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INTRODUCTION: Despite rapid technological progress, some arrhythmias are still resistant to standard unipolar ablation. These include arrhythmias arising from the base of the heart, cardiac crux, or epicardium. Bipolar radiofrequency ablation (B-RFA) may be useful in some cases, however, data on the efficacy of this approach in various arrhythmia localizations are scarce. The aim of this study was to assess the efficacy of B-RFA in patients with ventricular arrhythmias originating from various locations, occurring refractory to standard unipolar ablation approaches. METHODS: An observational, single center study was conducted over a 30-month period. B-RFA were performed using dedicated radio frequency (RF) generator and electroanatomic mapping system. RESULTS: Twenty-four procedures, in 23 patients with a median (range) of 1 (1-2) previously failed unipolar ablation procedures, were included in the final analysis. There were 12 ablations of ventricular arrhythmias originating from interventricular septum with an acute success rate of 75%, and 12 from left ventricular (LV) summit with an acute success rate of 58%. The midterm success rate (median interquartile range follow-up of 205 days [188-338]) was 66% and 50%, respectively. CONCLUSIONS: B-RFA is a promising method of catheter ablation for refractory cardiac arrhythmias. A higher success rate was observed in ablation for difficult ventricular arrhythmias originating from interventricular septal region than LV summit.
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Ablação por Cateter , Taquicardia Ventricular , Humanos , Taquicardia Ventricular/diagnóstico , Taquicardia Ventricular/cirurgia , Resultado do Tratamento , Arritmias Cardíacas , Ventrículos do Coração , Ablação por Cateter/efeitos adversos , Ablação por Cateter/métodosRESUMO
AIMS: Bipolar radiofrequency ablation (B-RFA) has been reported as a bail-out strategy for the treatment of therapy refractory ventricular arrhythmias (VA). Currently, existing setups have not been standardized for B-RFA, while the impact of conventional B-RFA approaches on lesion formation remains unclear. METHODS AND RESULTS: (i) In a multicentre observational study, patients undergoing B-RFA for previously therapy-refractory VA using a dedicated B-RFA setup were retrospectively analysed. (ii) Additionally, in an ex vivo model lesion formation during B-RFA was evaluated using porcine hearts. In a total of 26 procedures (24 patients), acute success was achieved in all 14 ventricular tachycardia (VT) procedures and 7/12 procedures with premature ventricular contractions (PVC), with major complications occurring in 1 procedure (atrioventricular block). During a median follow-up of 211 days in 21 patients, 6/11 patients (VT) and 5/10 patients (PVC) remained arrhythmia-free. Lesion formation in the ex vivo model during energy titration from 30 to 50 W led to similar lesion volumes compared with initial high-power 50 W B-RFA. Lesion size significantly increased when combining sequential unipolar and B-RFA (1429 mm3 vs. titration 501 mm3 vs. B-RFA 50 W 423 mm3, P < 0.001), an approach used in overall 58% of procedures and more frequently applied in procedures without VA recurrence (92% vs. 36%, P = 0.009). Adipose tissue severely limited lesion formation during B-RFA. CONCLUSION: Using a dedicated device for B-RFA for therapy-refractory VA appears feasible and safe. While some patients need repeat ablation, success rates were encouraging. Sequential unipolar and B-RFA may be favourable for lesion formation.
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Ablação por Cateter , Taquicardia Ventricular , Complexos Ventriculares Prematuros , Animais , Ablação por Cateter/métodos , Estudos Retrospectivos , Suínos , Taquicardia Ventricular/diagnóstico , Taquicardia Ventricular/cirurgia , Resultado do Tratamento , Complexos Ventriculares Prematuros/diagnóstico , Complexos Ventriculares Prematuros/cirurgiaRESUMO
Head motion is a major source of image artefacts in neuroimaging studies and can lead to degradation of the quantitative accuracy of reconstructed PET images. Simultaneous magnetic resonance-positron emission tomography (MR-PET) makes it possible to estimate head motion information from high-resolution MR images and then correct motion artefacts in PET images. In this article, we introduce a fully automated PET motion correction method, MR-guided MAF, based on the co-registration of multicontrast MR images. The performance of the MR-guided MAF method was evaluated using MR-PET data acquired from a cohort of ten healthy participants who received a slow infusion of fluorodeoxyglucose ([18-F]FDG). Compared with conventional methods, MR-guided PET image reconstruction can reduce head motion introduced artefacts and improve the image sharpness and quantitative accuracy of PET images acquired using simultaneous MR-PET scanners. The fully automated motion estimation method has been implemented as a publicly available web-service.
