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KNbO3 single crystals are grown by the self-flux method using K2CO3 as a flux, but often suffer from discolouration. In this work, KNbO3 single crystals were grown by the flux method using KBO2 as a flux. KNbO3 powder was prepared by the solid-state reaction of K2CO3 and Nb2O5. KBO2 was fabricated by the reaction of K2B4O7·4H2O and K2CO3. Single crystals of KNbO3 were grown in a Pt crucible and the structure and dielectric properties of the single crystals were investigated. X-ray diffraction showed the KNbO3 single crystals to have an orthorhombic Cmm2 perovskite unit cell at room temperature. The existence of ferroelastic domains was revealed by transmission electron microscopy. Electron probe microanalysis showed the single crystals to be stoichiometric and contain small amounts of B. Differential thermal analysis, Raman scattering and impedance spectroscopy were used to study the phase transitions. KBO2 may be a suitable flux for the growth of KNbO3 single crystals. [ABSTRACT FROM AUTHOR]

The structural features and optical properties of supramolecular cyanoiron salts containing bis-pyridinium-4-oxime Toxogonin® (TOXO) as an electron acceptor are presented. The properties of the new TOXO-based cyanoiron materials were probed by employing two cyanoiron platforms: hexacyanoferrate(II), [Fe(CN)6]4– (HCF); and nitroprusside, [Fe(CN)5(NO)]2– (NP). Two water-insoluble inter-ionic donor–acceptor phases were characterized: the as-prepared microcrystalline reddish-brown (TOXO)2[Fe(CN)6]·8H2O (1a) with a medium-responsive, hydrochromic character; and the dark violet crystalline (TOXO)2[Fe(CN)6]·3.5H2O (1cr). Complex 1a, upon external stimulation, transforms to the violet anhydrous phase (TOXO)2[Fe(CN)6] (1b), which upon water uptake transforms back to 1a. Using the NP platform resulted in the water-insoluble crystalline salt TOXO[Fe(CN)5(NO)]·2H2O (2). The structures of 1cr and 2, solved by single-crystal X-ray diffraction, along with a comparative spectroscopic (UV–vis–NIR diffuse reflectance, IR, solid-state MAS-NMR, Mössbauer), thermal, powder X-ray diffraction, and microscopic analysis (SEM, TEM) of the isolated materials, provided insight for the supramolecular binding, electron-accepting, and H-bonding capabilities of TOXO in the self-assembly of these functionalized materials. [ABSTRACT FROM AUTHOR]

Amphibole asbestos is related to multiple diseases, mainly those targeting the lungs. Asbestos-related malignancies can also be caused by non-regulated asbestiform minerals and some elongated mineral particles (EMPs). In particular, the role of nano- and micro-sized EMPs internalized by lung epithelial cells must be clarified. This is of major importance when considering that EMPs to which humans are exposed are likely a highly heterogeneous mix of different mineral types, shapes, and sizes. Here, we document that particles smaller than 4.54 µm in length and smaller than 0.89 µm in width (e.g., particles that do not fit the regulatory categories to be identified as asbestos) are easily internalized because of their specific dimensions, surface charge, and shape (mostly dictated by the aspect ratio L/w). Once internalized, these particles can be found in proximity to the cell nucleus, in vesicles, and in the cytoplasm. Examining the localization of particles in cells provides important information, which helps in determining the physicochemical environment found inside the biological compartment, thus allowing for a better comprehension of the mineralogical transformation that might happen after internalization by cells. [ABSTRACT FROM AUTHOR]

In the search for electronic phenomena in high-entropy alloys (HEAs) that go beyond the independent-electron description, we have synthesized a series of hexagonal rare earth (RE)-based HEAs: CexLaLuScY (x = 0.05–1.0). The measurements of electrical resistivity, magnetic susceptibility and specific heat have shown that the CexLaLuScY HEAs exhibit the Kondo effect, which is of a single impurity type in the entire range of employed Ce concentrations despite the alloys being classified as dense (concentrated) Kondo systems. A comparison to other known dense Kondo systems has revealed that the Kondo effect in the CexLaLuScY HEAs behaves quite differently from the chemically ordered Kondo lattices but quite similar to the RE-containing magnetic metallic glasses and randomly chemically disordered Kondo lattices of the chemical formula RE1xRE21−xM (with RE1 being magnetic and RE2 being nonmagnetic). The main reason for the similarity between HEAs and the metallic glasses and chemically disordered Kondo lattices appears to be the absence of a periodic 4f sublattice in these systems, which prevents the formation of a coherent state between the 4f-scattering sites in the T → 0 limit. The crystal-glass duality of HEAs does not bring conceptually new features to the Kondo effect that would not be already present in other disordered dense Kondo systems. This study broadens the classification of HEAs to correlated electron systems. [ABSTRACT FROM AUTHOR]

