Manganese Defective Clustering: Influence on the Spectroscopic Features of Ceria-Based Nanomaterials.

The influence of manganese modification on the spectroscopic features of manganese-doped CeO2 systems synthesized by the microwave-assisted hydrothermal route and their correlation with the presence of O defective structures were verified, focusing on their interaction with poisonous atmospheres. Raman and electron paramagnetic resonance studies confirmed the presence of defective clusters formed by dipoles and/or quadrupoles. The number of paramagnetic species was found to be inversely proportional to the doping concentration, resulting in an increase in the Mn2+ signal, likely due to the reduction of Mn3+ species after the interaction with CO. X-ray photoelectron spectroscopy data showed the pure system with 33% of its cerium species in the Ce3+ configuration, with an abrupt decrease to 19%, after the first modification with Mn, suggesting that 14% of the Ce3+ species are donating one electron to the Mn2+ ions, thus becoming nonparamagnetic Ce4+ species. On the contrary, 58% of the manganese species remain in the Mn2+ configuration with five unpaired electrons, corroborating the paramagnetic feature of the samples seen in the electron paramagnetic resonance study.

Assigning F-words as ingredients of interventions for children with cerebral palsy functioning at GMFCS IV and V: A scoping review protocol.

Introduction: Children with Cerebral Palsy (CP) functioning at Gross Motor Function Classification System (GMFCS) levels IV and V require "on time" identification and intervention. Interventions offered continue to be a challenge, in high-, but even more so in middle-, and low-income countries. Aim: To describe the methods developed to explore the ingredients of published studies on early interventions in young children with cerebral palsy (CP) at highest risk of being non-ambulant based on the "F-words for child development framework" and the design of a scoping review exploring these ingredients. Method: An operational procedure was developed through expert panels to identify ingredients of published interventions and related F-words. After sufficient agreement among researchers was reached, a scoping review was designed. The review is registered in the Open Science Framework database. The "Population, Concept and Context" framework was used. Population: young children (0-5 years with CP and at highest risk for being non-ambulant (GMFCS levels IV or V); Concept: non-surgical and non-pharmacological early intervention services measuring outcomes from any ICF domain; Context: studies published from 2001 to 2021. After duplicated screening and selection, data will be extracted and quality will be assessed with the American Academy for Cerebral Palsy and Developmental Medicine (AACPDM) and Mixed Methods Appraisal (MMAT) tools. Results: We present the protocol to identify the explicit (directly measured outcomes and respective ICF domains) and implicit (intervention features not explicitly intended or measured) ingredients. Conclusion: Findings will support the implementation of the F-words in interventions for young children with non-ambulant CP.

Significant enhancement of ferromagnetism above room temperature in epitaxial 2D van der Waals ferromagnet Fe5-δGeTe2/Bi2Te3 heterostructures.

Two-dimensional (2D) van der Waals (vdW) ferromagnetic metals FexGeTe2 with x = 3-5 have raised significant interest in the scientific community. Fe5GeTe2 shows prospects for spintronic applications since the Curie temperature Tc has been reported near or higher than 300 K. In the present work, epitaxial Fe5-δGeTe2 (FGT) heterostructures were grown by Molecular Beam Epitaxy (MBE) on insulating crystalline substrates. The FGT films were combined with Bi2Te3 topological insulator (TI) aiming to investigate the possible beneficial effect of the TI on the magnetic properties of FGT. FGT/Bi2Te3 films were compared to FGT capped only with AlOx to prevent oxidation. SQUID and MOKE measurements revealed that the growth of Bi2Te3 TI on FGT films significantly enhances the saturation magnetization of FGT as well as the Tc well above room temperature (RT) reaching record values of 570 K. First-principles calculations predict a shift of the Fermi level and an associated enhancement of the majority spin (primarily) as well as the total density of states at the Fermi level suggesting that effective doping of FGT from Bi2Te3 could explain the enhancement of ferromagnetism in FGT. It is also predicted that strain induced stabilization of a high magnetic moment phase in FGT/Bi2Te3 could be an alternative explanation of magnetization and Tc enhancement. Ferromagnetic resonance measurements evidence an enhanced broadening in the FGT/Bi2Te3 heterostructure when compared to FGT. We obtain a large spin mixing conductance of g↑↓eff = 4.4 × 1020 m-2, which demonstrates the great potential of FGT/Bi2Te3 systems for spin-charge conversion applications at room temperature.

