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1.
N Engl J Med ; 388(5): 427-438, 2023 02 02.
Artigo em Inglês | MEDLINE | ID: mdl-36724329

RESUMO

BACKGROUND: In September 2015, the four-component, protein-based meningococcal serogroup B vaccine (4CMenB; Bexsero) became available for private purchase in Spain. METHODS: We conducted a nationwide matched case-control study to assess the effectiveness of 4CMenB in preventing invasive meningococcal disease in children. The study included all laboratory-confirmed cases of invasive meningococcal disease in children younger than 60 months of age between October 5, 2015, and October 6, 2019, in Spain. Each case patient was matched with four controls according to date of birth and province. 4CMenB vaccination status of the case patients and controls was compared with the use of multivariate conditional logistic regression. RESULTS: We compared 306 case patients (243 [79.4%] with serogroup B disease) with 1224 controls. A total of 35 case patients (11.4%) and 298 controls (24.3%) had received at least one dose of 4CMenB. The effectiveness of complete vaccination with 4CMenB (defined as receipt of at least 2 doses, administered in accordance with the manufacturer's recommendations) was 76% (95% confidence interval [CI], 57 to 87) against invasive meningococcal disease caused by any serogroup, and partial vaccination was 54% (95% CI, 18 to 74) effective. Complete vaccination resulted in an effectiveness of 71% (95% CI, 45 to 85) against meningococcal serogroup B disease. Vaccine effectiveness with at least one dose of 4CMenB was 64% (95% CI, 41 to 78) against serogroup B disease and 82% (95% CI, 21 to 96) against non-serogroup B disease. With the use of the genetic Meningococcal Antigen Typing System, serogroup B strains that were expected to be covered by 4CMenB were detected in 44 case patients, none of whom had been vaccinated. CONCLUSIONS: Complete vaccination with 4CMenB was found to be effective in preventing invasive disease by serogroup B and non-serogroup B meningococci in children younger than 5 years of age.


Assuntos
Infecções Meningocócicas , Vacinas Meningocócicas , Neisseria meningitidis Sorogrupo B , Criança , Humanos , Lactente , Estudos de Casos e Controles , Infecções Meningocócicas/microbiologia , Infecções Meningocócicas/prevenção & controle , Vacinas Meningocócicas/uso terapêutico , Neisseria meningitidis , Espanha
2.
Phys Rev Lett ; 132(15): 156701, 2024 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-38682975

RESUMO

A new perovskite KOsO_{3} has been stabilized under high-pressure and high-temperature conditions. It is cubic at 500 K (Pm-3m) and undergoes subsequent phase transitions to tetragonal at 320 K (P4/mmm) and rhombohedral (R-3m) at 230 K as shown from refining synchrotron x-ray powder diffraction (SXRD) data. The larger orbital overlap integral and the extended wave function of 5d electrons in the perovskite KOsO_{3} allow to explore physics from the regime where Mott and Hund's rule couplings dominate to the state where the multiple interactions are on equal footing. We demonstrate an exotic magnetic ordering phase found by neutron powder diffraction along with physical properties via a suite of measurements including magnetic and transport properties, differential scanning calorimetry, and specific heat, which provide comprehensive information for a system at the crossover from localized to itinerant electronic behavior.

3.
Inorg Chem ; 61(14): 5502-5511, 2022 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-35344352

RESUMO

All-inorganic lead halide perovskites like CsPbBr3, CsPbI3, or RbPbI3 are good replacements for the classical hybrid organic-inorganic perovskites like CH3NH3PbI3, susceptible to fast degradation in the presence of humid air. They also exhibit outstanding light absorption properties suitable for solar energy applications. Here, we describe the synthesis of RbPbI3 by mechanochemical procedures with green credentials, avoiding toxic or expensive organic solvents; this specimen exhibits excellent crystallinity. We report neutron powder diffraction data, essential to revisit some subtle structural features around room temperature (200-400 K). In all these regimes, the orthorhombic Pnma crystal structure is characterized by the presence along the b direction of the crystal of double rows of edge-sharing PbI6 octahedra. The lone electron pairs of Pb2+ ions have a strong stereochemical effect on the PbI6 octahedral distortion. The relative covalency of Rb-I versus Pb-I bonds shows that the Pb-I-related motions are more rigid than Rb-I-related vibrations, as seen in the Debye temperatures from the evolution of the anisotropic displacements. The optical gap, measured by diffuse reflectance UV-vis spectroscopy, is ∼2.51 eV and agrees well with ab initio calculations. The thermoelectric Seebeck coefficient is 3 orders of magnitude larger than that of other halide perovskites, with a value of ∼117,000 µV·K-1 at 460 K.

