First-principles investigation of Ag-Cu alloy surfaces in an oxidizing environment

In this paper we investigate by means of first-principles density functional theory calculations the (111) surface of the Ag-Cu alloy under varying conditions of pressure of the surrounding oxygen atmosphere and temperature. This alloy has been recently proposed as a catalyst with improved selectivity for ethylene epoxidation with respect to pure silver, the catalyst commonly used in industrial applications. Here we show that the presence of oxygen leads to copper segregation to the surface. Considering the surface free energy as a function of the surface composition, we construct the convex hull to investigate the stability of various surface structures. By including the dependence of the free surface energy on the oxygen chemical potential, we are able compute the phase diagram of the alloy as a function of temperature, pressure and surface composition. We find that, at temperature and pressure typically used in ethylene epoxidation, a number of structures can be present on the surface of the alloy, including clean Ag(111), thin layers of copper oxide and thick oxide-like structures. These results are consistent with, and help explain, recent experimental results.Comment: 10 pages, 6 figure

Influence of the rainfall in the content of nutrients in litter in agroforestry systems managed with burning and without burning in Amazon.

This study evaluated the nutrient content of the litter, testing different treatments with burning and no burning, of the vegetation, to identify which one provides better efficiency in operation and production of nutrients in different seasonal conditions. The study area is located on the property of the family farmer, initially selected by a diagnosis socioeconomic, community Benjamin Constant, in northeastern Para. Litter was collected during two periods: dry season (November) and rainy (March) in 2009. For the collection of litter samples, we used collectors measuring (0.25 × 0.25 m2), which were placed directly on the soil surface. The collected material was stored in paper bags and taken to the laboratory for Chemical Analysis of the Brazilian Agricultural Research Corporation (EMBRAPA), which was determined by analyses of macronutrients (N, P, K, Ca, Mg, Na) and micronutrients (Fe, Cu, Mn, Zn). The highest concentrations of macronutrients were found in N for agroforestry systems with and without burning in two seasons (wet and dry). All macronutrients showed influence of seasonality, which was verified by the wide variation in nutritional behavior. The decreasing concentration of nutrients was presented N > Ca > Mg > Na > K > P in agroforestry system with burning, with maximum values of all nutrients in the rainy season, and N, P, K, Ca, Na in higher concentrations in agroforestry system without burning, and showed only the Mg peak in agroforestry system with burning. The behavior of the concentration of nutrients was opposite to that observed one, for all elements analyzed showed a reduction in the concentrations of nutrients in the dry season. The decreasing concentration of nutrients was presented Fe > Mn > Zn > Cu

Remote multiparametric monitoring and management of heart failure patients through cardiac implantable electronic devices

In this review we focus on heart failure (HF) which, as known, is associated with a substantial risk of hospitalizations and adverse cardiovascular outcomes, including death. In recent years, systems to monitor cardiac function and patient parameters have been developed with the aim to detect subclinical pathophysiological changes that precede worsening HF. Several patient-specific parameters can be remotely monitored through cardiac implantable electronic devices (CIED) and can be combined in multiparametric scores predicting patients’ risk of worsening HF with good sensitivity and moderate specificity. Early patient management at the time of pre-clinical alerts remotely transmitted by CIEDs to physicians might prevent hospitalizations. However, it is not clear yet which is the best diagnostic pathway for HF patients after a CIED alert, which kind of medications should be changed or escalated, and in which case in-hospital visits or in-hospital admissions are required. Finally, the specific role of healthcare professionals involved in HF patient management under remote monitoring is still matter of definition. We analyzed recent data on multiparametric monitoring of patients with HF through CIEDs. We provided practical insights on how to timely manage CIED alarms with the aim to prevent worsening HF. We also discussed the role of biomarkers and thoracic echo in this context, and potential organizational models including multidisciplinary teams for remote care of HF patients with CIEDs

Remote multiparametric monitoring and management of heart failure patients through cardiac implantable electronic devices

In this review we focus on heart failure (HF) which, as known, is associated with a substantial risk of hospitalizations and adverse cardiovascular outcomes, including death. In recent years, systems to monitor cardiac function and patient parameters have been developed with the aim to detect subclinical pathophysiological changes that precede worsening HF. Several patient-specific parameters can be remotely monitored through cardiac implantable electronic devices (CIED) and can be combined in multiparametric scores predicting patients' risk of worsening HF with good sensitivity and moderate specificity. Early patient management at the time of pre-clinical alerts remotely transmitted by CIEDs to physicians might prevent hospitalizations. However, it is not clear yet which is the best diagnostic pathway for HF patients after a CIED alert, which kind of medications should be changed or escalated, and in which case in-hospital visits or in-hospital admissions are required. Finally, the specific role of healthcare professionals involved in HF patient management under remote monitoring is still matter of definition. We analyzed recent data on multiparametric monitoring of patients with HF through CIEDs. We provided practical insights on how to timely manage CIED alarms with the aim to prevent worsening HF. We also discussed the role of biomarkers and thoracic echo in this context, and potential organizational models including multidisciplinary teams for remote care of HF patients with CIEDs

