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.

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.

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.

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.

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.

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.

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.

ZnWO4 nanocrystals: synthesis, morphology, photoluminescence and photocatalytic properties.

The present joint experimental and theoretical work provides in-depth understanding on the morphology and structural, electronic, and optical properties of ZnWO4 nanocrystals. Monoclinic ZnWO4 nanocrystals were prepared at three different temperatures (140, 150, and 160 °C) by a microwave hydrothermal method. Then, the samples were investigated by X-ray diffraction with Rietveld refinement analysis, field-emission scanning electron microscopy, transmission electronic microscopy, micro-Raman and Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and photoluminescence measurements. First-principles theoretical calculations within the framework of density functional theory were employed to provide information at the atomic level. The band structure diagram, density of states, Raman and infrared spectra were calculated to understand the effect of structural order-disorder on the properties of ZnWO4. The effects of the synthesis temperature on the above properties were rationalized. The band structure revealed direct allowed transitions between the VB and CB and the experimental results in the ultraviolet-visible region were consistent with the theoretical results. Moreover, the surface calculations allowed the association of the surface energy stabilization with the temperature used in the synthesis of the ZnWO4 nanocrystals. The photoluminescence properties of the ZnWO4 nanocrystals prepared at 140, 150, and 160 °C were attributed to oxygen vacancies in the [WO6] and [ZnO6] clusters, causing a red shift of the spectra. The ZnWO4 nanocrystals obtained at 160 °C exhibited excellent photodegradation of Rhodamine under ultraviolet light irradiation, which was found to be related to the surface energy and the types of clusters formed on the surface of the catalyst.

Structural evolution, growth mechanism and photoluminescence properties of CuWO4 nanocrystals.

Copper tungstate (CuWO4) crystals were synthesized by the sonochemistry (SC) method, and then, heat treated in a conventional furnace at different temperatures for 1h. The structural evolution, growth mechanism and photoluminescence (PL) properties of these crystals were thoroughly investigated. X-ray diffraction patterns, micro-Raman spectra and Fourier transformed infrared spectra indicated that crystals heat treated and 100°C and 200°C have water molecules in their lattice (copper tungstate dihydrate (CuWO4·2H2O) with monoclinic structure), when the crystals are calcinated at 300°C have the presence of two phase (CuWO4·2H2O and CuWO4), while the others heat treated at 400°C and 500°C have a single CuWO4 triclinic structure. Field emission scanning electron microscopy revealed a change in the morphological features of these crystals with the increase of the heat treatment temperature. Transmission electron microscopy (TEM), high resolution-TEM images and selected area electron diffraction were employed to examine the shape, size and structure of these crystals. Ultraviolet-Visible spectra evidenced a decrease of band gap values with the increase of the temperature, which were correlated with the reduction of intermediary energy levels within the band gap. The intense photoluminescence (PL) emission was detected for the sample heat treat at 300°C for 1h, which have a mixture of CuWO4·2H2O and CuWO4 phases. Therefore, there is a synergic effect between the intermediary energy levels arising from these two phases during the electronic transitions responsible for PL emissions.

Microwave-assisted hydrothermal synthesis of Ag2(W(1-x)Mox)O4 heterostructures: Nucleation of Ag, morphology, and photoluminescence properties.

Ag2W(1-x)MoxO4 (x=0.0 and 0.50) powders were synthesized by the co-precipitation (drop-by-drop) method and processed using a microwave-assisted hydrothermal method. We report the real-time in situ formation and growth of Ag filaments on the Ag2W(1-x)MoxO4 crystals using an accelerated electron beam under high vacuum. Various techniques were used to evaluate the influence of the network-former substitution on the structural and optical properties, including photoluminescence (PL) emission, of these materials. X-ray diffraction results confirmed the phases obtained by the synthesis methods. Raman spectroscopy revealed significant changes in local order-disorder as a function of the network-former substitution. Field-emission scanning electron microscopy was used to determine the shape as well as dimensions of the Ag2W(1-x)MoxO4 heterostructures. The PL spectra showed that the PL-emission intensities of Ag2W(1-x)MoxO4 were greater than those of pure Ag2WO4, probably because of the increase of intermediary energy levels within the band gap of the Ag2W(1-x)MoxO4 heterostructures, as evidenced by the decrease in the band-gap values measured by ultraviolet-visible spectroscopy.