4.
J Cardiovasc Pharmacol ; 78(3): 463-473, 2021 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-34117181

RESUMO

ABSTRACT: The aim of our study is to assess the impact of anemia, chronic kidney disease, and diabetes mellitus on platelet reactivity (PR) in patients with severe aortic stenosis, both at baseline and after transcatheter aortic valve implantation (TAVI). This study is a prespecified subanalysis of the REAC-TAVI prospective, multicenter trial that included patients pretreated with aspirin + clopidogrel before TAVI. PR was measured at baseline and at 5 different time points after TAVI with the VerifyNow assay (Accriva Diagnostics, San Diego, CA), over a 3-month follow-up period. Patients with high PR (HPR) at baseline, before TAVI (n = 48) were randomized to aspirin + clopidogrel or aspirin + ticagrelor for 3 months, whereas those with normal PR (NPR) (n = 20) were continued on aspirin + clopidogrel. A "raiser response" in PR was defined as an increase in PR units >20% of baseline after TAVI. Patients with HPR before TAVI presented concomitant anemia and chronic kidney disease more frequently than their counterparts with NPR. Anemia and higher body mass index were independently associated with HPR to clopidogrel at baseline. Moreover, anemic patients with baseline HPR who were continued on clopidogrel presented higher PR after TAVI than patients with HPR switched to ticagrelor. All patients with baseline NPR presented a "raiser response" after TAVI, which was nonexistent among patients with HPR managed with ticagrelor. In summary, anemia seems as a relevant factor associated with baseline HPR and higher PR after TAVI in patients with baseline HPR randomized to clopidogrel, whereas ticagrelor proved more effective than clopidogrel at attaining sustained reductions in PR during follow-up, regardless of baseline comorbidities.


Assuntos
Estenose da Valva Aórtica/cirurgia , Aspirina/uso terapêutico , Plaquetas/efeitos dos fármacos , Clopidogrel/uso terapêutico , Terapia Antiplaquetária Dupla , Inibidores da Agregação Plaquetária/uso terapêutico , Ticagrelor/uso terapêutico , Substituição da Valva Aórtica Transcateter/efeitos adversos , Idoso , Idoso de 80 Anos ou mais , Anemia/sangue , Anemia/epidemiologia , Estenose da Valva Aórtica/sangue , Estenose da Valva Aórtica/diagnóstico , Estenose da Valva Aórtica/epidemiologia , Aspirina/efeitos adversos , Plaquetas/metabolismo , Clopidogrel/efeitos adversos , Comorbidade , Diabetes Mellitus/sangue , Diabetes Mellitus/epidemiologia , Terapia Antiplaquetária Dupla/efeitos adversos , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Inibidores da Agregação Plaquetária/efeitos adversos , Testes de Função Plaquetária , Prevalência , Estudos Prospectivos , Insuficiência Renal Crônica/sangue , Insuficiência Renal Crônica/epidemiologia , Índice de Gravidade de Doença , Espanha/epidemiologia , Ticagrelor/efeitos adversos , Fatores de Tempo , Resultado do Tratamento
5.
Inorg Chem ; 60(10): 7413-7421, 2021 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-33900757

