Structural characterization of vanadium oxide catalysts supported on nanostructured silica SBA-15 using X-ray absorption spectroscopy

The local structure of vanadium oxide supported on nanostructured SiO2 (VxOy/SBA-15) was investigated by in situ X-ray absorption spectroscopy (XAS). Because the number of potential parameters in XAS data analysis often exceeds the number of "independent" parameters, evaluating the reliability and significance of a particular fitting procedure is mandatory. The number of independent parameters (Nyquist) may not be sufficient. Hence, in addition to the number of independent parameters, a novel approach to evaluate the significance of structural fitting parameters in XAS data analysis is introduced. Three samples with different V loadings (i.e. 2.7 wt %, 5.4 wt %, and 10.8 wt %) were employed. Thermal treatment in air at 623 K resulted in characteristic structural changes of the V oxide species. Independent of the V loading, the local structure around V centers in dehydrated VxOy/SBA-15 corresponded to an ordered arrangement of adjacent V2O7 units. Moreover, the V2O7 units were found to persist under selective oxidation reaction conditions

The challenge of acute-stroke management: does telemedicine offer a solution?

<p><b>Background:</b> Several studies have described successful experiences with the use of telemedicine in acute stroke. The objective of this study was to assess the feasibility, acceptability, and treatment delivery reliability, of telemedicine systems for the clinical and radiological assessment, and management of acute-stroke patients.</p> <p><b>Summary of Review:</b> A systematic review of the literature was carried out. Studies were included if they met the following criteria: (1) study population included participants with a diagnosis of suspected acute stroke, (2) intervention included the use of telemedicine systems to aid assessment, diagnosis, or treatment in acute stroke, and (3) outcomes measured related to feasibility in clinical practice, acceptability to patients, carers, and staff, reliability of telemedicine systems, and effectiveness in delivering treatment, especially tissue plasminogen activator (tPA). Overall, 17 relevant non-randomised studies reported that telemedicine systems were feasible and acceptable. Interrater reliability was excellent for global clinical assessments and decisions on radiological exclusion criteria although agreement for individual assessment items was more variable. Telemedicine systems were associated with increased use of tPA.</p> <p><b>Conclusion:</b> Although there is limited reliable evidence, observational studies have indicated that telemedicine systems can be feasible, acceptable, and reliable in acute-stroke management. In addition, telemedicine consultations were associated with improved delivery of tPA.</p&gt

Topological inversions in coalescing granular media control fluid-flow regimes

Sintering—or coalescence—of viscous droplets is an essential process in many natural and industrial scenarios. Current physical models of the dynamics of sintering are limited by the lack of an explicit account of the evolution of microstructural geometry. Here, we use high-speed time-resolved x-ray tomography to image the evolving geometry of a sintering system of viscous droplets, and use lattice Boltzmann simulations of creeping fluid flow through the reconstructed pore space to determine its permeability. We identify and characterize a topological inversion, from spherical droplets in a continuous interstitial gas, to isolated bubbles in a continuous liquid. We find that the topological inversion is associated with a transition in permeability-porosity behavior, from Stokes permeability at high porosity, to percolation theory at low porosity. We use these findings to construct a unified physical description that reconciles previously incompatible models for the evolution of porosity and permeability during sintering

Process-based classification of Mediterranean cyclones using potential vorticity

This is the final version. Available on open access from Copernicus Publications via the DOI in this recordCode availability:The code for the SOM classification algorithm is openly available at https://www.mathworks.com/help/deeplearning/gs/cluster-data-with-a-self-organizingmap.html (last access: 29 January 2024).Data availability: The composite cyclone tracks with the resulting cluster attribution are available in the supplementary assets of this paper. The track labels correspond to the composite cyclone track dataset at confidence level 5, made available as a Supplement by Flaounas et al. (2023) (“TRACKS_CL5.dat”).Mediterranean cyclones (MCs) govern extreme weather events across the Euro-African Basin, affecting the lives of hundreds of millions. Despite many studies addressing MCs in the last few decades, their correct simulation and prediction remain a significant challenge to the present day, which may be attributed to the large variability among MCs. Past classifications of MCs are primarily based on geographical and/or seasonal separations; however, here we focus on cyclone genesis and deepening mechanisms. A variety of processes combine to govern MC genesis and evolution, including adiabatic and diabatic processes, topographic influences, land-sea contrasts, and local temperature anomalies. As each process bears a distinct signature on the potential vorticity (PV) field, a PV approach is used to distinguish among different "types"of MCs. Here, a combined cyclone-tracking algorithm is used to detect 3190 Mediterranean cyclone tracks in ECMWF ERA5 from 1979-2020. Cyclone-centered, upper-level isentropic PV structures in the peak time of each cyclone track are classified using a self-organizing map (SOM). The SOM analysis reveals nine classes of Mediterranean cyclones, with distinct Rossby-wave-breaking patterns, discernible in corresponding PV structures. Although classified by upper-level PV structures, each class shows different contributions of lower-tropospheric PV and flow structures down to the surface. Unique cyclone life cycle characteristics, associated hazards (precipitation, winds, and temperature anomalies), and long-term trends, as well as synoptic, thermal, dynamical, seasonal, and geographical features of each cyclone class, indicate dominant processes in their evolution. Among others, the classification reveals the importance of topographically induced Rossby wave breaking to the generation of the most extreme Mediterranean cyclones. These results enhance our understanding of MC predictability by linking the large-scale Rossby wave formations and life cycles to coherent classes of under-predicted cyclone aspects.de Botton Center for Marine ScienceIsraeli Council for Higher Education (CHE)Weizmann Data Science Research CenterWeizmann Institute Sustainability and Energy Research Initiative (SAERI

