were selected and include different pathologies with diagnosis using imaging tests and treatments, both conservative and surgical; as well as aspects from the biomechanics of the metatarsal-sesamoid joint. Conclusion: Sesamoids due of his anatomy, topography and function can be involved in a lot of pathologies; with similar signs and symptoms that can confuse the podiatry when he has to make a correct diagnosis or treatment.

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Les ruptures amoureuses et les divorces sont très fréquents dans la société actuelle. La rupture d’une relation amoureuse est une épreuve difficile (Holmes & Rahe, 1967; Scully, Tosi, & Banning, 2000) qui génère une détresse émotionnelle importante (Birnbaum, Orr, Mikulincer, & Florian, 1997; Sbarra, 2006). Certains individus qui vivent une rupture iront même jusqu’à poser un geste suicidaire. En effet, le lien entre la rupture amoureuse et le comportement suicidaire est bien documenté à ce jour (Ide, Wyder, Kolves, & De Leo, 2010). La présente étude a investigué le rôle des insécurités d’attachement amoureux (anxiété d’abandon, évitement de l’intimité) dans la survenue des symptômes dépressifs et des comportements suicidaires (pensées et tentatives) à la suite d’une rupture. Pour ce faire, 50 participants adultes ayant vécu une rupture amoureuse dans les six derniers mois ont été recrutés auprès d’organismes d’aide (centre de prévention de suicide, centre psychologique, organisme communautaire), ainsi qu’à l’aide de publicités affichées en milieu universitaire, sur les réseaux sociaux et sur des réseaux de partenaires. Un intervenant formé en crise suicidaire a administré verbalement des questionnaires validés d’attachement amoureux, de symptômes dépressifs et de comportements suicidaires lors d’une entrevue individuelle. Les résultats des analyses de régressions multiples ont montré que l’anxiété d’abandon des adultes qui vivent une rupture est liée à davantage de symptômes dépressifs, ainsi qu’à la sévérité et l’intensité des idées suicidaires. Ces effets demeurent lorsque l’utilisation du réseau social est contrôlée. L’évitement de l’intimité n’est pas lié à ces variables. La discussion porte sur l’importance de l’anxiété d’abandon comme facteur de vulnérabilité dans les difficultés d’adaptation à la rupture, au-delà du réseau social, et propose des pistes d’évaluation et d’intervention pour les cliniciens.

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Bis-(3´-5´)-cyclic dimeric guanosine monophosphate, or cyclic di-GMP (c-di-GMP) is a ubiquitous bacterial second messenger that regulates processes such biofilm formation, motility, and virulence. C-di-GMP is synthesized by diguanylate cyclases (DGCs), while phosphodiesterases (PDE-As) end signaling by linearizing c-di-GMP to 5ʹ-phosphoguanylyl-(3ʹ,5ʹ)-guanosine (pGpG), which is then hydrolyzed to two GMPs by previously unidentified enzymes termed PDE-Bs. To identify the PDE-B responsible for pGpG turnover, a screen for pGpG binding proteins in a Vibrio cholerae open reading frame library was conducted to identify potential pGpG binding proteins. This screen led to identification of oligoribonuclease (Orn). Purified Orn binds to pGpG and can cleave pGpG to GMP in vitro. A deletion mutant of orn in Pseudomonas aeruginosa was highly defective in pGpG turnover and accumulated pGpG. Deletion of orn also resulted in accumulation c-di-GMP, likely through pGpG-mediated inhibition of the PDE-As, causing an increase in c-di-GMP-governed auto-aggregation and biofilm. Thus, we found that Orn serves as the primary PDE-B enzyme in P. aeruginosa that removes pGpG, which is necessary to complete the final step in the c-di-GMP degradation pathway. However, not all bacteria that utilize c-di-GMP signaling also have an ortholog of orn, suggesting that other PDE-Bs must be present. Therefore, we asked whether RNases that cleave small oligoribonucleotides in other species could also act as PDE-Bs. NrnA, NrnB, and NrnC can rapidly degrade pGpG to GMP. Furthermore, they can reduce the elevated aggregation and biofilm formation in P. aeruginosa ∆orn. Together, these results indicate that rather than having a single dedicated PDE-B, different bacteria utilize distinct RNases to cleave pGpG and complete c-di-GMP signaling. The ∆orn strain also has a growth defect, indicating changes in other regulatory processes that could be due to pGpG accumulation, c-di-GMP accumulation, or another effect due to loss of Orn. We sought to investigate the genetic pathways responsible for these growth defect phenotypes by use of a transposon suppressor screen, and also investigated transcriptional changes using RNA-Seq. This work identifies that c-di-GMP degradation intersects with RNA degradation at the point of the Orn and the functionally related RNases.