RESUMO

Skutterudite-type compounds based on □Co4Sb12 pnictide are promising for thermoelectric application due to their good Seebeck values and high carrier mobility. Filling the 8a voids (in the cubic space group Im3̅) with different elements (alkali, alkali earth, and rare earth) helps to reduce the thermal conductivity and thus increases the thermoelectric performance. A systematic characterization by synchrotron X-ray powder diffraction of different M-filled Co4Sb12 (M = K, Sr, La, Ce, and Yb) skutterudites was carried out under high pressure in the range ∼0-12 GPa. The isothermal equations of state (EOS) were obtained in this pressure range and the Bulk moduli (B0) were calculated for all the filled skutterudites, yielding unexpected results. A lattice expansion due to the filler elements fails in the description of the Bulk moduli. Topochemical studies of the filler site environment exhibited a slight disturbance and an increased ionic character when the filler is incorporated. The mechanical properties by means of Bulk moduli resulted in being sensitive to the presence of filler atoms inside the skutterudite voids, being affected by the covalent/ionic exchange of the Co-Sb and Sb-Sb bonds.

6.
J Am Chem Soc ; 140(6): 2214-2220, 2018 02 14.
Artigo em Inglês | MEDLINE | ID: mdl-29334457

RESUMO

Perovskite oxides hosting ferroelectricity are particularly important materials for modern technologies. The ferroelectric transition in the well-known oxides BaTiO3 and PbTiO3 is realized by softening of a vibration mode in the cubic perovskite structure. For most perovskite oxides, octahedral-site tilting systems are developed to accommodate the bonding mismatch due to a geometric tolerance factor t = (A-O)/[√2(B-O)] < 1. In the absence of cations having lone-pair electrons, e.g., Bi3+ and Pb2+, all simple and complex A-site and B-site ordered perovskite oxides with a t < 1 show a variety of tilting systems, and none of them become ferroelectric. The ferroelectric CaMnTi2O6 oxide is, up to now, the only one that breaks this rule. It exhibits a columnar A-site ordering with a pronounced octahedral-site tilting and yet becomes ferroelectric at Tc ≈ 650 K. Most importantly, the ferroelectricity at T < Tc is caused by an order-disorder transition instead of a displacive transition; this character may be useful to overcome the critical thickness problem experienced in all proper ferroelectrics. Application of this new ferroelectric material can greatly simplify the structure of microelectronic devices. However, CaMnTi2O6 is a high-pressure phase obtained at 7 GPa and 1200 °C, which limits its application. Here we report a new method to synthesize a gram-level sample of ferroelectric Ca2-xMnxTi2O6, having the same crystal structure as CaMnTi2O6 and a similarly high Curie temperature. The new finding paves the way for the mass production of this important ferroelectric oxide. We have used neutron powder diffraction to identify the origin of the peculiar ferroelectric transition in this double perovskite and to reveal the interplay between magnetic ordering and the ferroelectric displacement at low temperatures.

7.
Inorg Chem ; 56(22): 14214-14219, 2017 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-29116775

RESUMO

Hybrid organic-inorganic perovskites, MAPbX3 (X = halogen), containing methylammonium (MA: CH3-NH3+) in the large voids conformed by the PbX6 octahedral network, are the active absorption materials in the new generation of solar cells. CH3NH3PbBr3 is a promising member with a large band gap that gives rise to a high open circuit voltage. A deep knowledge of the crystal structure and, in particular, the MA conformation inside the perovskite cage across the phase transitions undergone below room temperature, seems essential to establish structure-property correlations that may drive to further improvements. The presence of protons requires the use of neutrons, combined with synchrotron XRD data that help to depict subtle symmetry changes undergone upon cooling. We present a consistent picture of the structural features of this fascinating material, in complement with photocurrent measurements from a photodetector device, demonstrating the potential of MAPbBr3 in optoelectronics.

8.
Inorg Chem ; 53(9): 4281-3, 2014 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-24716725

RESUMO

The search for new double-perovskite oxides has grown rapidly in recent years because of their interesting physical properties like ferroelectricity, magnetism, and multiferroics. The synthesis of double perovskites, especially the A-site-ordered perovskites, in most cases needs to be made under high pressure, which is a drawback for applying these materials. Here we have demonstrated synthetic routes at ambient pressure by which we have obtained a high-quality duo-sites-ordered double perovskite, CaCu3Fe2Sb2O12, which has been previously synthesized under high pressure. The availability of a large quantity of the powder sample allows us to determine the crystal and magnetic structures by neutron powder diffraction (NPD) at 300 and 1.3 K. Measurements of the magnetization and heat capacity showed a ferrimagnetic transition at 160 K. A ferrimagnetic structure consisting of the uncompensated antiferromagnetic coupling between neighboring collinear copper and iron spins has been resolved from the low-temperature NPD data.