Correction: Synthesis and evaluation of photocatalytic and photoluminescent properties of Zn2+-doped Bi2WO6.

Correction for 'Synthesis and evaluation of photocatalytic and photoluminescent properties of Zn2+-doped Bi2WO6' by L. X. Lovisa, et al., Dalton Trans., 2022, https://doi.org/10.1039/d2dt03175b.

Synthesis and evaluation of photocatalytic and photoluminescent properties of Zn2+-doped Bi2WO6.

This study consists of the synthesis of zinc-doped Bi2WO6 obtained by the sonochemical method. The XRD results indicated that the samples showed an orthorhombic phase with the P21ab space group without the presence of secondary phases, demonstrating success in the doping process. The results of the photocatalytic tests under the photodegradation of methylene blue showed better performance for the pure sample with 80% degradation during 2 hours of exposure to radiation. The high rate of photogenerated charges accompanied by the low recombination rate of the pairs and e-/h+ were responsible for forming hydroxyl radicals, the predominant oxidative agent of the mechanism. The increase in Zn2+ concentration in the Bi2WO6 matrix promoted inhibition of the photocatalytic properties by the appearance of oxygen vacancies that acted as a charge recombination center. In contrast, photoluminescence was improved by doping with Zn2+. The Bi2WO6:8% Zn2+ sample showed the highest PL intensity. The characteristics of the emitted colors are modulated from the emission spectra and are quantified in terms of the photometric parameters: chromaticity coordinates (x, y), color reproduction index (CRI), luminous radiation efficiency (LER), and purity of color (%) of samples. The adjustment in the colors is promoted as a function of the increase in the Zn2+ concentration observing the transition from: yellow → orange → green. PL is favored by the effect of the dopant (Zn2+) in the matrix, which allows Bi2WO6:Zn2+ to be considered a promising candidate for applications in optical devices. In addition, Bi2WO6 constitutes a high performance photocatalyst for the degradation of methylene blue.

Magnetotransport and ARPES studies of the topological insulators Sb2Te3 and Bi2Te3 grown by MOCVD on large-area Si substrates.

Recently, the topological insulators (TIs) antimony telluride (Sb2Te3) and bismuth telluride (Bi2Te3) are attracting high interest for applications based on spin-charge interconversion mechanisms. Aiming to make a step toward the technology transfer, it is of major importance to achieve and investigate epitaxial quality-TIs on large area Si-based substrates. In view of that, we report here magnetotransport and angle-resolved photoemission spectroscopy (ARPES) studies on Sb2Te3 and Bi2Te3 thin films grown by metal organic chemical vapor deposition (MOCVD) on top of 4″ Si(111) substrates. Clear weak antilocalization (WAL) effects are observed in both TIs, proving the existence of quantum transport mechanism, and the data are successfully interpreted in the framework of the Hikami-Larkin-Nagaoka model. Further, by dedicated magnetotransport experiments, it has been confirmed that the investigated WAL originates from two-dimensional (2D) topological states. ARPES has been performed ex-situ, and in both TIs the gapless Dirac cones have been observed and attributed to the topological surface states. Combining the proofs of the existence of quantum 2D transport as deduced from the analysis of the magnetoconductance curve with the direct observation of the Dirac-like band structure revealed by the ARPES spectra, it is possible to unambiguously confirm the topological nature of our Sb2Te3 and Bi2Te3 thin films. The results obtained on thin films grown by MOCVD on 4'' Si(111) substrate mark an important step towards the technology transfer of the topological insulators studied in this work.

Synthesis and defect characterization of hybrid ceria nanostructures as a possible novel therapeutic material towards COVID-19 mitigation.