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Encéfalo/diagnóstico por imagem , Processamento de Imagem Assistida por Computador/métodos , Imageamento por Ressonância Magnética/métodos , Neuroimagem/métodos , Tomografia por Emissão de Pósitrons/métodos , Adulto , Humanos , Imagem MultimodalRESUMO
Experimental studies demonstrated a shift in the leading pacemaker site based on parasympathetic or sympathetic dominance. Radiofrequency catheter ablation of ganglionated plexi (GP) might be used to overcome deleterious effects of enhanced parasympathetic tone. Herein, we present two patients who underwent GP ablation due to cardioinhibitory type reflex syncope and symptomatic bradycardia, respectively. In both cases complete vagal denervation was achieved and was associated with a cranial shift of sinus node activation area with corresponding changes in surface P wave morphology. This unique phenomenon needs to be confirmed in the larger prospective study.
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Ablação por Cateter , Nó Sinoatrial , Denervação , Eletrocardiografia , Humanos , Estudos Prospectivos , Nervo Vago/cirurgiaRESUMO
Studies of task-evoked brain activity are the cornerstone of cognitive neuroscience, and unravel the spatial and temporal brain dynamics of cognition in health and disease. Blood oxygenation level dependent functional magnetic resonance imaging (BOLD-fMRI) is one of the most common methods of studying brain function in humans. BOLD-fMRI indirectly infers neuronal activity from regional changes in blood oxygenation and is not a quantitative metric of brain function. Regional variation in glucose metabolism, measured using [18-F] fluorodeoxyglucose positron emission tomography (FDG-PET), provides a more direct and interpretable measure of neuronal activity. However, while the temporal resolution of BOLD-fMRI is in the order of seconds, standard FDG-PET protocols provide a static snapshot of glucose metabolism. Here, we develop a novel experimental design for measurement of task-evoked changes in regional blood oxygenation and glucose metabolism with high temporal resolution. Over a 90-min simultaneous BOLD-fMRI/FDG-PET scan, [18F] FDG was constantly infused to 10 healthy volunteers, who viewed a flickering checkerboard presented in a hierarchical block design. Dynamic task-related changes in blood oxygenation and glucose metabolism were examined with temporal resolution of 2.5sec and 1-min, respectively. Task-related, temporally coherent brain networks of haemodynamic and metabolic connectivity were jointly coupled in the visual cortex, as expected. Results demonstrate that the hierarchical block design, together with the infusion FDG-PET technique, enabled both modalities to track task-related neural responses with high temporal resolution. The simultaneous MR-PET approach has the potential to provide unique insights into the dynamic haemodynamic and metabolic interactions that underlie cognition in health and disease.