9.
Inorg Chem ; 53(11): 5609-18, 2014 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-24819938

RESUMO

The synthesis and crystal structure evolution of the double perovskite Pb2YSbO6 is reported for the first time. The structure has been analyzed in the temperature range between 100 and 500 K by using a combination of synchrotron and neutron powder diffraction. This compound shows two consecutive first order phase transformations as previously observed for a subgroup of Pb2RSbO6 perovkites (R = rare earths). The thermodynamic parameters associated with the phase transitions were calculated using differential scanning calorimetry (DSC), and the role of the diverse cations of the structure was studied from DFT calculations for the room temperature polymorph. The crystal structure evolves from a C2/c monoclinic structure (a(-)b(-)b(-) tilting system in Glazer's notation) to another monoclinic P2(1)/n (a(-)a(-)b(+)) phase with an incommensurate modulation and finally to a cubic Fm3m perovskite (a(0)a(0)a(0)). The highly distorted nature of the room temperature crystal structure seems to be driven by the polarization of the Pb lone pair which shows a marked local effect in the atomic spatial arrangements. Moreover, the lone pairs have been localized from DFT calculations and show an antiferroelectric ordering along the b monoclinic axis.

10.
ACS Appl Mater Interfaces ; 15(43): 50290-50301, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37862555

RESUMO

Transition-metal chalcogenides with intercalated layered structures are interesting systems in material physics due to their attractive electronic and magnetic properties, with applications in the fields of magnetic refrigerators, catalysts, and thermoelectrics, among others. In this work, we studied in detail the structural, electronic, and magnetic properties of (Fe,Ti)-based sulfides with formula FexTi2S4 (x = 0.24, 0.32, and 0.42), prepared as polycrystalline materials under high-pressure conditions. They present a layered Heideite-type crystal structure, as assessed by synchrotron X-ray diffraction. A local structure analysis using Fe K-edge extended X-ray-absorption fine structure (EXAFS) data unveiled a conspicuous contraction of the main Fe-S bond in Fe0.24Ti2S4 at the vicinity of the magnetic transition 60-80 K. We suggest that this anomaly is related to magnetoelastic coupling effects. The EXAFS analysis allowed extraction of the Einstein temperatures (θE), i.e., the phonon contribution to the specific heat, for the two bond pairs Fe-S(1) [θE ≈318 K; 290 K (C/T)] and Fe-Ti(1) [θE ≈218 K; 190 K (C/T)]. In addition to the structural and local vibrational measurements, we probed the magnetic properties using magneto-calorimetry, magnetometry under applied pressure, magnetoresistance (MR), and Hall effect measurements. We observed the appearance of a broad peak in the specific heat around 120 K in the x = 0.42 compound that we associated with an antiferromagnetic ordering electronic transition. We found that the antiferromagnetic transition temperature is pressure and composition sensitive and reduces at 1.2 GPa by ∼12 and ∼3 K, for the members with x = 0.24 and x = 0.42, respectively. Similarly, the saturation magnetization in the ordered phase depends on both pressure and iron content, reducing its value by 50, 90, and 30% for x = 0.24, 0.32, and 0.42, respectively. We observed clear jumps in the magnetic hysteresis loops, MR, and anomalous Hall effect (AHE) below 2 K at fields around 2-4 T. We associated this observation with the metamagnetic transitions; from the Berry-curvature a decoupling parameter of SH = 0.12 V-1 is determined. Comparison of the results on the temperature-dependent magnetization, MR, and AHE elucidates a strong inelastic scattering contribution to the AHE at higher temperatures due to the cluster spin-glass phase.