In this study, we present a new approach for the synthesis of Pt/SnO2 catalysts using microwave radiation. Pt(IV) and Sn(IV) inorganic precursors (H2PtCl6 and SnCl4) and ammonia were used, which allowed the controlled formation of platinum particles on the anisotropic SnO2 support. The synthesized Pt/SnO2 samples are mesoporous and exhibit a reversible physisorption isotherm of type IV. The XRD patterns confirmed the presence of platinum maxima in all Pt/SnO2 samples. The Williamson-Hall diagram showed SnO2 anisotropy with crystallite sizes of ~10 nm along the c-axis (< 00l >) and ~5 nm along the a-axis (< h00 >). SEM analysis revealed anisotropic, urchin-like SnO2 particles. XPS results indicated relatively low average oxidation states of platinum, close to Pt metal. 119Sn Mössbauer spectroscopy indicated electronic interactions between Pt and SnO2 particles. The synthesized samples were used for the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of excess NaBH4. The catalytic activity of the Pt/SnO2 samples for the reduction of 4-NP to 4-AP was optimized by varying the synthesis parameters and Pt loading. The optimal platinum loading for the reduction of 4-NP to 4-AP on the anisotropic SnO2 support is 5 mol% with an apparent rate constant k = 0.59 × 10–2 s–1. The Pt/SnO2 sample showed exceptional reusability and retained an efficiency of 81.4% after ten cycles. [ABSTRACT FROM AUTHOR]

The dynamics of domain walls (DWs) during polarization switching has a great influence on the electromechanical response of ferroelectrics. To understand the influence of DWs on the functional performance of the material, their local structure and properties must be revealed. There are many investigations of the DWs in ferroelectric thin films, while investigations of the DWs in polycrystalline ferroelectrics are fewer. Here, we report on a comparative study of uncharged and charged ("tail-to-tail") DWs in BiFeO3 ceramics from the point of view of the atomically resolved strain and structure using scanning-transmission electron microscopy. Both types of DWs have a step-like morphology and have a non-Ising behavior. The strain, expressed as the unit-cell distortion, is higher and more concentrated in the case of uncharged walls, which we associate with a narrower transition region of the Fe-displacement vectors. Conversely, in the case of "tail-to-tail" charged DWs, the unit-cell distortion is smaller and more dispersed because of the wider transition region of the Fe-displacement vectors. All the types of step-like DWs reported here, regardless of their charge state, exhibit a comparable amount of Bi-vacancies segregation. Further details about the structural differences are discussed from the point of view of the Fe-displacement evolution through the wall for uncharged/"tail-to-tail" charged DWs. The results are useful as they provide an insight into the local structure and chemistry of charged and uncharged DWs in polycrystalline BiFeO3. [ABSTRACT FROM AUTHOR]

TiO2 nanotubes constitute very promising nanomaterials for water decontamination by the removal of cations. We combined a range of experimental techniques from structural analyses to measurements of the properties of aqueous suspensions of nanotubes, with (i) continuous solvent modeling and (ii) quantum DFT-based simulations to assess the adsorption of Cs+ on TiO2 nanotubes and to predict the separation of metal ions. The methodology is set to be operable under realistic conditions, which, in this case, include the presence of CO2 that needs to be treated as a substantial contaminant, both in experiments and in models. The mesoscopic model, based on the Poisson–Boltzmann equation and surface adsorption equilibrium, predicts that H+ ions are the charge-determining species, while Cs+ ions are in the diffuse layer of the outer surface with a significant contribution only at high concentrations and high pH. The effect of the size of nanotubes in terms of the polydispersity and the distribution of the inner and outer radii is shown to be a third-order effect that is very small when the nanotube layer is not very thick (ranging from 1 to 2 nm). Besides, DFT-based molecular dynamics simulations demonstrate that, for protonation, the one-site and successive association assumption is correct, while, for Cs+ adsorption, the size of the cation is important and the adsorption sites should be carefully defined. [ABSTRACT FROM AUTHOR]

Volatile memory devices relying on the Mott-type insulator-to-metal transition of vanadium oxide (VO2) are widely utilized in the field of neuromorphic computing. Such devices, however, are realized in a nanoscale geometry, where the switching relies on the self-heating of an ultrasmall spot as well as the presence of extremely high electric fields in the active region. In this paper, we investigate the interplay of such nanoscale thermal and nonlinear electronic phenomena by investigating the temperature and voltage dependent conduction properties of our custom-designed VO2 devices, where a V-shaped electrode focuses the switching to an ultrasmall single-spot active region. This simplified spatial structure of the active volume facilitates the device modeling and the identification of physical mechanisms behind the phase transition. We find that purely thermal or electronic effects fail to describe the device operation, however, according to our finite element simulations, a combined electronic and thermal model provides a precise description of the device characteristics. These results facilitate the understanding as well as the thermal and electronic design of novel VO2-based neuronal devices. [ABSTRACT FROM AUTHOR]

Ferroelectric domain dynamics is at the heart of any ferroelectric-based application. In situ transmission electron microscopy (TEM) offers an exciting opportunity to directly image ferroelectric switching and domain dynamics, revealing phenomena that might be concealed in macroscopic measurements. Here, we investigate the voltage-driven response of the mobile, needlelike domains and domain walls (DWs) of a (K,Na)NbO3 single crystal (KNNsc) using in situ TEM in a miniaturized capacitor. Our experimental results reveal that the immobile DWs can act as random bound pinning centers, pinning an area of up to 0.35 μm2. The edge of the sample can promote the nucleation of new domains. Domain growth and coalescence are not always continuous but can be interrupted at a certain voltage in favor of fine domain splitting and the formation of nanoscale domains. Other discontinuities are generated in the functional response when two orthogonal, needlelike domains meet and soft-pinning events occur. These findings shed light on the kinetics of ferroelectric domains and are probably not limited to KNNsc, being applicable to other perovskite-based ferroelectric materials where a needlelike domain morphology is present or where mobile and immobile DWs coexist. [ABSTRACT FROM AUTHOR]