This study reports the synthesis of hybrid nanostructures composed of cerium dioxide and microcrystalline cellulose prepared by the microwave-assisted hydrothermal route under distinct temperature and pH values. Their structural, morphological and spectroscopic behaviors were investigated by X-Rays Diffraction, Field Emission Gun Scanning Electron Microscopy, High-Resolution Transmission Electron Microscopy, and Fourier-Transform Infrared, Ultraviolet-Visible, Raman and Positron Annihilation Lifetime spectroscopies to evaluate the presence of structural defects and their correlation with the underlying mechanism regarding the biocide activity of the studied material. The samples showed mean crystallite sizes around 10 nm, characterizing the formation of quantum dots unevenly distributed along the cellulose surface with a certain agglomeration degree. The samples presented the characteristic Ce-O vibration close to 450 cm-1 and a second-order mode around 1050 cm-1, which is indicative of distribution of localized energetic levels originated from defective species, essential in the scavenging of reactive oxygen species. Positron spectroscopic studies showed first and second lifetime components ranging between 202-223 ps and 360-373 ps, respectively, revealing the presence of two distinct defective oxygen species, in addition to an increment in the concentration of Ce3+-oxygen vacancy associates as a function of temperature. Therefore, we have successfully synthesized hybrid nanoceria structures with potential multifunctional therapeutic properties to be further evaluated against the COVID-19.

Knowledge translation in rehabilitation settings in low, lower-middle and upper-middle-income countries: a scoping review.

PURPOSE: This review aims to identify the barriers and facilitators to knowledge use and Knowledge Translation (KT) strategies in rehabilitation in low, lower-middle, and upper-middle-income countries (LMICs). MATERIALS AND METHODS: A scoping review of studies of KT in rehabilitation in LMICs contexts using the Arksey and O'Malley Framework was conducted. A comprehensive search of MEDLINE and 10 other databases was undertaken to identify studies conducted primarily in LMICs. RESULTS: From the initial 15.606 titles identified; 27 articles were included for final analysis. Our analysis identified the following themes: Professional culture and context; KT interventions; and the conceptualization and application of KT and Evidence Based Practice (EBP). Individual-level barriers to KT included lack of skills, knowledge about EBP and English language, lack of motivation, and decision-making power. Facilitators to KT included positive attitudes and motivation. Organization-level barriers included lack of time, lack of financial resources, limited access to scientific journals, and applicability of research to rural settings. Facilitators included adequate financial and physical resources, a supportive management environment, and the existence of training and continuing education programs. CONCLUSION: This review identified common and unique barriers and facilitators to KT in LMICs when compared to KT studies conducted in high-income settings.IMPLICATIONS FOR REHABILITATIONKnowledge Translation from academic institutions to rehabilitation clinical practice in low and upper-middle-income countries is important to support evidence-based practice and patient outcomes.Barriers at the individual level include professionals' ability to understand English and knowledge of the evidence-based practice.Organization-level barriers included lack of time to access and implement new practices, lack of financial and personal resources, limited access to scientific journals, and applicability of research to rural settings.Training and continuing education programs are needed to support rehabilitation professionals' efforts to achieve the application of evidence-based practice in clinical practice.

Placental magnetic resonance imaging: normal appearance, anatomical variations, and pathological findings.

Placental magnetic resonance imaging (MRI) has been increasingly requested, especially for the evaluation of suspected cases of placental adhesive disorders, generally known as placenta accreta. Abdominal radiologists need to become familiar with normal placental anatomy, anatomical variations, the current terminology, and major placental diseases that, although rare, are important causes of maternal and fetal morbidity and mortality. The aim of this didactic pictorial essay is to illustrate various findings on placental MRI, as well as to emphasize the importance of communication between radiologists and obstetricians in the search for best practices in the management of the affected patients.

A ressonância magnética placentária tem sido cada vez mais solicitada, sobretudo na avaliação de casos suspeitos de acretismo. Os radiologistas abdominais precisam se familiarizar com a anatomia placentária normal, variações anatômicas, terminologias atuais e principais doenças placentárias que, embora raras, são causas importantes de morbimortalidade materno-fetal. O objetivo deste ensaio é ilustrar, de maneira didática, diferentes achados placentários e enfatizar a importância da comunicação entre radiologistas e obstetras na busca da melhor conduta para as pacientes.

Placental magnetic resonance imaging: normal appearance, anatomical variations, and pathological findings / Ressonância magnética placentária: aspecto normal, variações anatômicas e achados patológicos

Abstract Placental magnetic resonance imaging (MRI) has been increasingly requested, especially for the evaluation of suspected cases of placental adhesive disorders, generally known as placenta accreta. Abdominal radiologists need to become familiar with normal placental anatomy, anatomical variations, the current terminology, and major placental diseases that, although rare, are important causes of maternal and fetal morbidity and mortality. The aim of this didactic pictorial essay is to illustrate various findings on placental MRI, as well as to emphasize the importance of communication between radiologists and obstetricians in the search for best practices in the management of the affected patients.