11.
Parasit Vectors ; 16(1): 292, 2023 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-37592348

RESUMO

BACKGROUND: In recent years, the usefulness of echocardiography and serum biomarkers in the diagnosis of pulmonary hypertension (PH) in dogs with heartworm disease has been studied. Previously, N-terminal pro B-type natriuretic peptide (NT-proBNP) has shown high concentrations in dogs with heart disease and/or PH as well as its usefulness as a prognostic indicator, but it has never been evaluated in the diagnosis and prognosis of PH in dogs with heartworm disease. The aim was to evaluate the serum concentrations of NT-proBNP in dogs infected by Dirofilaria immitis to determine its usefulness as a tool to detect precapillary PH. METHODS: NT-proBNP was determined in 50 heartworm-infected dogs. Presence/absence of PH was determined echocardiographically, using the Right Pulmonary Artery Distensibility Index (RPAD Index) and the systolic flow of tricuspid regurgitation mainly, together with other echocardiographic measurements following the guidelines of the American College of Veterinary Internal Medicine (ACVIM) for the diagnosis of PH. Other epidemiological parameters (breed, age, sex, status: client-owned or shelter dogs) and clinical parameters (microfilaremia, parasite burden, presence of symptoms, body condition) were collected as well. RESULTS: Moderate-severe PH was present in 40% of the dogs (RPAD Index < 29.5%), NT-proBNP concentrations being significantly higher compared with dogs that did not have PH. A cutoff for NT-proBNP of ≥ 1178.45 pmol/l showed a sensitivity of 64.3% and a specificity of 95.5% for the presence of moderate-severe PH. Older dogs and dogs from shelters showed significantly higher NT-proBNP concentrations. Dogs with symptoms and low body condition presented significantly higher NT-proBNP concentrations as well. CONCLUSIONS: The determination of NT-pro-BNP concentration can be a useful tool in the diagnostic work-up of dogs with heartworm disease and associated PH and can help to identify animals in the more advanced stage of this disorder.


Assuntos
Dirofilaria immitis , Dirofilariose , Cardiopatias , Hipertensão Pulmonar , Cães , Animais , Hipertensão Pulmonar/diagnóstico , Hipertensão Pulmonar/veterinária , Peptídeo Natriurético Encefálico , Dirofilariose/diagnóstico , Biomarcadores
12.
Parasit Vectors ; 16(1): 192, 2023 Jun 09.
Artigo em Inglês | MEDLINE | ID: mdl-37291670

RESUMO

BACKGROUND: Cats can be infected by Dirofilaria immitis, the causative agent of heartworm disease, characterized by respiratory signs, airway hyperreactivity, remodelling and inflammation. Allergy is a multifactorial pathology, and the role of a number of helminth parasites in the development of allergies in humans and other species has been demonstrated in many studies. The aim of the present study was to verify whether cats seropositive for D. immitis present hypersensitivity to some environmental allergens. METHODS: Blood samples were collected from 120 cats and tested for the presence of specific immunoglobulin G antibodies against D. immitis and for hypersensitivity to 20 allergens, using commercial allergen test kits. RESULTS: Of the 120 cats tested, 72 (60.0%) were seropositive for anti-D. immitis IgG and 55 (45.8%) showed clinical signs of heartworm disease of a respiratory nature. The results of testing with the allergen kits showed that 50.8% of cats were seropositive for ≥ 1 allergens, with the most common allergens being Dermatophagoides farinae (25.8%), Dermatophagoides pteronyssinus (20.0%), Malassezia (17.5%) and Ctenocephalides felis (14.2%). The prevalence of allergies was significantly higher-by almost threefold-in cats seropositive for D. immitis (68.1% vs. 25%). There were no significant differences between the prevalence of allergic cats and presence/absence of symptoms, and the results confirmed that symptoms were not a decisive factor for the presence of allergies. The risk for developing allergies was 6.3-fold higher in cats seropositive for D. immitis than in cats that were seronegative, confirming that seropositivity for D. immitis is a risk factor. CONCLUSIONS: Cats with confirmed heartworm can develop serious respiratory signs, potentially leading to progression to permanent lung injury and predisposing cats to hyperresponsive airway disease. Previous studies have shown that seropositivity for D. immitis and Wolbachia is related to the presence of bronchoconstriction and bronchospasm in the affected cat. The results support the suspicion that contact with D. immitis may be a risk factor for the presence of allergies.