The thermal treatment of electromechanically active thick films prepared by aerosol deposition (AD) is a common practice to improve their electrical and electromechanical properties. We report on how post-deposition annealing in air affects the unique cross-sectional microstructure and mechanical properties of 0.9Pb(Mg1/3Nb2/3)O3−0.1PbTiO3 thick films prepared by AD. Transmission electron microscopy revealed minor but detectable changes, such as pore redistribution and grain growth after annealing at 500 °C. We also showed that the stainless-steel substrate is strongly affected by the annealing. The hardness and Young's modulus of the films increased after annealing, with both properties being discussed in terms of their distribution over the cross-sections of the films. [ABSTRACT FROM AUTHOR]

In this work, we bring the first large-scale study of grain growth kinetics of copper-doped ceria nanoparticles. Since most of the notable applications of ceria nanoparticles, such as catalysis or solid oxide fuel cells, require its use at elevated temperatures, particle agglomeration and aggregation occur, which diminish the favorable properties of ceria. Doping with copper was chosen as a strategy for the increase of ceria thermal stability. Pure ceria and ceria doped with 10, 20, 30 and 40 mol.% of copper were prepared by hydrothermal synthesis, thermally treated at temperatures in the range between 300 and 700 °C at various annealing times and analyzed using X-ray diffraction analysis and transmission electron microscopy. An isothermal grain growth kinetics analysis was conducted based on the crystallite sizes calculated through the Scherrer equation in order to determine the influence of copper doping on ceria thermal stability. Three temperature ranges with different grain growth regimes and kinetic parameters were defined. The activation energies increase, while the grain growth exponents decrease from low to high temperature range, which is in concordance with the change in the growth mechanism from diffusion to Ostwald-Ripening. It was established that the thermal stability of ceria does not solely depend on the lattice defects introduced by copper, but also on microstructure, porosity and sample preparation. Still, the addition of copper has a positive influence on thermal stability of ceria up to 650 °C, and the sample with 40 mol.% of added copper has the slowest grain growth in the full studied temperature range. [ABSTRACT FROM AUTHOR]

Searching for materials that possess a combination of excellent magnetic softness and vanishing magnetostriction, the ferromagnetic high‐entropy alloy (HEA) system AlCoFeNiCux (x = 0.6–3.0) is investigated. Superior magnetostriction and magnetic softness parameters are obtained for the composition AlCoFeNiCu2.0, which shows zero magnetostriction, λs = 0, low coercivity Hc ≈ 650 A m−1 and substantial saturation magnetic polarization of Js ≈ 0.55 T. The parameters of other AlCoFeNiCux compositions in the range x = 2.0–3.0 are only slightly different, so that the entire set of the AlCoFeNiCux HEAs in that Cu content range can be classified as magnetically soft and vanishing‐magnetostriction alloys. The alloys develop a multiphase (up to three phases) composite microstructure that is further nanostructured on the 10 nm scale. Magnetic softness of the alloys originates from the exchange‐averaging of magnetic anisotropy, while vanishing magnetostriction coefficient of the AlCoFeNiCu2.0 alloy results from its three‐phase microstructure, where the magnetostrictions of different signs exactly compensate each other at particular volume fractions. The AlCoFeNiCux (x = 2.0–3.0) HEAs are expected to find applications as supersilent (inaudible to a human ear) materials for transformers, magnetocaloric coolers, and other "humming" electromagnetic machinery. [ABSTRACT FROM AUTHOR]

Bioapplication is an emerging field of metal-organic frameworks (MOF) utilization, but biocompatible MOFs with permanent porosity are still a rarity in the field. In addition, biocompatibility of MOF constituents is often overlooked when designing bioMOF systems, intended for drug delivery. Herein, we present the a Zn(II) bioMOF based on vitamin C as an independent ligand (bioNICS-1) forming a three-dimensional chiral framework with permanent microporosity. Comprehensive study of structure stability in biorelavant media in static and dynamic conditions demonstrates relatively high structure resistivity, retaining a high degree of its parent specific surface area. Robustness of the 3D framework enables a slow degradation process, resulting in controllable release of bioactive components, as confirmed by kinetic studies. BioNICS-1 can thus be considered as a suitable candidate for the design of a small drug molecule delivery system, which was demonstrated by successful loading and release of urea—a model drug for topical application—within and from the MOF pores. Metal–organic frameworks have demonstrated great potential as drug delivery systems, but the biocompatibility of the MOF components is often overlooked. Here, a vitamin C and zinc-based MOF with permanent microporosity is designed, and successful loading and release of model drug urea from the MOF pores, as well as degradation of the framework, are demonstrated. [ABSTRACT FROM AUTHOR]