Resumo A ressonância magnética placentária tem sido cada vez mais solicitada, sobretudo na avaliação de casos suspeitos de acretismo. Os radiologistas abdominais precisam se familiarizar com a anatomia placentária normal, variações anatômicas, terminologias atuais e principais doenças placentárias que, embora raras, são causas importantes de morbimortalidade materno-fetal. O objetivo deste ensaio é ilustrar, de maneira didática, diferentes achados placentários e enfatizar a importância da comunicação entre radiologistas e obstetras na busca da melhor conduta para as pacientes.

Structure, electronic properties, morphology evolution, and photocatalytic activity in PbMoO4 and Pb1-2xCaxSrxMoO4 (x = 0.1, 0.2, 0.3, 0.4 and 0.5) solid solutions.

In this work PbMoO4 and Pb1-2xCaxSrxMoO4 (x = 0.1, 0.2, 0.3, 0.4 and 0.5) solid solutions have been successfully prepared, for the first time, by a simple co-precipitation method and the as-synthesized samples were subjected to a water-based reflux treatment. Structural characterization of these samples was performed using X-ray diffraction with Rietveld refinement analysis and Raman spectroscopy. Their optical properties were investigated by UV-Vis absorption spectroscopy and PL emissions, and the photocatalytic activity of the as-synthesized samples for the degradation process of Rhodamine B has been demonstrated. The surface structure and morphologies were characterized by field emission scanning electron microscopy. To complement and rationalize the experimental results, the geometry, electronic structures, and morphologies of as-synthesized samples were characterized by first-principles quantum-mechanical calculations at the density functional theory level. By using Wulff construction, based on the values of the surface energies for the (001), (100), (110), (111), (011) and (112) surfaces, a complete map of the available morphologies for PbMoO4 was obtained and a good agreement between the experimental and theoretical predicted morphologies was found. The structural and electronic changes induced by the substitution of Pb by Ca and Sr allow us to find a relationship among morphology, the electron-transfer process at the exposed surfaces, optical properties, and photocatalytic activity. We believe that our results offer new insights regarding the local coordination of superficial Pb/Ca/Sr and Mo cations (i.e., clusters) on each exposed surface of the corresponding morphology, which dictate the photocatalytic activities of the as-synthesized samples, a field that has so far remained unexplored. The present study, which combines multiple experimental methods and first-principles calculations, provides a deep understanding of the local structures, bonding, morphologies, band gaps, and electronic and optical properties, and opens the door to exploit the electrical, optical and photocatalytic activity of this very promising family of materials.

X-ray Zernike phase contrast tomography: 3D ROI visualization of mm-sized mice organ tissues down to sub-cellular components.

Thanks to its non-invasive nature, X-ray phase contrast tomography is a very versatile imaging tool for biomedical studies. In contrast, histology is a well-established method, though having its limitations: it requires extensive sample preparation and it is quite time consuming. Therefore, the development of nano-imaging techniques for studying anatomic details at the cellular level is gaining more and more importance. In this article, full field transmission X-ray nanotomography is used in combination with Zernike phase contrast to image millimeter sized unstained tissue samples at high spatial resolution. The regions of interest (ROI) scans of different tissues were obtained from mouse kidney, spleen and mammalian carcinoma. Thanks to the relatively large field of view and effective pixel sizes down to 36 nm, this 3D approach enabled the visualization of the specific morphology of each tissue type without staining or complex sample preparation. As a proof of concept technique, we show that the high-quality images even permitted the 3D segmentation of multiple structures down to a sub-cellular level. Using stitching techniques, volumes larger than the field of view are accessible. This method can lead to a deeper understanding of the organs' nano-anatomy, filling the resolution gap between histology and transmission electron microscopy.

Influence of elastase on alanine-rich peptide hydrogels.

