Structural evolution, optical gap and thermoelectric properties of CH3NH3SnBr3 hybrid perovskite, prepared by mechanochemistry

Direct bandgap semiconductors of the hybrid-perovskite family CH3NH3PbX3 (X = I, Br, Cl) exhibit outstanding light absorption properties and are the materials of choice for solar energy applications. As an alternative to poisonous Pb, tin-containing perovskites would show a lower effective mass thus exhibiting a higher charge carrier mobility. An auspicious candidate is CH3NH3SnBr3, with an estimated band gap of 1.902 eV, anticipating applications in photovoltaic devices for the visible to ultra-violet wavelength region. We describe that this perovskite can be prepared by ball milling in a straightforward way, yielding specimens with a superior crystallinity. A structural investigation from synchrotron X-ray powder diffraction (SXRD) data was essential to revisit the successive phase transitions this compound experiences down to 120 K, guided by specific heat capacity and DSC measurements. From the cubic structure identified at RT and 270 K, there is a gradual evolution of the patterns, analysed as a phase admixture between the cubic and the low-symmetry phase present at 160 K. This corresponds to an orthorhombic Pmc21 superstructure; this acentric space group enables polarization along the c-axis where there is a twofold screw axis, evidenced in the distribution of Sn-Br distances. Furthermore, there are two conspicuous changes in the orthorhombic framework, yet keeping the Pmc21 space group, which agree with the main calorimetric events (observed at 224 and 147 K). We interpret these changes as an interplay between the tilting of the SnBr6 octahedra of the inorganic framework and the breaking and reconstruction of H-bond interactions with the organic CH3NH+3 unit. The stereochemical effect of the lone electron pair of the Sn2+ ion is clear in the SnBr6 octahedral distortion. Diffuse reflectance UV/Vis spectroscopy yields an optical gap of ∼2.1 eV, in agreement with ab- initio calculations. A Seebeck coefficient of ∼2000 μV K-1 is determined near RT, which is one order of magnitude higher than those reported for other halide perovskites.Fil: Lopez, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; Argentina. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Abia, Carmen. Institut Laue Langevin; Francia. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Gainza, Javier. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Kayser, Paula. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Nemes, Norbert. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Dura, Oscar J.. Universidad de Castilla-La Mancha; EspañaFil: Martinez, Jose L.. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Fernandez Diaz, Maria Teresa. Institut Laue Langevin; FranciaFil: Alvarez Galvan, M. Consuelo. Consejo Superior de Investigaciones Científicas; EspañaFil: Alonso, José Antonio. Instituto de Ciencia de Materiales de Madrid; Españ

Partial Oxidation of Methane to Syngas Over Nickel-Based Catalysts: Influence of Support Type, Addition of Rhodium, and Preparation Method

There is great economic incentive in developing efficient catalysts to produce hydrogen or syngas by catalytic partial oxidation of methane (CPOM) since this is a much less energy-intensive reaction than the highly endothermic methane steam reforming reaction, which is the prominent reaction in industry. Herein, we report the catalytic behavior of nickel-based catalysts supported on different oxide substrates (Al2O3, CeO2, La2O3, MgO, and ZrO2) synthesized via wet impregnation and solid-state reaction. Furthermore, the impact of Rh doping was investigated. The catalysts have been characterized by X-ray diffraction, N2 adsorptiondesorption at −196°C, temperature-programmed reduction, X-ray photoelectron spectroscopy, O2-pulse chemisorption, transmission electron microscopy, and Raman spectroscopy. Supported Ni catalysts were found to be active for CPOM but can suffer from fast deactivation caused by the formation of carbon deposits as well as via the sintering of Ni nanoparticles (NPs). It has been found that the presence of Rh favors nickel reduction, which leads to an increase in the methane conversion and yield. For both synthesis methods, the catalysts supported on alumina and ceria show the best performance. This could be explained by the higher surface area of the Ni NPs on the alumina surface and presence of oxygen vacancies in the CeO2 lattice, which favor the proportion of oxygen adsorbed on defect sites. The catalysts supported on MgO suffer quick deactivation due to formation of a NiO/MgO solid solution, which is not reducible under the reaction conditions. The low level of carbon formation over the catalysts supported on La2O3 is ascribed to the very high dispersion of the nickel NPs and to the formation of lanthanum oxycarbonate, through which carbon deposits are gasified. The catalytic behavior for catalysts with ZrO2 as support depends on the synthesis method; however, in both cases, the catalysts undergo deactivation by carbon deposits