Titanium oxynitride carbon composite nanofibers (TiON/C-CNFs) were synthesised with electrospinning and subsequent heat treatment in ammonia gas. In situ four-probe electrical conductivity measurements of individual TiON/C-CNFs were performed. Additionally, the TiON/C-CNFs were thoroughly analysed with various techniques, such as X-ray and electron diffractions, electron microscopies and spectroscopies, thermogravimetric analysis and chemical analysis to determine the crystal structure, morphology, chemical composition, and N/O at. ratio. It was found that nanofibers were composed of 2–5 nm sized titanium oxynitride (TiON) nanoparticles embedded in an amorphous carbon matrix with a small degree of porosity. The average electrical conductivity of a single TiON/C-CNF was 1.2 kS/m and the bulk electrical conductivity of the TiON/C-CNF fabric was 0.053 kS/m. From the available data, the mesh density of the TiON/C-CNF fabric was estimated to have a characteristic length of 1.0 µm and electrical conductivity of a single TiON/C-CNF was estimated to be from 0.45 kS/m to 19 kS/m. The electrical conductivity of the measured TiON/C-CNFs is better than that of amorphous carbon nanofibers and has ohmic behaviour, which indicates that it can effectively serve as a new type of support material for electrocatalysts, batteries, sensors or supercapacitors. [ABSTRACT FROM AUTHOR]

The formation and the evolution of electronic metallic states localized at the surface, commonly termed 2D electron gas (2DEG), represents a peculiar phenomenon occurring at the surface and interface of many transition metal oxides (TMO). Among TMO, titanium dioxide (TiO2), particularly in its anatase polymorph, stands as a prototypical system for the development of novel applications related to renewable energy, devices and sensors, where understanding the carrier dynamics is of utmost importance. In this study, angle‐resolved photo‐electron spectroscopy (ARPES) and X‐ray absorption spectroscopy (XAS) are used, supported by density functional theory (DFT), to follow the formation and the evolution of the 2DEG in TiO2 thin films. Unlike other TMO systems, it is revealed that, once the anatase fingerprint is present, the 2DEG in TiO2 is robust and stable down to a single‐unit‐cell, and that the electron filling of the 2DEG increases with thickness and eventually saturates. These results prove that no critical thickness triggers the occurrence of the 2DEG in anatase TiO2 and give insight in formation mechanism of electronic states at the surface of TMO. [ABSTRACT FROM AUTHOR]

Dislocations are becoming vastly popular in the field of oxide perovskites, including the subgroup of ferroelectric martials, as functional defects used to tailor their macroscopic responses, i.e. their mechanical and ferroelectric properties [1, 2]. The brittle nature of perovskites at room temperature presents an obstacle in engineering dislocation post-synthesis via controlled mechanical deformation. Understanding the mechanisms leading to remnant deformation of these materials at macroscopic and local scales and their competition is therefore of central importance. In this work, we focus on the local deformation mecha nisms of BiFeO3 deformed using a cube-corner indentation probe with a force between 200 μN and 2 mN. Analysis of the indentation curves, focusing on the first pop-in events, in combination with electron microscopy techniques revealed homogeneous dislocation nucleation, dislocation movement and propagation, grain subdivision in the immediate vicinity of the indented surface as well as cracking which was only observed above 1 mN. The influence of ferroelastic domain wall dynamics on deformation will also be discussed [3]. [ABSTRACT FROM AUTHOR]

In situ polymerization was used to produce novel AgFeO2@PEG/polyurethane network nanocomposites (NP-PUs) with 30–60 wt% of soft poly(dimethylsiloxane) segments in polyurethane (PU), containing 1 wt% of PEG-coated AgFeO2 nanoparticles, AgFeO2@PEG. Physicochemical properties and in vitro biological activity of the NP-PUs were systematically evaluated in terms of AgFeO2@PEG (NP) addition and soft segment content. High-angle annular dark-field transmission electron microscopy showed that the nanoparticles were generally uniformly distributed in the PU matrix. Increased soft segment content caused significantly increased intensity of the broad, amorphous X-ray diffraction peaks of crystalline AgFeO2, probably because the chemical composition of PU affected the distribution of nanoparticles. The Young modulus, hardness, and plasticity of the NP-PUs were higher than for pure PU and increased with decreasing soft segment content. Decreased soft segment content induced higher microphase separation, increased hydrophilicity and swelling ability, but decreased cross-linking density. Additionally, NP-PUs had higher glass transition temperatures, improved thermal stability, and enhanced nanomechanical performance over pure PU. The NP-PUs demonstrated good selective inhibition of Candida albicans and Candida parapsilosis (30–55%) and no pronounced cytotoxicity to MRC5 human lung fibroblasts. Among the investigated AgFeO2@PEG/PUs, the best antifungal activity was shown by composites with 30 and 40 wt% soft segments. Consequently, the novel AgFeO2@PEG/polyurethane network nanocomposites could be further optimized to be used as biocompatible surfaces that also prevent formation of fungal biofilms. [ABSTRACT FROM AUTHOR]