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Since the end of the Cold War, recurring civil conflicts have been the dominant form of violent armed conflict in the world, accounting for 70% of conflicts active between 2000-2013. Duration and intensity of episodes within recurring conflicts in Africa exhibit four behaviors characteristic of archetypal dynamic system structures. The overarching questions asked in this study are whether these patterns are robustly correlated with fundamental concepts of resiliency in dynamic systems that scale from micro-to macro levels; are they consistent with theoretical risk factors and causal mechanisms; and what are the policy implications. Econometric analysis and dynamic systems modeling of 36 conflicts in Africa between 1989 -2014 are combined with process tracing in a case study of Somalia to evaluate correlations between state characteristics, peace operations and foreign aid on the likelihood of observed conflict patterns, test hypothesized causal mechanisms across scales, and develop policy recommendations for increasing human security while decreasing resiliency of belligerents. Findings are that observed conflict patterns scale from micro to macro levels; are strongly correlated with state characteristics that proxy a mix of cooperative (e.g., gender equality) and coercive (e.g., security forces) conflict-balancing mechanisms; and are weakly correlated with UN and regional peace operations and humanitarian aid. Interactions between peace operations and aid interventions that effect conflict persistence at micro levels are not seen in macro level analysis, due to interdependent, micro-level feedback mechanisms, sequencing, and lagged effects. This study finds that the dynamic system structures associated with observed conflict patterns contain tipping points between balancing mechanisms at the interface of micro-macro level interactions that are determined as much by factors related to how intervention policies are designed and implemented, as what they are. Policy implications are that reducing risk of conflict persistence requires that peace operations and aid interventions (1) simultaneously increase transparency, promote inclusivity (with emphasis on gender equality), and empower local civilian involvement in accountability measures at the local levels; (2) build bridges to horizontally and vertically integrate across levels; and (3) pave pathways towards conflict transformation mechanisms and justice that scale from the individual, to community, regional, and national levels.

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This dissertation studies refugee resettlement in the United States utilizing the Integration Indicator’s framework developed by Ager and Strang for the U.S. context. The study highlights the U.S. refugee admissions program and the policies in the states of Maryland and Massachusetts while analyzing the service delivery models and its effects on refugee integration in these locations. Though immigration policy and funding for refugee services are primarily the domain of the federal government, funds are allocated through and services are delivered at the state level. The Office of Refugee Resettlement (ORR), which operates under the Department of Health and Human Services, was established after the Refugee Act of 1980 to deliver assistance to displaced persons. The ORR provides funds to individual states primarily through The Refugee Social Service and Targeted Assistance Formula Grant programs. Since the inauguration of the ORR three primary models of refugee integration through service delivery have emerged. Two of the models include the publicly/privately administered programs, where resources are allocated to the state in conjunction with private voluntary agencies; and the Wilson/Fish Alternative programs, where states sub-contract all elements of the resettlement program to voluntary agencies and private organizations —in which they can cease all state level participation and voluntary agencies or private organizations contract directly from the ORR in order for all states to deliver refugee services where the live. The specific goals of this program are early employment and economic self-sufficiency. This project utilizes US Census, state, and ORR data in conjunction with interviews of refugee resettlement practitioners involved in the service delivery and refugees. The findings show that delivery models emphasizing job training, English instruction courses, institutional collaboration, and monetary assistance, increases refugee acclimation and adaptation, providing insight into their potential for integration into the United States.

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The Ocean Model Intercomparison Project (OMIP) aims to provide a framework for evaluating, understanding, and improving the ocean and sea-ice components of global climate and earth system models contributing to the Coupled Model Intercomparison Project Phase 6 (CMIP6). OMIP addresses these aims in two complementary manners: (A) by providing an experimental protocol for global ocean/sea-ice models run with a prescribed atmospheric forcing, (B) by providing a protocol for ocean diagnostics to be saved as part of CMIP6. We focus here on the physical component of OMIP, with a companion paper (Orr et al., 2016) offering details for the inert chemistry and interactive biogeochemistry. The physical portion of the OMIP experimental protocol follows that of the interannual Coordinated Ocean-ice Reference Experiments (CORE-II). Since 2009, CORE-I (Normal Year Forcing) and CORE-II have become the standard method to evaluate global ocean/sea-ice simulations and to examine mechanisms for forced ocean climate variability. The OMIP diagnostic protocol is relevant for any ocean model component of CMIP6, including the DECK (Diagnostic, Evaluation and Characterization of Klima experiments), historical simulations, FAFMIP (Flux Anomaly Forced MIP), C4MIP (Coupled Carbon Cycle Climate MIP), DAMIP (Detection and Attribution MIP), DCPP (Decadal Climate Prediction Project), ScenarioMIP (Scenario MIP), as well as the ocean-sea ice OMIP simulations. The bulk of this paper offers scientific rationale for saving these diagnostics.

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The Ocean Model Intercomparison Project (OMIP) is an endorsed project in the Coupled Model Intercomparison Project Phase 6 (CMIP6). OMIP addresses CMIP6 science questions, investigating the origins and consequences of systematic model biases. It does so by providing a framework for evaluating (including assessment of systematic biases), understanding, and improving ocean, sea-ice, tracer, and biogeochemical components of climate and earth system models contributing to CMIP6. Among the WCRP Grand Challenges in climate science (GCs), OMIP primarily contributes to the regional sea level change and near-term (climate/decadal) prediction GCs. OMIP provides (a) an experimental protocol for global ocean/sea-ice models run with a prescribed atmospheric forcing; and (b) a protocol for ocean diagnostics to be saved as part of CMIP6. We focus here on the physical component of OMIP, with a companion paper (Orr et al., 2016) detailing methods for the inert chemistry and interactive biogeochemistry. The physical portion of the OMIP experimental protocol follows the interannual Coordinated Ocean-ice Reference Experiments (CORE-II). Since 2009, CORE-I (Normal Year Forcing) and CORE-II (Interannual Forcing) have become the standard methods to evaluate global ocean/sea-ice simulations and to examine mechanisms for forced ocean climate variability. The OMIP diagnostic protocol is relevant for any ocean model component of CMIP6, including the DECK (Diagnostic, Evaluation and Characterization of Klima experiments), historical simulations, FAFMIP (Flux Anomaly Forced MIP), C4MIP (Coupled Carbon Cycle Climate MIP), DAMIP (Detection and Attribution MIP), DCPP (Decadal Climate Prediction Project), ScenarioMIP, HighResMIP (High Resolution MIP), as well as the ocean/sea-ice OMIP simulations.