Assuntos
Doenças do Gato , Dirofilaria immitis , Dirofilariose , Hipersensibilidade , Humanos , Gatos , Animais , Dirofilariose/parasitologia , Alérgenos , Hipersensibilidade/epidemiologia , Hipersensibilidade/veterinária , Anticorpos , Doenças do Gato/epidemiologia
13.
J Clin Med ; 12(4)2023 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-36835907

RESUMO

Tricuspid regurgitation (TR) is one of the most common heart valve diseases, associated a with poor prognosis since significant TR is associated with an increased mortality risk compared to no TR or mild regurgitation. Surgery is the standard treatment for TR, although it is associated with high morbidity, mortality, and prolonged hospitalization, particularly in tricuspid reoperation after left-sided surgery. Thus, several innovative percutaneous transcatheter approaches for repair and replacement of the tricuspid valve have gathered significant momentum and have undergone extensive clinical development in recent years, with favorable clinical outcomes in terms of mortality and rehospitalization during the first year of follow-up. We present three clinical cases of transcatheter tricuspid valve replacement in an orthotopic position with two different innovative systems along with a review of the state-of-the-art of this emergent topic.

14.
JACC Case Rep ; 15: 101848, 2023 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-37283839

RESUMO

A 79-year-old woman with a history of dilated cardiomyopathy who required a permanent peacemaker, recently upgraded to implantable cardioverter-defibrillator cardiac resynchronization therapy, was admitted for right heart failure. On echocardiography, torrential tricuspid regurgitation was noted, with 2 leads across the valve. After multidisciplinary evaluation, a dedicated transcatheter valve replacement was successfully implanted. (Level of Difficulty: Intermediate.).

15.
Sci Rep ; 12(1): 18647, 2022 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-36333345

RESUMO

Methylammonium (MA) lead trihalide perovskites, CH3NH3PbX3 (X = I, Br, Cl), have emerged as a new class of light-absorbing materials for photovoltaic applications, reaching efficiencies of 23% when implemented in solar cell heterojunctions. In particular, MAPbBr3 is a promising member with a large bandgap that gives rise to a high open circuit voltage. Here we present a structural study from neutron diffraction (ND) data of an undeuterated MAPbBr3 specimen, carried out to follow its crystallographic behaviour in the 2-298 K temperature range. Besides the known crystallographic phases, i.e. the high-temperature Pm[Formula: see text]m cubic structure, the intermediate I4/mcm tetragonal symmetry and the low-temperature Pnma orthorhombic phase, we additionally identified, from a detailed sequential ND analysis, a novel intermediate phase within the 148.5-154.0 K temperature range as an orthorhombic Imma structure, early associated with a coexistence of phases. Moreover, our ND data allowed us to unveil the configuration of the organic MA units and their complete localization within the mentioned temperature range, thus improving the crystallographic description of this compound. The evolution with temperature of the H-bonds between the organic molecule and the inorganic cage is also followed. A deep knowledge of the crystal structure and, in particular, the MA conformation inside the perovskite cage seems essential to establish structure-property correlations that may drive further improvements.

16.
ACS Appl Mater Interfaces ; 14(45): 50739-50750, 2022 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-36321841

RESUMO

The design of an active, effective, and economically viable catalyst for CO2 conversion into value-added products is crucial in the fight against global warming and energy demand. We have developed very efficient catalysts for reverse water-gas shift (rWGS) reaction. Specific conditions of the synthesis by combustion allow the obtention of macroporous materials based on nanosized Ni particles supported on a mixed oxide of high purity and crystallinity. Here, we show that Ni/La-doped CeO2 catalysts─with the "right" Ni and La proportions─have an unprecedented catalytic performance per unit mass of catalyst for the rWGS reaction as the first step toward CO2 valorization. Correlations between physicochemical properties and catalytic activity, obtained using a combination of different techniques such as X-ray and neutron powder diffraction, Raman spectroscopy, in situ near ambient pressure X-ray photoelectron spectroscopy, electron microscopy, and catalytic testing, point out to optimum values for the Ni loading and the La proportion. Density functional theory calculations of elementary steps of the reaction on model Ni/ceria catalysts aid toward the microscopic understanding of the nature of the active sites. This finding offers a fundamental basis for developing economical catalysts that can be effectively used for CO2 reduction with hydrogen. A catalyst based on Ni0.07/(Ce0.9La0.1Ox)0.93 shows a CO production of 58 × 10-5 molCO·gcat-1·s-1 (700 °C, H2/CO2 = 2; selectivity to CO > 99.5), being stable for 100 h under continuous reaction.