Synthesis and characterization of metastable ß-Ag2WO4: an experimental and theoretical approach.

Metastable silver tungstate (ß-Ag2WO4) has attracted much attention lately because of its many potential applications. However, the synthesis of metastable phases of inorganic compounds is challenging because of the ease of transformation to the stable phase. We have overcome this challenge and have successfully synthesized ß-Ag2WO4 microcrystals using a dropwise precipitation (DP) method in aqueous media at low temperature. The microcrystals were characterized by X-ray diffraction (XRD), including powder X-ray diffraction structural determination, field-emission scanning electron microscopy (FE-SEM), and micro-Raman/ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy. To complement the experimental data, we present first-principles quantum-mechanical density functional theory (DFT) calculations. Using XRD data, Raman/UV-vis data, and the determined optical band gap, together with geometric optimization calculations, we confirmed the structure of this compound. ß-Ag2WO4 has a hexagonal structure with a P63/m space group. The building blocks of the lattice comprise two types of W-O clusters, [WO4] and [WO5], coordinated to four and five O atoms, respectively, and two types of Ag-O clusters, [AgO6], and [AgO5], linked to six and five O atoms, respectively. This type of fundamental study, combining multiple experimental methods and first-principles calculations, helps to obtain a basic understanding of the local structure and bonding in the material.

Scaling like behaviour of resistivity observed in LaNiO3 thin films grown on SrTiO3 substrate by pulsed laser deposition.

We discuss the origin of the temperature dependence of resistivity ρ observed in highly oriented LaNiO3 thin films grown on SrTiO3 substrate by a pulsed laser deposition technique. All the experimental data are found to collapse into a single universal curve ρ(T, d) ∝ [T/T(sf)(d)]3/2 for the entire temperature interval (20K

Monitoring a CuO gas sensor at work: an advanced in situ X-ray absorption spectroscopy study.

X-ray absorption near edge structure (XANES) and electrical measurements were used to elucidate the local structure and electronic changes of copper(II) oxide (CuO) nanostructures under working conditions. For this purpose, a sample holder layout was developed enabling the simultaneous analysis of the spectroscopic and electrical properties of the sensor material under identical operating conditions. The influence of different carrier gases (e.g., air and N2) on the CuO nanostructures behavior under reducing conditions (H2 gas) was studied to analyze how a particular gas atmosphere can modify the oxidation state of the sensor material in real time.

Metronomic chemotherapy in the neoadjuvant setting: results of two parallel feasibility trials (TraQme and TAME) in patients with HER2+ and HER2− locally advanced breast cancer

Neoadjuvant chemotherapy has practical and theoretical advantages over adjuvant chemotherapy strategy in breast cancer (BC) management. Moreover, metronomic delivery has a more favorable toxicity profile. The present study examined the feasibility of neoadjuvant metronomic chemotherapy in two cohorts [HER2+ (TraQme) and HER2− (TAME)] of locally advanced BC. Twenty patients were prospectively enrolled (TraQme, n=9; TAME, n=11). Both cohorts received weekly paclitaxel at 100 mg/m2 during 8 weeks followed by weekly doxorubicin at 24 mg/m2 for 9 weeks in combination with oral cyclophosphamide at 100 mg/day (fixed dose). The HER2+ cohort received weekly trastuzumab. The study was interrupted because of safety issues. Thirty-six percent of patients in the TAME cohort and all patients from the TraQme cohort had stage III BC. Of note, 33% from the TraQme cohort and 66% from the TAME cohort displayed hormone receptor positivity in tumor tissue. The pathological complete response rates were 55% and 18% among patients enrolled in the TraQme and TAME cohorts, respectively. Patients in the TraQme cohort had more advanced BC stages at diagnosis, higher-grade pathological classification, and more tumors lacking hormone receptor expression, compared to the TAME cohort. The toxicity profile was also different. Two patients in the TraQme cohort developed pneumonitis, and in the TAME cohort we observed more hematological toxicity and hand-foot syndrome. The neoadjuvant metronomic chemotherapy regimen evaluated in this trial was highly effective in achieving a tumor response, especially in the HER2+ cohort. Pneumonitis was a serious, unexpected adverse event observed in this group. Further larger and randomized trials are warranted to evaluate the association between metronomic chemotherapy and trastuzumab treatment.