Spontaneous metallic Pb whisker formation from Pb and Bi containing Al-alloy's surfaces is a newly discovered phenomenon. The whiskers display unique formations, growth and morphology, which give the opportunity to be applied for specialized sensor and electronics applications. Within this work, the impact of environmental conditions (gas composition and moisture) is investigated and correlated with the modification of whisker evolution and growth dynamics. Furthermore, the residual stress state of the aluminum matrix using deep cryogenic treatment is modified and used to further increase whisker nucleation and growth by up to three- and seven-fold, respectively, supported by quantitative results. The results of this paper indicate the possibility to manipulate the whisker not only in terms of their kinetics but also their morphology (optimal conditions are 20% O2 and 35% humidity). Such features allow the tailoring of the whisker structure and surface to volume ratio, which can be optimized for different applications. Finally, this research provides new insight into the growth dynamics of the whiskers through in situ and ex situ measurements, providing further evidence of the complex nucleation and growth mechanisms that dictate the spontaneous growth of Pb whiskers from Al-alloy 6026 surfaces with growth velocities up to 1.15 µm/s. [ABSTRACT FROM AUTHOR]

Bioapplication is an emerging field of metal-organic frameworks (MOF) utilization, but biocompatible MOFs with permanent porosity are still a rarity in the field. In addition, biocompatibility of MOF constituents is often overlooked when designing bioMOF systems, intended for drug delivery. Herein, we present the a Zn(II) bioMOF based on vitamin C as an independent ligand (bioNICS-1) forming a three-dimensional chiral framework with permanent microporosity. Comprehensive study of structure stability in biorelavant media in static and dynamic conditions demonstrates relatively high structure resistivity, retaining a high degree of its parent specific surface area. Robustness of the 3D framework enables a slow degradation process, resulting in controllable release of bioactive components, as confirmed by kinetic studies. BioNICS-1 can thus be considered as a suitable candidate for the design of a small drug molecule delivery system, which was demonstrated by successful loading and release of urea—a model drug for topical application—within and from the MOF pores. Metal–organic frameworks have demonstrated great potential as drug delivery systems, but the biocompatibility of the MOF components is often overlooked. Here, a vitamin C and zinc-based MOF with permanent microporosity is designed, and successful loading and release of model drug urea from the MOF pores, as well as degradation of the framework, are demonstrated. [ABSTRACT FROM AUTHOR]

Amphibole asbestos is related to lung fibrosis and several types of lung tumors. The disease-triggering mechanisms still challenge our diagnostic capabilities and are still far from being fully understood. The literature focuses primarily on the role and formation of asbestos bodies in lung tissues, but there is a distinct lack of studies on amphibole particles that have been internalized by alveolar epithelial cells (AECs). These internalized particles may directly interact with the cell nucleus and the organelles, exerting a synergistic action with asbestos bodies (AB) from a different location. Here we document the near-atomic- to nano-scale transformations induced by, and taking place within, AECs of three distinct amphiboles (anthophyllite, grunerite, "amosite") with different Fe-content and morphologic features. We show that: (i) an Fe-rich layer is formed on the internalized particles, (ii) particle grain boundaries are transformed abiotically by the internal chemical environment of AECs and/or by a biologically induced mineralization mechanism, (iii) the Fe-rich material produced on the particle surface does not contain large amounts of P, in stark contrast to extracellular ABs, and (iv) the iron in the Fe-rich layer is derived from the particle itself. Internalized particles and ABs follow two distinct formation mechanisms reaching different physicochemical end-states. [ABSTRACT FROM AUTHOR]

The understanding of the origin of a two-dimensional electron gas (2DEG) at the surface of anatase TiO2 remains a challenging issue. In particular, in TiO2 ultra-thin films, it is extremely difficult to distinguish intrinsic effects, due to the physics of the TiO2, from extrinsic effects, such as those arising from structural defects, dislocations, and the presence of competing phases at the film/substrate interface. It is, therefore, mandatory to unambiguously ascertain the structure of the TiO2/substrate interface. In this work, by combining high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), density functional theory calculations, and multislice image simulations, we have investigated the nature of strainless anatase TiO2 thin films grown on LaAlO3 substrate. In particular, the presence of oxygen vacancies in anatase TiO2 has been proved to stabilize the formation of an extra alloy layer, Ti2AlO4, by means of interface rearrangement. Our results, therefore, elucidate why the growth of anatase TiO2 directly on LaAlO3 substrate has required the deposition of a TiOx extra-layer to have a 2DEG established, thus confirming the absence of a critical thickness for the TiO2 to stabilize a 2DEG at its surface. These findings provide fundamental insights on the underlying formation mechanism of the 2DEG in TiO2/LAO hetero-interfaces to engineer the 2DEG formation in anatase TiO2 for tailored applications. [ABSTRACT FROM AUTHOR]

This work brings a thorough investigation of hydrothermally derived ceria nanoparticles doped with copper in a wide range of concentrations: CuxCe1-xO2, where x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5, respectively. X-ray diffraction (XRD) analysis showed no additional phases for all samples up to x = 0.4, which exceeds the maximum amount of copper incorporated into ceria without the appearance of copper oxide phase reported in the literature. However, the inductively coupled plasma mass spectrometry (ICP-MS) and energy-dispersive X-ray spectroscopy (EDS) analyses showed that copper is incorporated into the ceria crystal lattice in amounts far lower than the nominal. Nevertheless, the addition of copper has a significant influence on the ceria properties. The size of the obtained nanoparticles was determined by transmission electron microscopy (TEM) and it decreases with the increase of the copper amount from 6 nm for the pure sample to 3.8 nm for the 40 mol. % Cu-doped CeO2 sample. In accordance with the small particle size, the specific surface area, determined from nitrogen adsorption–desorption isotherms at 77 K, is in the range of 196 to 222 m2 g−1. The increase in the copper amount also causes the reduction of the band gap, as determined by UV–Vis reflectance analysis (UV–Vis DRS), and an increase of reducibility, as proven by temperature-programmed reduction by hydrogen (H2-TPR). [ABSTRACT FROM AUTHOR]