17.
Inorg Chem ; 50(12): 5545-57, 2011 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-21618974

RESUMO

The synthesis, crystal structure, and dielectric properties of four novel members of the family of double perovskites Pb(2)LnSbO(6) are described. The room-temperature crystal structures were refined from neutron powder diffraction (NPD) data in the monoclinic C2/c (No. 15) space group. They contain a completely ordered array of alternating LnO(6) and SbO(6) octahedra sharing corners, tilted in antiphase along the three pseudocubic axes, with a a(-)b(-)b(-) tilting scheme, which is very unusual in the crystallochemistry of perovskites. The lead atoms occupy highly asymmetric voids with 8-fold coordination due to the stereoactivity of the Pb(2+) electron lone-pair. Several trends are observed for the entire family of compounds upon heating. The Ln = Lu, Yb, and Er oxides display three successive phase transitions in a narrow temperature range, as shown by differential scanning calorimetry (DSC) data, while the Ln = Ho shows only two transitions. Different crystal structure evolutions have been found from temperature-dependent NPD and DSC, following the space-group sequence C2/c → P2(1)/n → R ̅3 → Fm ̅3m for Ln = Lu and Yb, the sequence C2/c → unknown → P2(1)/n → Fm ̅3m for Ln = Er, and C2/c → P2(1)/n → Fm ̅3m for Ln = Ho. The Ln/Sb long-range ordering is preserved across the consecutive phase transitions. Dielectric permittivity measurements indicate the presence of a paraelectric/antiferroelectric transition (associated with the last structural transition), as suggested by the negative Curie temperature from the Curie-Weiss fit of the reciprocal permittivity.


Assuntos
Antimônio/química , Elementos da Série dos Lantanídeos/química , Chumbo/química , Oxigênio/química , Temperatura , Modelos Moleculares
18.
Inorg Chem ; 50(21): 10929-36, 2011 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-21973275

RESUMO

A series of layered oxides of nominal composition SrFe(1-x)Mn(x)O(2) (x = 0, 0.1, 0.2, 0.3) have been prepared by the reduction of three-dimensional perovskites SrFe(1-x)Mn(x)O(3-δ) with CaH(2) under mild temperature conditions of 583 K for 2 days. The samples with x = 0, 0.1, and 0.2 exhibit an infinite-layer crystal structure where all of the apical O atoms have been selectively removed upon reduction. A selected sample (x = 0.2) has been studied by neutron powder diffraction (NPD) and X-ray absorption spectroscopy. Both techniques indicate that Fe and Mn adopt a divalent oxidation state, although Fe(2+) ions are under tensile stress whereas Mn(2+) ions undergo compressive stress in the structure. The unit-cell parameters progressively evolve from a = 3.9932(4) Å and c = 3.4790(4) Å for x = 0 to a = 4.00861(15) Å and c = 3.46769(16) Å for x = 0.2; the cell volume presents an expansion across the series from V = 55.47(1) to 55.722(4) Å(3) for x = 0 and 0.2, respectively, because of the larger effective ionic radius of Mn(2+) versus Fe(2+) in four-fold coordination. Attempts to prepare Mn-rich compositions beyond x = 0.2 were unsuccessful. For SrFe(0.8)Mn(0.2)O(2), the magnetic properties indicate a strong magnetic coupling between Fe(2+) and Mn(2+) magnetic moments, with an antiferromagnetic temperature T(N) above room temperature, between 453 and 523 K, according to temperature-dependent NPD data. The NPD data include Bragg reflections of magnetic origin, accounted for with a propagation vector k = ((1)/(2), (1)/(2), (1)/(2)). A G-type antiferromagnetic structure was modeled with magnetic moments at the Fe/Mn position. The refined ordered magnetic moment at this position is 1.71(3) µ(B)/f.u. at 295 K. This is an extraordinary example where Mn(2+) and Fe(2+) ions are stabilized in a square-planar oxygen coordination within an infinite-layer structure. The layered SrFe(1-x)Mn(x)O(2) oxides are kinetically stable at room temperature, but in air at ~170 °C, they reoxidize and form the perovskites SrFe(1-x)Mn(x)O(3-δ). A cubic phase is obtained upon reoxidation of the layered compound, whereas the starting precursor SrFeO(2.875) (Sr(8)Fe(8)O(23)) was a tetragonal superstructure of perovskite.