Metronomic chemotherapy in the neoadjuvant setting: results of two parallel feasibility trials (TraQme and TAME) in patients with HER2+ and HER2- locally advanced breast cancer.

Neoadjuvant chemotherapy has practical and theoretical advantages over adjuvant chemotherapy strategy in breast cancer (BC) management. Moreover, metronomic delivery has a more favorable toxicity profile. The present study examined the feasibility of neoadjuvant metronomic chemotherapy in two cohorts [HER2+ (TraQme) and HER2- (TAME)] of locally advanced BC. Twenty patients were prospectively enrolled (TraQme, n=9; TAME, n=11). Both cohorts received weekly paclitaxel at 100 mg/m(2) during 8 weeks followed by weekly doxorubicin at 24 mg/m(2) for 9 weeks in combination with oral cyclophosphamide at 100 mg/day (fixed dose). The HER2+ cohort received weekly trastuzumab. The study was interrupted because of safety issues. Thirty-six percent of patients in the TAME cohort and all patients from the TraQme cohort had stage III BC. Of note, 33% from the TraQme cohort and 66% from the TAME cohort displayed hormone receptor positivity in tumor tissue. The pathological complete response rates were 55% and 18% among patients enrolled in the TraQme and TAME cohorts, respectively. Patients in the TraQme cohort had more advanced BC stages at diagnosis, higher-grade pathological classification, and more tumors lacking hormone receptor expression, compared to the TAME cohort. The toxicity profile was also different. Two patients in the TraQme cohort developed pneumonitis, and in the TAME cohort we observed more hematological toxicity and hand-foot syndrome. The neoadjuvant metronomic chemotherapy regimen evaluated in this trial was highly effective in achieving a tumor response, especially in the HER2+ cohort. Pneumonitis was a serious, unexpected adverse event observed in this group. Further larger and randomized trials are warranted to evaluate the association between metronomic chemotherapy and trastuzumab treatment.

A relationship between structural and electronic order-disorder effects and optical properties in crystalline TiO2 nanomaterials.

The focus of this paper is on the analysis of the structural and electronic order-disorder effects at long, medium and short ranges of titanium dioxide (TiO2) nanoparticles synthesized by the sol-gel process followed by the microwave-assisted solvothermal (MAS) method at low temperatures and short reaction times. X-ray diffraction (XRD), Rietveld refinement, micro-Raman (MR) spectroscopy, transmission electron microscopy (TEM) and X-ray spectroscopy (EDX) were used to characterize the TiO2 nanoparticles. Optical properties were investigated by ultraviolet-visible (UV-vis) and photoluminescence (PL) measurements performed at room temperature. XRD and Rietveld refinement confirmed the presence of the anatase and brookite phases; nonetheless anatase is the major phase. The X-ray photoelectron spectroscopy (XPS) analysis revealed the presence of only Ti(4+) but the nonstoichiometry revealed that TiO2 NPs contain defects assigned to oxygen vacancies that lead to structural and electronic order-disorder effects observed by band gap narrowing and PL wide band emission. These intermediary energy levels (shallow and deep levels) created within the band gap act as acceptors/donors of electrons and recombination centers. The oxygen vacancies (VO(x), VO˙ and VO˙˙) responsible by degree of structural order-disorder are related to distortions (tilts) on the [TiO6] octahedron and changes in the bond lengths and bond angles between oxygen and titanium atoms that gave rise to new species of cluster makers such as [TiO6]', [TiO5·VO(x)], [TiO5·VO˙] and [TiO5·VO˙˙]. This structural transformation is consistent with a redistribution of electron density from highly ordered [TiO6](x) clusters which form distorted [TiO6]' as well as complex [TiO5·VO(x)], [TiO5·VO˙] and [TiO5·VO˙˙] clusters assigned to oxygen vacancies which were understood as displacements in the oxygen atoms' position in the bond lengths (Ti-O).