We parametrize rational D(q)-triples for q 2 Q which is not a square. We use this parametrization to describe all rational D(q)-triples which are also D(0)-triples, and to describe all rational D(q)-quadruples which contain at least one regular D(q)-triple. [ABSTRACT FROM AUTHOR]

In this paper, we present the results of a multi-analytical characterization of a glaucophane sample collected in the Piedmont region of northwestern Italy. Investigation methods included optical microscopy, powder X-ray diffraction, Fourier-transform infrared spectroscopy, µ-Raman spectroscopy, Mössbauer spectroscopy, electron probe microanalysis, environmental scanning electron microscopy and energy-dispersive X-ray spectroscopy, and scanning/transmission electron microscopy combined with energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy. In addition to the crystal-chemical characterization of the sample from the mesoscale to the near-atomic scale, we have also conducted an extended study on the morphology and dimensions of the mineral particles. The main finding is that studying the same particle population at different magnifications yields different results for mineral habit, dimensions, and dimensional distributions. As glaucophane may occur as an elongate mineral particle (e.g., asbestiform glaucophane occurrences in California and Nevada), the observed discrepancies therefore need to be considered when assessing potential breathability of such particles, with implications for future regulations on elongate mineral particles. While the sample preparation and particle counting methods are not directly investigated in this work, our findings suggest that different magnifications should be used when characterizing an elongate mineral particle population, irrespective of whether or not it contains asbestiform material. These results further reveal the need for developing improved regulation for elongate mineral particles. We thus propose a simple methodology to merge the datasets collected at different magnifications to provide a more complete description and a better risk evaluation of the studied particle population. [ABSTRACT FROM AUTHOR]

Lead‐based relaxor ferroelectrics are characterized by outstanding piezoelectric and dielectric properties, making them useful in a wide range of applications. Despite the numerous models proposed to describe the relation between their nanoscale polar structure and the large properties, the multiple contributions to these properties are not yet revealed. Here, by combining atomistic and mesoscopic‐scale structural analyses with macroscopic piezoelectric and dielectric measurements across the (100–x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 (PMN–xPT) phase diagram, a direct link is established between the multiscale structure and the large nonlinear macroscopic response observed in the monoclinic PMN‐xPT compositions. The approach reveals a previously unrecognized softening effect, which is common to Pb‐based relaxor ferroelectrics and arises from the displacements of low‐angle nanodomain walls, facilitated by the nanoscale polar character and lattice strain disorder. This comprehensive comparative study points to the multiple, distinct mechanisms that are responsible for the large piezoelectric response in relaxor ferroelectrics. [ABSTRACT FROM AUTHOR]

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Neutrophilic, microaerobic Fe(II)‐oxidizing bacteria (FeOB) from marine and freshwater environments are known to generate twisted ribbon‐like organo‐mineral stalks. These structures, which are extracellularly precipitated, are susceptible to chemical influences in the environment once synthesized. In this paper, we characterize the minerals associated with freshwater FeOB stalks in order to evaluate key organo‐mineral mechanisms involved in biomineral formation. Micro‐Raman spectroscopy and Field Emission Scanning Electron Microscopy revealed that FeOB isolated from drinking water wells in Sweden produced stalks with ferrihydrite, lepidocrocite and goethite as main mineral components. Based on our observations made by micro‐Raman Spectroscopy, field emission scanning electron microscopy and scanning transmission electron microscope combined with electron energy‐loss spectroscopy, we propose a model that describes the crystal‐growth mechanism, the Fe‐oxidation state, and the mineralogical state of the stalks, as well as the biogenic contribution to these features. Our study suggests that the main crystal‐growth mechanism in stalks includes nanoparticle aggregation and dissolution/re‐precipitation reactions, which are dominant near the organic exopolymeric material produced by the microorganism and in the peripheral region of the stalk, respectively. [ABSTRACT FROM AUTHOR]

Spectroelectrochemistry can offer important insights into the performance of materials that change properties during electrochemical treatment. The benefits of spectroelectrochemical measurements are shown through the example of an electrochromic sol–gel vanadium(V) oxide (V2O5) film. In situ UV-visible absorbance spectroelectrochemistry is indispensable to reveal the optical modulation, which reached about 28% during the first coloration in the unsafe potential range, but then diminished to around 12% during the following cycles. Ex situ IR and Raman spectroscopy were used to probe the structural modifications that occur during the intercalation of small ions into the orthorhombic structure of the crystalline V2O5 film. In particular, infrared reflection–absorption (IR RA) and IR absorption spectroelectrochemistry confirmed the red shift of the vanadyl band and the disappearance of the bridging oxygen band due to the puckering of layers of VO5 square pyramids following intercalation. In addition, Raman spectra reveal the broad and low-intensity bands of the V2O5 film after it has been coloured in the unsafe potential range. Electron energy-loss spectroscopy (EELS) revealed the presence of vanadium in oxidation states V4+, V4+/V5+, and V5+ on different positions on the bleached film. Highlights: Vibrational and UV-visible spectroelectrochemistry of sol–gel electrochromic V2O5 films. In situ UV-visible absorbance of V2O5 film defines its optical modulation. Ex situ IR reflection–absorption, IR absorption during coloration and bleaching. Ex situ Raman reveals significant band changes in the unsafe potential range. Ex situ EELS spectra confirm V4+, V4+/V5+, and V5+ sites on the bleached film. [ABSTRACT FROM AUTHOR]