On the origin of multihole oxygen evolution in haematite photoanodes

The oxygen evolution reaction (OER) plays a crucial role in (photo)electrochemical devices that use renewable energy to produce synthetic fuels. Recent measurements on semiconducting oxides have found a power law dependence of the OER rate on surface hole density, suggesting a multihole mechanism. In this study, using transient photocurrent measurements, density functional theory simulations and microkinetic modelling, we have uncovered the origin of this behaviour in haematite. We show here that the OER rate has a third-order dependence on the surface hole density. We propose a mechanism wherein the reaction proceeds by accumulating oxidizing equivalents through a sequence of one-electron oxidations of surface hydroxy groups. The key O–O bond formation step occurs by the dissociative chemisorption of a hydroxide ion involving three oxyl sites. At variance with the case of metallic oxides, the activation energy of this step is weakly dependent on the surface hole coverage, leading to the observed power law

Inflammation subverts hippocampal synaptic plasticity in experimental multiple sclerosis

Abnormal use-dependent synaptic plasticity is universally accepted as the main physiological correlate of memory deficits in neurodegenerative disorders. It is unclear whether synaptic plasticity deficits take place during neuroinflammatory diseases, such as multiple sclerosis (MS) and its mouse model, experimental autoimmune encephalomyelitis (EAE). In EAE mice, we found significant alterations of synaptic plasticity rules in the hippocampus. When compared to control mice, in fact, hippocampal long-term potentiation (LTP) induction was favored over long-term depression (LTD) in EAE, as shown by a significant rightward shift in the frequency-synaptic response function. Notably, LTP induction was also enhanced in hippocampal slices from control mice following interleukin-1β (IL-1β) perfusion, and both EAE and IL-1β inhibited GABAergic spontaneous inhibitory postsynaptic currents (sIPSC) without affecting glutamatergic transmission and AMPA/NMDA ratio. EAE was also associated with selective loss of GABAergic interneurons and with reduced gamma-frequency oscillations in the CA1 region of the hippocampus. Finally, we provided evidence that microglial activation in the EAE hippocampus was associated with IL-1β expression, and hippocampal slices from control mice incubated with activated microglia displayed alterations of GABAergic transmission similar to those seen in EAE brains, through a mechanism dependent on enhanced IL-1β signaling. These data may yield novel insights into the basis of cognitive deficits in EAE and possibly of MS

Qualidade de sementes de soja submetidas a diferentes volumes de calda no tratamento de sementes, sob efeito do armazenamento.

Edição Especial contendo os Anais do XVIII Congresso Brasileiro de Sementes, Florianópolis, set. 2013

RANTES correlates with inflammatory activity and synaptic excitability in multiple sclerosis

BACKGROUND: Alterations of synaptic transmission induced by inflammatory activity have been linked to the pathogenic mechanisms of multiple sclerosis (MS). Regulated upon activation, normal T-cell expressed, and secreted (RANTES) is a pro-inflammatory chemokine involved in MS pathophysiology, potentially able to regulate glutamate release and plasticity in MS brains, with relevant consequences on the clinical manifestations of the disease. OBJECTIVE: To assess the role of RANTES in the regulation of cortical excitability. METHODS: We explored the association of RANTES levels in the cerebrospinal fluid (CSF) of newly diagnosed MS patients with magnetic resonance imaging (MRI) and laboratory measures of inflammatory activity, as well its role in the control of cortical excitability and plasticity explored by means of transcranial magnetic stimulation (TMS), and in hippocampal mouse slices in vitro. RESULTS: CSF levels of RANTES were remarkably high only in active MS patients and were correlated with the concentrations of interleukin-1β. RANTES levels were associated with TMS measures of cortical synaptic excitability, but not with long-term potentiation (LTP)-like plasticity. Similar findings were obtained in mouse hippocampal slices in vitro, where we observed that RANTES enhanced basal excitatory synaptic transmission with no effect on LTP. CONCLUSION: RANTES correlates with inflammation and synaptic excitability in MS brains

Density functional calculations of nanoscale conductance

Density functional calculations for the electronic conductance of single molecules are now common. We examine the methodology from a rigorous point of view, discussing where it can be expected to work, and where it should fail. When molecules are weakly coupled to leads, local and gradient-corrected approximations fail, as the Kohn-Sham levels are misaligned. In the weak bias regime, XC corrections to the current are missed by the standard methodology. For finite bias, a new methodology for performing calculations can be rigorously derived using an extension of time-dependent current density functional theory from the Schroedinger equation to a Master equation.Comment: topical review, 28 pages, updated version with some revision