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Neuroimagem Funcional/métodos , Imageamento por Ressonância Magnética/métodos , Reconhecimento Visual de Modelos/fisiologia , Tomografia por Emissão de Pósitrons/métodos , Córtex Visual/diagnóstico por imagem , Córtex Visual/fisiologia , Adolescente , Adulto , Feminino , Fluordesoxiglucose F18 , Glucose/metabolismo , Humanos , Masculino , Pessoa de Meia-Idade , Imagem Multimodal , Projetos de Pesquisa , Fatores de Tempo , Córtex Visual/metabolismo , Adulto JovemRESUMO
The aim of the study was to provide quantitative data and to look for new landmarks useful during transseptal puncture (TSP) using a fluoroscopy-guided approach. METHODS AND RESULTS: A total of 104 patients at mean age 57 ± 12 years, of whom 92% underwent pulmonary vein isolation, were analysed. Before TSP catheters were placed in the coronary sinus (CS) and His bundle region. A guidewire running from femoral vein through great veins was left loose in superior vena cava. Before TSP X-ray images were taken in right anterior oblique (RAO) 45° and RAO 53° projections. Locations posterior to TSP site in RAO were described with negative values and those anterior with positive values. The measured distances in millimeters were as follows: (a) between TSP site and posterior atrial wall (RAO 45 = -21 ± 7 mm; RAO 53 = -19 ± 6 mm (b) between TSP site and free guidewire (RAO 45 = -5 ± 4 mm, RAO 53 = -3 ± 4 mm (c) between TSP site and CS ostium (RAO 45 = 9 ± 6 mm; RAO 53 = 8 ± 5 mm (d) between TSP site and His region (RAO 45 = 29 ± 8 mm; RAO 53 = 30 ± 8 mm). We observed correlations between measured distances and age, body mass index and sizes of cardiac chambers. The distance between TSP site and the line projected by the guidewire running between great veins, measured in mid-RAO projections, was very small. CONCLUSION: The distances between TSP site and standard anatomical landmarks used during TSP vary with regard to age, physique and cardiac chamber dimensions. TSP site, as assessed in mid RAO, is in direct vicinity to the line projected by a guidewire running between the great veins.
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Pontos de Referência Anatômicos , Fibrilação Atrial/diagnóstico por imagem , Cateterismo Cardíaco , Cateterismo Periférico , Veia Femoral/diagnóstico por imagem , Septos Cardíacos/diagnóstico por imagem , Radiografia Intervencionista , Tomografia Computadorizada por Raios X , Adolescente , Adulto , Idoso , Fibrilação Atrial/cirurgia , Cateterismo Cardíaco/efeitos adversos , Ablação por Cateter , Cateterismo Periférico/efeitos adversos , Feminino , Fluoroscopia , Humanos , Masculino , Pessoa de Meia-Idade , Valor Preditivo dos Testes , Punções , Adulto JovemRESUMO
BACKGROUND: Iatrogenic pseudoaneurysms (IPA) are treated with ultrasound-guided thrombin injections (UGTI). We describe a novel technique for IPA repair that applies UGTI with thrombin foam (UGTFI). METHODS AND RESULTS: Successful obliteration of 6 IPAs (IPA without a neck, n = 5; with a neck, n = 1) in 6 patients (2 males, aged 68 ± 1 years, 4 females, aged 59 ± 11 years) was performed by using UGTFI. The dose of administered thrombin was 25-75 IU. No microembolization phenomenon and no serious clinical complications were observed. CONCLUSIONS: Treatment of IPA with UGTFI may reduce the embolization rate, risk of IPA cavity thrombin leakage, required drug dose. Use of the thrombin foam could be the next step in the development of the UGTI, particularly in the treatment of IPA without a neck.
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Falso Aneurisma , Hemostáticos , Idoso , Feminino , Artéria Femoral , Humanos , Doença Iatrogênica , Masculino , Pessoa de Meia-Idade , Trombina , Resultado do Tratamento , UltrassonografiaRESUMO
Simultaneous Magnetic Resonance Imaging (MRI) and Positron Emission Tomography (PET) scanning is a recent major development in biomedical imaging. The full integration of the PET detector ring and electronics within the MR system has been a technologically challenging design to develop but provides capacity for simultaneous imaging and the potential for new diagnostic and research capability. This article reviews state-of-the-art MR-PET hardware and software, and discusses future developments focusing on neuroimaging methodologies for MR-PET scanning. We particularly focus on the methodologies that lead to an improved synergy between MRI and PET, including optimal data acquisition, PET attenuation and motion correction, and joint image reconstruction and processing methods based on the underlying complementary and mutual information. We further review the current and potential future applications of simultaneous MR-PET in both systems neuroscience and clinical neuroimaging research. We demonstrate a simultaneous data acquisition protocol to highlight new applications of MR-PET neuroimaging research studies.