Safety perspectives on presently considered drugs for the treatment of COVID‐19

Intense efforts are underway to evaluate potential therapeutic agents for the treatment of COVID‐19. In order to respond quickly to the crisis, the repurposing of existing drugs is the primary pharmacological strategy. Despite the urgent clinical need for these therapies, it is imperative to consider potential safety issues. This is important due to the harm–benefit ratios that may be encountered when treating COVID‐19, which can depend on the stage of the disease, when therapy is administered and underlying clinical factors in individual patients. Treatments are currently being trialled for a range of scenarios from prophylaxis (where benefit must greatly exceed risk) to severe life‐threatening disease (where a degree of potential risk may be tolerated if it is exceeded by the potential benefit). In this perspective, we have reviewed some of the most widely researched repurposed agents in order to identify potential safety considerations using existing information in the context of COVID‐19

Is prolonged infusion of piperacillin/tazobactam and meropenem in critically ill patients associated with improved pharmacokinetic/pharmacodynamic and patient outcomes? An observation from the Defining Antibiotic Levels in Intensive care unit patients (DALI) cohort

Objectives:We utilized the database of the Defining Antibiotic Levels in Intensive care unit patients (DALI) study to statistically compare the pharmacokinetic/pharmacodynamic and clinical outcomes between prolonged-infusion and intermittent-bolus dosing of piperacillin/tazobactam and meropenem in critically ill patients using inclusion criteria similar to those used in previous prospective studies.Methods: This was a post hoc analysis of a prospective, multicentre pharmacokinetic point-prevalence study (DALI), which recruited a large cohort of critically ill patients from 68 ICUs across 10 countries.Results: Of the 211 patients receiving piperacillin/tazobactam and meropenem in the DALI study, 182 met inclusion criteria. Overall, 89.0% (162/182) of patients achieved the most conservative target of 50% fT(> MIC) (time over which unbound or free drug concentration remains above the MIC). Decreasing creatinine clearance and the use of prolonged infusion significantly increased the PTA for most pharmacokinetic/pharmacodynamic targets. In the subgroup of patients who had respiratory infection, patients receiving beta-lactams via prolonged infusion demonstrated significantly better 30 day survival when compared with intermittent-bolus patients [86.2% (25/29) versus 56.7% (17/30); P=0.012]. Additionally, in patients with a SOFA score of >= 9, administration by prolonged infusion compared with intermittent-bolus dosing demonstrated significantly better clinical cure [73.3% (11/15) versus 35.0% (7/20); P=0.035] and survival rates [73.3% (11/15) versus 25.0% (5/20); P=0.025].Conclusions: Analysis of this large dataset has provided additional data on the niche benefits of administration of piperacillin/tazobactam and meropenem by prolonged infusion in critically ill patients, particularly for patients with respiratory infections

Galactic Gamma-Ray Diffuse Emission at TeV energies with HAWC Data

The Galactic gamma-ray diffuse emission (GDE) is emitted by cosmic rays (CRs), ultra-relativistic protons and electrons, interacting with gas and electromagnetic radiation fields in the interstellar medium. Here we present the analysis of TeV diffuse emission from a region of the Galactic Plane over the range in longitude of $l\in[43^\circ,73^\circ]$, using data collected with the High Altitude Water Cherenkov (HAWC) detector. Spectral, longitudinal and latitudinal distributions of the TeV diffuse emission are shown. The radiation spectrum is compatible with the spectrum of the emission arising from a CR population with an "index" similar to that of the observed CRs. When comparing with the \texttt{DRAGON} \textit{base model}, the HAWC GDE flux is higher by about a factor of two. Unresolved sources such as pulsar wind nebulae and TeV halos could explain the excess emission. Finally, deviations of the Galactic CR flux from the locally measured CR flux may additionally explain the difference between the predicted and measured diffuse fluxes

Mortality and pulmonary complications in patients undergoing surgery with perioperative sars-cov-2 infection: An international cohort study