Determination of the oxidation state and coordination geometry of iron in Fe-bearing minerals expands our knowledge obtained by standard mineralogical characterization. It provides information that is crucial in assessing the potential of minerals to interact with their surrounding environment and to generate reactive oxygen species, which can disrupt the normal function of living organisms. Aberration-corrected scanning transmission electron microscopy dual-electron energy-loss spectroscopy (acSTEM Dual-EELS) has only rarely been applied in environmental and medical mineralogy, but it can yield data that are essential for the description of near-surface and surface mechanisms involved in many environmental and health-related processes. In this study, we have applied the energy loss near-edge structure (ELNES) and L2,3 white-line intensity-ratio methods using both the universal curve and progressively larger integrating windows to verify their effectiveness in satisfactorily describing the valence state of iron at amosite grain boundaries, and, at the same time, to estimate thickness in the same region of interest. The average valence state obtained from acSTEM Dual-EELS and from a simplified geometrical model were in good agreement, and within the range defined by the bulk and the measured surface-valence states. In the specific case presented here, the use of the universal curve was most suitable in defining the valence state of iron at amosite grain boundaries. The study of ELNES revealed an excellent correspondence with the valence state determined by the L2,3 white-line intensity-ratio method through the use of the universal curve, and it seems that the spectra carry some information regarding the coordination geometry of Fe. The combination of visual examination, reconstruction of the grain boundaries through a simple geometrical model, and Dual-EELS investigation is a powerful tool for characterizing the grain boundaries of hazardous minerals and foreseeing their potential activity in an organism, with the possibility to describe toxic mechanisms in a stepwise fashion. [ABSTRACT FROM AUTHOR]

The majority of bladder cancers in humans are non-muscle-invasive cancers that recur frequently after standard treatment procedures. Mouse models are widely used to develop anti-tumor treatments. The purpose of our work was to establish an orthotopic mouse bladder tumor model and to explore early stages of implantation of cancerous MB49 cells in vivo using various labeling and microscopic techniques. To distinguish cancer cells from normal urothelial cells in mouse urinary bladders, we performed molecular characterization of MB49 cells before intravesical injection experiments. In this new approach we applied internalized metal nanoparticles to unequivocally discriminate cancer cells from normal cells. This method revealed that cancer cells attached to the urothelium or basal lamina within just 1 hour of intravesical injection, whereas small tumors and localized hyperplastic urothelial regions developed within two days. We found that cancer cells initially adhere to normal urothelial cells through filopodia and by focal contacts with basal lamina. This is the first in vivo characterization of intercellular contacts between cancerous and normal urothelial cells in the bladder. Our study yields new data about poorly known early events of tumorigenesis in vivo, which could be helpful for the translation into clinic. [ABSTRACT FROM AUTHOR]

There is a wide range of factors affecting bacterial adhesion and biofilm formation. However, in both food processing and medical settings, it is very hard to obtain suitably controlled conditions so that the factors that reduce surface colonisation and biofouling can be studied. The aim of this study was to evaluate the effect of glucose concentration, temperature and stainless steel (SS) surface roughness on biofouling by four common pathogens (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and L. monocytogenes). Among the tested variables, the untreated SS surface (3C) was shown to be fouled more than 3D polished, brushed or electropolished SS surfaces. Although an array of parameters influenced biofouling, the most promising control measure was the influence of low temperature (4 °C) that reduced biofouling even in the case of the psychrophilic Listeria monocytogenes. The study findings could significantly contribute to the prevention of SS surface contamination and consequential biofouling by food and healthcare associated pathogens. [ABSTRACT FROM AUTHOR]

The conversion of the biomass-derived lipid, lignocellulosic and carbohydrate resources into renewable platform intermediates, chemicals and biofuels has been lately increasing in interest. The mechanistic reaction pathways, like hydro-deoxygenation, decarboxylation and hydrocracking, of the selected palmitic acid, as a model fatty acid, over Ni/ZSM-5 zeolite catalysts were studied. The ZSM-5 material with different Al/Si molar ratios was synthesized via a green template-free hydrothermal synthesis procedure, treated and subsequent functionalised with various Ni metal loadings. However, Ni/Al molar ratio was kept stoichiometric (Ni/Al = 0.5). The characteristic physicochemical properties of composite catalysts were studied by numerous characterization techniques, such as X-ray powder diffraction (XRD), scanning-, as well as high-resolution transmission electron microscopy (SEM/HRTEM), and X-ray photoelectron spectroscopy (XPS). NiO with an average particle size of 10-20 nm was found on ZSM-5 support. The relative Ni/Al atom fraction in Ni/ZSM-5 systems influenced their Lewis/Brønsted acidic sites, as well as the external exposed area of prepared heterogeneous structures. Furthermore, the mentioned morphological parameters affected predominant catalytic routes. Species’ production mechanism, as a consequence of Lewis/Brønsted centre weak/strong acidity, as well as their integral concentration, was proposed, mirroring the observed process kinetics, selectivity and turnover. It was demonstrated that the main obtained products were esters, aldehydes, alcohols, hydrocarbons and gases (CO2, CO…), produced by deoxygenation (e.g. decarbonylation), hydrogenation and cracking, less, though, through isomerisation. [ABSTRACT FROM AUTHOR]