Sequential decoupling of negative-energy states in Douglas-Kroll-Hess theory

Here, we review the historical development, current status, and prospects of Douglas--Kroll--Hess theory as a quantum chemical relativistic electrons-only theory.Comment: 15 page

Exploring out-of-equilibrium quantum magnetism and thermalization in a spin-3 many-body dipolar lattice system

Understanding quantum thermalization through entanglement build-up in isolated quantum systems addresses fundamental questions on how unitary dynamics connects to statistical physics. Here, we study the spin dynamics and approach towards local thermal equilibrium of a macroscopic ensemble of S = 3 spins prepared in a pure coherent spin state, tilted compared to the magnetic field, under the effect of magnetic dipole-dipole interactions. The experiment uses a unit filled array of 104 chromium atoms in a three dimensional optical lattice, realizing the spin-3 XXZ Heisenberg model. The buildup of quantum correlation during the dynamics, especially as the angle approaches pi/2, is supported by comparison with an improved numerical quantum phase-space method and further confirmed by the observation that our isolated system thermalizes under its own dynamics, reaching a steady state consistent with the one extracted from a thermal ensemble with a temperature dictated from the system's energy. This indicates a scenario of quantum thermalization which is tied to the growth of entanglement entropy. Although direct experimental measurements of the Renyi entropy in our macroscopic system are unfeasible, the excellent agreement with the theory, which can compute this entropy, does indicate entanglement build-up.Comment: 12 figure

Acidic microenvironment plays a key role in human melanoma progression through a sustained exosome mediated transfer of clinically relevant metastatic molecules

Background: Microenvironment cues involved in melanoma progression are largely unknown. Melanoma is highly influenced in its aggressive phenotype by the changes it determinates in its microenvironment, such as pH decrease, in turn influencing cancer cell invasiveness, progression and tissue remodelling through an abundant secretion of exosomes, dictating cancer strategy to the whole host. A role of exosomes in driving melanoma progression under microenvironmental acidity was never described. Methods: We studied four differently staged human melanoma lines, reflecting melanoma progression, under microenvironmental acidic pHs pressure ranging between pH 6.0-6.7. To estimate exosome secretion as a function of tumor stage and environmental pH, we applied a technique to generate native fluorescent exosomes characterized by vesicles integrity, size, density, markers expression, and quantifiable by direct FACS analysis. Functional roles of exosomes were tested in migration and invasion tests. Then we performed a comparative proteomic analysis of acid versus control exosomes to elucidate a specific signature involved in melanoma progression. Results: We found that metastatic melanoma secretes a higher exosome amount than primary melanoma, and that acidic pH increases exosome secretion when melanoma is in an intermediate stage, i.e. metastatic non-invasive. We were thus able to show that acidic pH influences the intercellular cross-talk mediated by exosomes. In fact when exposed to exosomes produced in an acidic medium, pH naïve melanoma cells acquire migratory and invasive capacities likely due to transfer of metastatic exosomal proteins, favoring cell motility and angiogenesis. A Prognoscan-based meta-analysis study of proteins enriched in acidic exosomes, identified 11 genes (HRAS, GANAB, CFL2, HSP90B1, HSP90AB1, GSN, HSPA1L, NRAS, HSPA5, TIMP3, HYOU1), significantly correlating with poor prognosis, whose high expression was in part confirmed in bioptic samples of lymph node metastases. Conclusions: A crucial step of melanoma progression does occur at melanoma intermediate -stage, when extracellular acidic pH induces an abundant release and intra-tumoral uptake of exosomes. Such exosomes are endowed with pro-invasive molecules of clinical relevance, which may provide a signature of melanoma advancement

An exact expression to calculate the derivatives of position-dependent observables in molecular simulations with flexible constraints

In this work, we introduce an algorithm to compute the derivatives of physical observables along the constrained subspace when flexible constraints are imposed on the system (i.e., constraints in which the hard coordinates are fixed to configuration-dependent values). The presented scheme is exact, it does not contain any tunable parameter, and it only requires the calculation and inversion of a sub-block of the Hessian matrix of second derivatives of the function through which the constraints are defined. We also present a practical application to the case in which the sought observables are the Euclidean coordinates of complex molecular systems, and the function whose minimization defines the constraints is the potential energy. Finally, and in order to validate the method, which, as far as we are aware, is the first of its kind in the literature, we compare it to the natural and straightforward finite-differences approach in three molecules of biological relevance: methanol, N-methyl-acetamide and a tri-glycine peptideComment: 13 pages, 8 figures, published versio

Inhalation Therapy in Patients Receiving Mechanical Ventilation: An Update

Incremental gains in understanding the influence of various factors on aerosol delivery in concert with technological advancements over the past 2 decades have fueled an ever burgeoning literature on aerosol therapy during mechanical ventilation. In-line use of pressurized metered-dose inhalers (pMDIs) and nebulizers is influenced by a host of factors, some of which are unique to ventilator-supported patients. This article reviews the impact of various factors on aerosol delivery with pMDIs and nebulizers, and elucidates the correlation between in-vitro estimates and in-vivo measurement of aerosol deposition in the lung. Aerosolized bronchodilator therapy with pMDIs and nebulizers is commonly employed in intensive care units (ICUs), and bronchodilators are among the most frequently used therapies in mechanically ventilated patients. The use of inhaled bronchodilators is not restricted to mechanically ventilated patients with chronic obstructive pulmonary disease (COPD) and asthma, as they are routinely employed in other ventilator-dependent patients without confirmed airflow obstruction. The efficacy and safety of bronchodilator therapy has generated a great deal of interest in employing other inhaled therapies, such as surfactant, antibiotics, prostacyclins, diuretics, anticoagulants and mucoactive agents, among others, in attempts to improve outcomes in critically ill ICU patients receiving mechanical ventilation