Background The impact of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) on postoperative recovery needs to be understood to inform clinical decision making during and after the COVID-19 pandemic. This study reports 30-day mortality and pulmonary complication rates in patients with perioperative SARS-CoV-2 infection. Methods This international, multicentre, cohort study at 235 hospitals in 24 countries included all patients undergoing surgery who had SARS-CoV-2 infection confirmed within 7 days before or 30 days after surgery. The primary outcome measure was 30-day postoperative mortality and was assessed in all enrolled patients. The main secondary outcome measure was pulmonary complications, defined as pneumonia, acute respiratory distress syndrome, or unexpected postoperative ventilation. Findings This analysis includes 1128 patients who had surgery between Jan 1 and March 31, 2020, of whom 835 (740%) had emergency surgery and 280 (248%) had elective surgery. SARS-CoV-2 infection was confirmed preoperatively in 294 (261%) patients. 30-day mortality was 238% (268 of 1128). Pulmonary complications occurred in 577 (512%) of 1128 patients; 30-day mortality in these patients was 380% (219 of 577), accounting for 817% (219 of 268) of all deaths. In adjusted analyses, 30-day mortality was associated with male sex (odds ratio 175 [95% CI 128-240], p<00001), age 70 years or older versus younger than 70 years (230 [165-322], p<00001), American Society of Anesthesiologists grades 3-5 versus grades 1-2 (235 [157-353], p<00001), malignant versus benign or obstetric diagnosis (155 [101-239], p=0046), emergency versus elective surgery (167 [106-263], p=0026), and major versus minor surgery (152 [101-231], p=0047). Interpretation Postoperative pulmonary complications occur in half of patients with perioperative SARS-CoV-2 infection and are associated with high mortality. Thresholds for surgery during the COVID-19 pandemic should be higher than during normal practice, particularly in men aged 70 years and older. Consideration should be given for postponing non-urgent procedures and promoting non-operative treatment to delay or avoid the need for surgery. Funding National Institute for Health Research (NIHR), Association of Coloproctology of Great Britain and Ireland, Bowel and Cancer Research, Bowel Disease Research Foundation, Association of Upper Gastrointestinal Surgeons, British Association of Surgical Oncology, British Gynaecological Cancer Society, European Society of Coloproctology, NIHR Academy, Sarcoma UK, Vascular Society for Great Britain and Ireland, and Yorkshire Cancer Research

Cause of Death and Predictors of All-Cause Mortality in Anticoagulated Patients With Nonvalvular Atrial Fibrillation : Data From ROCKET AF

M. Kaste on työryhmän ROCKET AF Steering Comm jäsen.Background-Atrial fibrillation is associated with higher mortality. Identification of causes of death and contemporary risk factors for all-cause mortality may guide interventions. Methods and Results-In the Rivaroxaban Once Daily Oral Direct Factor Xa Inhibition Compared with Vitamin K Antagonism for Prevention of Stroke and Embolism Trial in Atrial Fibrillation (ROCKET AF) study, patients with nonvalvular atrial fibrillation were randomized to rivaroxaban or dose-adjusted warfarin. Cox proportional hazards regression with backward elimination identified factors at randomization that were independently associated with all-cause mortality in the 14 171 participants in the intention-to-treat population. The median age was 73 years, and the mean CHADS(2) score was 3.5. Over 1.9 years of median follow-up, 1214 (8.6%) patients died. Kaplan-Meier mortality rates were 4.2% at 1 year and 8.9% at 2 years. The majority of classified deaths (1081) were cardiovascular (72%), whereas only 6% were nonhemorrhagic stroke or systemic embolism. No significant difference in all-cause mortality was observed between the rivaroxaban and warfarin arms (P=0.15). Heart failure (hazard ratio 1.51, 95% CI 1.33-1.70, P= 75 years (hazard ratio 1.69, 95% CI 1.51-1.90, P Conclusions-In a large population of patients anticoagulated for nonvalvular atrial fibrillation, approximate to 7 in 10 deaths were cardiovascular, whereasPeer reviewe

Studies of new Higgs boson interactions through nonresonant HH production in the b¯bγγ fnal state in pp collisions at √s = 13 TeV with the ATLAS detector

A search for nonresonant Higgs boson pair production in the b ¯bγγ fnal state is performed using 140 fb−1 of proton-proton collisions at a centre-of-mass energy of 13 TeV recorded by the ATLAS detector at the CERN Large Hadron Collider. This analysis supersedes and expands upon the previous nonresonant ATLAS results in this fnal state based on the same data sample. The analysis strategy is optimised to probe anomalous values not only of the Higgs (H) boson self-coupling modifer κλ but also of the quartic HHV V (V = W, Z) coupling modifer κ2V . No signifcant excess above the expected background from Standard Model processes is observed. An observed upper limit µHH < 4.0 is set at 95% confdence level on the Higgs boson pair production cross-section normalised to its Standard Model prediction. The 95% confdence intervals for the coupling modifers are −1.4 < κλ < 6.9 and −0.5 < κ2V < 2.7, assuming all other Higgs boson couplings except the one under study are fxed to the Standard Model predictions. The results are interpreted in the Standard Model efective feld theory and Higgs efective feld theory frameworks in terms of constraints on the couplings of anomalous Higgs boson (self-)interactions