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Processamento de Imagem Assistida por Computador/métodos , Imageamento por Ressonância Magnética/métodos , Imagem Multimodal/métodos , Neuroimagem/métodos , Neurociências/métodos , Tomografia por Emissão de Pósitrons/métodos , Humanos , Processamento de Imagem Assistida por Computador/normas , Imageamento por Ressonância Magnética/normas , Imagem Multimodal/normas , Neuroimagem/normas , Neurociências/normas , Tomografia por Emissão de Pósitrons/normasRESUMO
INTRODUCTION: Frequent ventricular premature complexes (VPCs) may cause symptoms and/or lead to deterioration of LV systolic function. Although frequent VPCs may be abolished by catheter ablation, it may be challenging in case of their origin from the LV papillary muscles (PMs). Our collaborative study aimed to analyze in detail the site of origin and the outcome of ablation. METHODS: Consecutive 34 patients (males: 68%; aged 62 ± 12 years; LV ejection fraction: 50 ± 9%) undergoing catheter ablation of VPCs originating from PMs were included. All procedures were guided by intracardiac echocardiography. RESULTS: The size and shape of PMs were highly variable. The length of anterolateral and posteromedial PM was 23 ± 4 mm and 28 ± 7 mm, respectively. In about one-third of patients, the PM was formed by two distinctly separate heads. The ectopic foci were located on anterolateral, posteromedial or both PM in 35%, 56% and 9% of cases, respectively. Their location was found within the distal, mid, or proximal (basal) third of PM in the 67%, 19%, and 14%, respectively. A total of 86% of PM foci were acutely abolished and long-term success was achieved in 65% of patients. Absence of VPCs of other morphologies and a high burden of ectopic activity before ablation were associated with favorable clinical outcome. CONCLUSION: VPCs originate predominantly from the distal portion of the PM. This knowledge may facilitate the mapping in patients with infrequent ectopic beats. Intracardiac echocardiography is of crucial importance for navigation of the ablation catheter and for assessment of its stability at PM target sites.
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Frequência Cardíaca , Ventrículos do Coração/fisiopatologia , Músculos Papilares/fisiopatologia , Função Ventricular Esquerda , Complexos Ventriculares Prematuros/fisiopatologia , Potenciais de Ação , Idoso , Ablação por Cateter , Ecocardiografia , Técnicas Eletrofisiológicas Cardíacas , Europa (Continente) , Feminino , Ventrículos do Coração/diagnóstico por imagem , Ventrículos do Coração/cirurgia , Humanos , Masculino , Pessoa de Meia-Idade , Músculos Papilares/diagnóstico por imagem , Músculos Papilares/cirurgia , Fatores de Tempo , Complexos Ventriculares Prematuros/diagnóstico , Complexos Ventriculares Prematuros/cirurgiaRESUMO
A combination of experimental and computational techniques has been employed to explore the crystal structure and thermoelectric properties of A-site-deficient perovskite La1/3NbO3 ceramics. Crystallographic data from X-ray and electron diffraction confirmed that the room temperature structure is orthorhombic with Cmmm as a space group. Atomically resolved imaging and analysis showed that there are two distinct A sites: one is occupied with La and vacancies, and the second site is fully unoccupied. The diffuse superstructure reflections observed through diffraction techniques are shown to originate from La vacancy ordering. La1/3NbO3 ceramics sintered in air showed promising high-temperature thermoelectric properties with a high Seebeck coefficient of S1 = -650 to -700 µV/K and a low and temperature-stable thermal conductivity of k = 2-2.2 W/m·K in the temperature range of 300-1000 K. First-principles electronic structure calculations are used to link the temperature dependence of the Seebeck coefficient measured experimentally to the evolution of the density of states with temperature and indicate possible avenues for further optimization through electron doping and control of the A-site occupancies. Moreover, lattice thermal conductivity calculations give insights into the dependence of the thermal conductivity on specific crystallographic directions of the material, which could be exploited via nanostructuring to create high-efficiency compound thermoelectrics.