The self-assembly of the alanine-rich amphiphilic peptides Lys(Ala)6Lys (KA6K) and Lys(Ala)6Glu (KA6E) with homotelechelic or heterotelechelic charged termini respectively has been investigated in aqueous solution. These peptides contain hexa-alanine sequences designed to serve as substrates for the enzyme elastase. Electrostatic repulsion of the lysine termini in KA6K prevents self-assembly, whereas in contrast KA6E is observed, through electron microscopy, to form tape-like fibrils, which based on X-ray scattering contain layers of thickness equal to the molecular length. The alanine residues enable efficient packing of the side-chains in a beta-sheet structure, as revealed by circular dichroism, FTIR and X-ray diffraction experiments. In buffer, KA6E is able to form hydrogels at sufficiently high concentration. These were used as substrates for elastase, and enzyme-induced de-gelation was observed due to the disruption of the beta-sheet fibrillar network. We propose that hydrogels of the simple designed amphiphilic peptide KA6E may serve as model substrates for elastase and this could ultimately lead to applications in biomedicine and regenerative medicine.

Ag Nanoparticles/α-Ag2WO4 Composite Formed by Electron Beam and Femtosecond Irradiation as Potent Antifungal and Antitumor Agents.

The ability to manipulate the structure and function of promising systems via external stimuli is emerging with the development of reconfigurable and programmable multifunctional materials. Increasing antifungal and antitumor activity requires novel, effective treatments to be diligently sought. In this work, the synthesis, characterization, and in vitro biological screening of pure α-Ag2WO4, irradiated with electrons and with non-focused and focused femtosecond laser beams are reported. We demonstrate, for the first time, that Ag nanoparticles/α-Ag2WO4 composite displays potent antifungal and antitumor activity. This composite had an extreme low inhibition concentration against Candida albicans, cause the modulation of α-Ag2WO4 perform the fungicidal activity more efficient. For tumor activity, it was found that the composite showed a high selectivity against the cancer cells (MB49), thus depleting the populations of cancer cells by necrosis and apoptosis, without the healthy cells (BALB/3T3) being affected.

Fast and simultaneous doping of Sr0.9-x-y-zCa0.1In2O4:(xEu3+, yTm3+, zTb3+) superstructure by ultrasonic spray pyrolysis.

In the present work, Sr0.9-x-y-zCa0.1In2O4:(xEu3+, yTm3+, zTb3+) particles were synthesized by the ultrasonic spray pyrolysis (USP) method to obtain a single-phase white phosphorus formed by six different cations in solution within the lattice (superstructure). The samples were also structurally and morphologically characterized by X-ray diffraction (XRD) techniques and by field emission scanning electron microscopy (FE-SEM). The photoluminescent behavior and the characteristics of the emitted colors were studied by the variation in the co-doping of the rare earth elements. The Sr0.9Ca0.1In2O4 sample showed a near blue color emission, but all co-doped samples showed emission in white with very close chromaticity coordinates to the standard white (x = 0.33 and y = 0.33). The Tm3+ → Tb3+ (ET1), Tm3+ → Eu3+ (ET2) and Tb3+ → Eu3+ (ET3) Energy Transfers were proposed and are considered necessary for adjusting and controlling the desired color properties.

A DFT investigation of the role of oxygen vacancies on the structural, electronic and magnetic properties of ATiO3 (A = Mn, Fe, Ni) multiferroic materials.

In order to achieve deep insight into the multiferroic behavior and electronic properties of intrinsic oxygen vacancies in ATiO3 (A = Mn, Fe, Ni), first-principles calculations based on hybrid density functional theory were carried out for bulk and non-polar (110) surface models. We found that the formation of an oxygen vacancy is accompanied by structural and electronic disorders in the constituent clusters of [TiO6] and [AO6] in ATiO3, that become [TiO5] and [AO5], respectively. This perturbation contributes to the generation of intermediary energy levels in the band gap region, thus narrowing the required excitation energy. In addition, the remaining electrons are mainly trapped in the empty 3d orbitals of the Ti cations neighboring the oxygen vacancy, generating [TiO5]' (3d1) that mediates an antiferromagnetic to ferromagnetic transition in MnTiO3 and FeTiO3 materials. In particular, MnTiO3 surfaces show exposed [TiO4]' species that are responsible for its half-metallic behavior. The present work provides compelling evidence that controlling oxygen vacancies can be a valuable strategy to tailor the multiferroic properties of ATiO3 materials.