19.
Trials ; 22(1): 423, 2021 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-34187554

RESUMO

BACKGROUND: Tracheostomy is one of the most frequent techniques in intensive care units (ICU). Fiberoptic bronchoscopy (FB) is a safety measure when performing a percutaneous dilatational tracheostomy (PDT), but the controversy surrounding the routine use of FB as part of the procedure remains open. National surveys in some European countries showed that the use of FB is non-standardized. Retrospective studies have not shown a significant difference in complications between procedures performed with or without a bronchoscope. International guidelines have not been able to establish recommendations regarding the use of FB in PDT due to lack of evidence. DESIGN: This is a multicenter (three centers at the time of  publishing this paper) randomized controlled clinical trial to examine the safety of percutaneous tracheostomy using FB. We will include all consecutive adult patients admitted to the ICU in whom percutaneous tracheostomy for prolonged mechanical ventilation is indicated and with no exclusion criteria for using FB. Eligible patients will be randomly assigned to receive blind PDT or PDT under endoscopic guidance. All procedures will be performed by experienced intensivists in PDT and FB. A Data Safety and Monitoring Board (DSMB) will monitor the trial. The primary outcome is the incidence of perioperative complications. DISCUSSION: FB is a safe technique when performing PDT although its use is not universally accepted in all ICUs as a routine practice. Should PDT be monitored routinely with endoscopic guidance? This study will assess the role of FB monitoring during PDT. TRIAL REGISTRATION: ClinicalTrials.gov NCT04265625. Registered on February 11, 2020.


Assuntos
Broncoscopia , Traqueostomia , Adulto , Broncoscopia/efeitos adversos , Dilatação/efeitos adversos , Europa (Continente) , Humanos , Estudos Multicêntricos como Assunto , Ensaios Clínicos Controlados Aleatórios como Assunto , Estudos Retrospectivos , Traqueostomia/efeitos adversos
20.
J Am Chem Soc ; 132(41): 14470-80, 2010 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-20866041

RESUMO

The synthesis, crystal structure, and dielectric properties of the novel double perovskite Pb(2)TmSbO(6) are described. The room-temperature crystal structure was determined by ab initio procedures from neutron powder diffraction (NPD) and synchrotron X-ray powder diffraction (SXRPD) data in the monoclinic C2/c (No. 15) space group. This double perovskite contains a completely ordered array of alternating TmO(6) and SbO(6) octahedra sharing corners, tilted in antiphase along the three pseudocubic axes, with an a(-)b(-)b(-) tilting scheme, which is very unusual in the crystallochemistry of perovskites. The lead atoms occupy a highly asymmetric void with 8-fold coordination due to the stereoactivity of the Pb(2+) lone electron pair. This compound presents three successive phase transitions in a narrow temperature range (at T1 = 385 K, T2 = 444 K, and T3 = 460 K in the heating run) as shown by differential scanning calorimetry (DSC) data. The crystal structure and temperature-dependent NPD follow the space-group sequence C2/c → P2(1)/n → R3 → Fm3m. This is a novel polymorph succession in the high-temperature evolution of perovskite-type oxides. The Tm/Sb long-range ordering is preserved across the consecutive phase transitions. Dielectric permittivity measurements indicate the presence of a paraelectric/antiferroelectric transition (associated with the last structural transition), as suggested by the negative Curie temperature obtained from the Curie-Weiss fit of the reciprocal permittivity.

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