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BACKGROUND: Attenuation correction is one of the most crucial correction factors for accurate PET data quantitation in hybrid PET/MR scanners, and computing accurate attenuation coefficient maps from MR brain acquisitions is challenging. Here, we develop a method for accurate bone and air segmentation using MR ultrashort echo time (UTE) images. METHODS: MR UTE images from simultaneous MR and PET imaging of five healthy volunteers was used to generate a whole head, bone and air template image for inclusion into an improved MR derived attenuation correction map, and applied to PET image data for quantitative analysis. Bone, air and soft tissue were segmented based on Gaussian Mixture Models with probabilistic tissue maps as a priori information. We present results for two approaches for bone attenuation coefficient assignments: one using a constant attenuation correction value; and another using an estimated continuous attenuation value based on a calibration fit. Quantitative comparisons were performed to evaluate the accuracy of the reconstructed PET images, with respect to a reference image reconstructed with manually segmented attenuation maps. RESULTS: The DICE coefficient analysis for the air and bone regions in the images demonstrated improvements compared to the UTE approach, and other state-of-the-art techniques. The most accurate whole brain and regional brain analyses were obtained using constant bone attenuation coefficient values. CONCLUSIONS: A novel attenuation correction method for PET data reconstruction is proposed. Analyses show improvements in the quantitative accuracy of the reconstructed PET images compared to other state-of-the-art AC methods for simultaneous PET/MR scanners. Further evaluation is needed with radiopharmaceuticals other than FDG, and in larger cohorts of participants.
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Encéfalo/diagnóstico por imagem , Imageamento por Ressonância Magnética/métodos , Tomografia por Emissão de Pósitrons/métodos , Interpretação de Imagem Radiográfica Assistida por Computador/normas , Adulto , Algoritmos , Fluordesoxiglucose F18/administração & dosagem , Voluntários Saudáveis , Humanos , Interpretação de Imagem Radiográfica Assistida por Computador/métodos , Compostos Radiofarmacêuticos/administração & dosagem , Adulto JovemRESUMO
AIM: Left atrial (LA) fibrosis promotes atrial fibrillation (AF), may predict poor radiofrequency catheter ablation (RFCA) outcome, and may be assessed invasively using electroanatomical mapping (EAM). Speckle tracking echocardiography (STE) enables quantitative assessment of LA function. The aim was to assess the relationship between LA fibrosis derived from EAM and LA echocardiographic parameters as well as biomarkers of fibrosis in patients with AF. METHODS: Sixty-six patients (64% males, mean age 56 ± 10) with nonvalvular AF treated with first RFCA were prospectively studied. Seventy-three percent of patients were in sinus rhythm at the time of examination. LA geometry, systolic, and diastolic function were assessed. In STE global, peak atrial longitudinal (PALS) and contractile (PACS) strain were calculated. LA stiffness index (LAs) - the ratio of E/e' to PALS - was assessed. The EAM of LA was build using Carto System before RFCA. Low amplitude potentials area (LAPA) was quantitatively analyzed and expressed as a percentage of LA surface using the cut-off <0.5 mV to detect potential sites of fibrosis. The serum concentrations of MMP-9, PIIINP, and TGFß1were estimated before RFCA. RESULTS: Pearson correlation analysis showed a significant correlation between LA diastolic function parameters: PALS (-0.54, P < .001), LAs (0.65, P < .001), and LAPA in patients who were in sinus rhythm. Also LA volume significantly correlated with LAPA (0.44, P < .002). None of biomarkers correlated with LAPA. CONCLUSION: Left atrial diastolic parameters derived from STE correlate well with the extent of LA fibrosis. Thus, STE may be useful in the noninvasive assessment of LA fibrosis and selection of candidates for RFCA.
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Fibrilação Atrial/diagnóstico por imagem , Fibrilação Atrial/patologia , Ecocardiografia/métodos , Fibrilação Atrial/sangue , Biomarcadores/sangue , Feminino , Fibrose , Átrios do Coração/diagnóstico por imagem , Átrios do Coração/patologia , Humanos , Masculino , Metaloproteinase 9 da Matriz/sangue , Pessoa de Meia-Idade , Fragmentos de Peptídeos/sangue , Pró-Colágeno/sangue , Estudos Prospectivos , Fator de Crescimento Transformador beta1/sangueRESUMO
INTRODUCTION: Core needle biopsy is a preferable breast biopsy technique under ultrasound guidance. However, fine-needle biopsy is considered equally popular. AIM OF THE STUDY: To redefine the role of fine-needle aspiration biopsy (FNAB) in the diagnosis of breast lesions. MATERIAL AND METHODS: We retrospectively analysed the medical records of 680 patients who underwent breast ultrasound examination. In most cases, no pathologic structures were observed within the mammary glands. In 321 patients, the presence of focal lesions was revealed, and 107 patients in this group qualified for FNAB according to current recommendations. Patients with suspicious smears were referred for core needle or surgical biopsy. Patients with benign cytological smears underwent repeated ultrasound checks at 6-month intervals during the following year. RESULTS: All the smears were diagnostic. The vast majority of the results were categorised as benign lesions. Cancer cells were detected in six women. In one patient the lesion was classified as suspicious, probably malignant. In all of these cases, open biopsy was performed, and histopathological examination confirmed the presence of a malignant tumour. The patients were given appropriate oncological treatment. For women with benign or suspicious, but probably benign, lesions, breast ultrasound was performed twice at six-month intervals. Control tests showed no significant changes compared to the baseline examination. None of the patients required extensive additional diagnostic tests. CONCLUSIONS: FNAB is a reliable method of assessing pathologic lesions in mammary glands.
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The prediction of the lattice constant of binary body centered cubic crystals is performed in terms of first principle calculations and machine learning. In particular, 1541 binary body centered cubic crystals are calculated using density functional theory. Results from first principle calculations, corresponding information from periodic table, and mathematically tailored data are stored as a dataset. Data mining reveals seven descriptors which are key to determining the lattice constant where the contribution of descriptors is also discussed and visualized. Support vector regression (SVR) technique is implemented to train the data where the predicted lattice constants have the mean score of 83.6% accuracy via cross-validation and maximum error of 4% when compared to experimentally determined lattice constants. In addition, trained SVR is successful in predicting material combinations from a desired lattice constant. Thus, a set of descriptors for determining the lattice constant is identified and can be used as a base descriptor for lattice constants of further complex crystals. This would allow for the acceleration of the search for lattice constants of desired atomic compositions as well as the prediction of new materials based on a specified lattice constant.
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BACKGROUND: Antazoline is an old antihistaminic and new antiarrhythmic agent with unknown mechanisms of action which recently has been shown to effectively terminate atrial fibrillation. The aim of study was to examine the effects of antazoline on hemodynamic and ECG parameters. METHODS: Antazoline was given intravenously in three 100 mg boluses to 10 healthy volunteers (four males, mean age 40 + 11 years). Hemodynamic and ECG parameters were measured using impedance cardiography [systolic (sBP), diastolic (dBP), mean (mBP) blood pressure, stroke volume (SV), cardiac output (CO), total peripheral resistance (TPR) and heart rate (HR), P wave, PR interval, QRS complex, QT and corrected QT (QTcF) interval]. Plasma concentration of antazoline was also measured. RESULTS: Antazoline caused significant prolongation of P wave, QRS as well as QT and QTcF (101 ± 10 vs 110 ± 16 ms, p < .05, and 101 ± 12 vs 107 ± 12 ms, p < .05, 399 ± 27 vs 444 ± 23 ms, p < .05, and 403 ± 21 vs 448 ± 27 ms, p < .05, respectively). Also, a significant decrease in SV was noted (94.9 ± 21.8 vs 82.4 ± 19.6 ml, p < .05). A significant correlation between changes in plasma drug concentration and changes in CO, HR, and dBP was found. CONCLUSIONS: Antazoline impairs slightly hemodynamics, significantly reducing SV. Significant prolongation of P wave and QRS duration corresponds to drug-induced prolongation of conduction, whereas QT prolongation represents drug-induced prolongation of repolarization.
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Antazolina/farmacologia , Antiarrítmicos/farmacologia , Eletrocardiografia/efeitos dos fármacos , Hemodinâmica/efeitos dos fármacos , Adulto , Pressão Sanguínea/efeitos dos fármacos , Feminino , Frequência Cardíaca/efeitos dos fármacos , Antagonistas dos Receptores Histamínicos H1/farmacologia , Humanos , Masculino , Valores de Referência , Volume Sistólico/efeitos dos fármacosRESUMO
We investigated the structure of the tungsten bronze barium neodymium titanates Ba(6-3n)Nd(8+2n)Ti(18)O(54), which are exploited as microwave dielectric ceramics. They form a complex nanostructure, which resembles a nanofilm with stacking layers of â¼12 Å thickness. The synthesized samples of Ba(6-3n)Nd(8+2n)Ti(18)O(54) (n = 0, 0.3, 0.4, 0.5) are characterized by pentagonal and tetragonal columns, where the A cations are distributed in three symmetrically inequivalent sites. Synchrotron X-ray diffraction and electron energy loss spectroscopy allowed for quantitative analysis of the site occupancy, which determines the defect distribution. This is corroborated by density functional theory calculations. Pentagonal columns are dominated by Ba, and tetragonal columns are dominated by Nd, although specific Nd sites exhibit significant concentrations of Ba. The data indicated significant elongation of the Ba columns in the pentagonal positions and of the Nd columns in tetragonal positions involving a zigzag arrangement of atoms along the b lattice direction. We found that the preferred Ba substitution occurs at Nd[3]/[4] followed by Nd[2] and Nd[1]/[5] sites, which is significantly different to that proposed in earlier studies. Our results on the Ba(6-3n)Nd(8+2n)Ti(18)O(54) "perovskite" superstructure and its defect distribution are particularly valuable in those applications where the optimization of material properties of oxides is imperative; these include not only microwave ceramics but also thermoelectric materials, where the nanostructure and the distribution of the dopants will reduce the thermal conductivity.
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Bioinspired structures are promising as improved catalysts for various redox reactions. One example is metal hangman-porphyrines (MHP), which recently have been suggested for oxygen reduction/evolution reaction (ORR/OER). The unique properties of the MHPs are attributed to both the hangman scaffold and the C6F5 side groups. Herein, the OER/ORR over various transition metal MHPs is investigated by density functional theory calculations within an electrochemical framework. A comparison of the reaction landscape for MHP, metal porphyrine (MP) and metaltetrafluorophenyloporphyrines (MTFPP), allow for a disentanglement of the different roles of the hangman motif and the side groups. In agreement with experimental studies, it is found that Fe and Co are the best MHP metal centers to catalyze these reactions. We find that the addition of the three-dimensional moiety in the form of hangman scaffold does not break the apparently universal energy relation between *OH and *OOH intermediates. However, the hangman motif is found to stabilize the oxygen intermediate, whereas addition of C6F5 groups reduces the binding energy of all reaction intermediates. Our results indicate that the combination of these two effects allow new design possibilities for macromolecular systems with enhanced catalytic OER/ORR activity.
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A first-principles account of the observed limiting thickness of oxide films formed on aluminum during oxidizing conditions is presented. The results uncover enhanced bonding of oxygen to thin alumina films in contact with metallic aluminum that stems from charge transfer between a reconstructed oxide-metal interface and the adsorbed molecules. The first-principles results are compared with the traditional Cabrera-Mott (CM) model, which is a classical continuum model. Within the CM model, charged surface oxygen species and metal ions generate a (Mott) potential that drives oxidation. An apparent limiting thickness is observed as the oxidation rate decreases rapidly with film growth. The present results support experimental estimates of the Mott potential and film thicknesses. In contrast to the CM model, however, the calculations reveal a real limiting thickness that originates from a diminishing oxygen adsorption energy beyond a certain oxide film thickness.