Abstract: A green, template‐free and easy‐to‐implement strategy was developed to access holey g‐C3N4 (GCN) nanosheets doped with carbon. The protocol involves heating dicyandiamide with β‐cyclodextrin (βCD) prior to polymerization. The local symmetry of the GCN skeleton is broken, yielding CxGCN (x corresponds to the initial amount of βCD used) with pores and a distorted structure. The electronic, emission, optical and textural properties of the best‐performing material, C2GCN, were significantly modified as compared to bulk GCN. The spectroscopic and luminescent features of C2GCN show the characteristic π–π* electronic transition of GCN, accompanied by much stronger n–π* electronic transitions owing to the porous and distorted network. These new electronic transitions, along with the presence of additional carbon synergistically contributed to enhanced visible light absorption and restrained recombination of electron–hole pairs. Steady‐state and time‐resolved photoluminescence showed an effective quench of the fluorescence emission, accompanied by a decrease of fluorescence lifetime of C2GCN (2.20 ns) in comparison with GCN (5.85 ns), owing to the delocalization of electron and holes to new recombination centers. The photocatalytic activity of C2GCN was attributed to efficient charge carrier separation and improved visible‐light absorbing ability. As result, C2GCN exhibited ∼5 times higher photocatalytic H2 generation under visible light than bulk GCN. [ABSTRACT FROM AUTHOR]

Abstract: Benzyl alcohol was selectively oxidized to benzaldehyde in aqueous solution, at ambient conditions of temperature and pressure, by using a photocatalytic approach, with two types of irradiation sources, namely monochromatic UV−A light (392 nm) and visible light (400‐700 nm). Conversion after 4 h of reaction was more efficient under UV than under visible, with selectivity in excess of 80% for both irradiating sources. Composites of graphitic carbon nitride (g‐C3N4) containing small amounts of reduced graphene oxide (rGO) (up to 1 wt.%) were used as photocatalysts. The presence of rGO was confirmed by spectroscopic and microscopic analyses. Results show that small amounts of rGO phase can considerably enhance the photocatalytic activity of g‐C3N4 based catalysts, the best load being 0.10 wt.%. This improvement is attributed to the critical modification of morphological and electronic properties provided by the presence of rGO. [ABSTRACT FROM AUTHOR]

Bacterial infections acquired in healthcare facilities including hospitals, the so called healthcare acquired or nosocomial infections, are still of great concern worldwide and represent a significant economical burden. One of the major causes of morbidity is infection with Methicillin Resistant Staphylococcus aureus (MRSA), which has been reported to survive on surfaces for several months. Bactericidal activity of copper-TiO2 thin films, which release copper ions and are deposited on glass surfaces and heated to high temperatures, is well known even when illuminated with very weak UVA light of about 10 μW/cm2. Lately, there is an increased intrerest for one-dimensional TiO2 nanomaterials, due to their unique properties, low cost, and high thermal and photochemical stability. Here we show that copper doped TiO2 nanotubes produce about five times more ·OH radicals as compared to undoped TiO2 nanotubes and that effective surface disinfection, determined by a modified ISO 22196:2011 test, can be achieved even at low intensity UVA light of 30 μW/cm2. The nanotubes can be deposited on a preformed surface at room temperature, resulting in a stable deposition resistant to multiple washings. Up to 103 microorganisms per cm2 can be inactivated in 24 hours, including resistant strains such as Methicillin-resistant Staphylococcus aureus (MRSA) and Extended-spectrum beta-lactamase Escherichia coli (E. coli ESBL). This disinfection method could provide a valuable alternative to the current surface disinfection methods. [ABSTRACT FROM AUTHOR]

Titanium dioxide has been widely used as an antimicrobial agent, UV-filter and catalyst for pollution abatement. Herein, surface modifications with selected transition metals (Me) over colloidal TiO2 nanoparticles and immobilization with a colloidal SiO2 binder as composite films (MeTiO2/SiO2) on a glass carrier were used to enhance solar-light photoactivity. Colloidal TiO2 nanoparticles were modified by loading selected transition metals (Me = Mn, Fe, Co, Ni, Cu, and Zn) in the form of chlorides on their surface. They were present primarily as oxo-nanoclusters and a portion as metal oxides. The structural characteristics of bare TiO2 were preserved up to an optimal metal loading of 0.5 wt%. We have shown in situ that metal-oxo-nanoclusters with a redox potential close to that of O2/O2Ṗ− were able to function as co-catalysts on the TiO2 surface which was excited by solar-light irradiation. The materials were tested for photocatalytic activity by two opposite methods; one detecting O2Ṗ− (reduction, Rz ink test) while the other detecting ṖOH (oxidation, terephthalic acid test). It was shown that the enhancement of the solar-light activity of TiO2 by the deposition of transition metal oxo-nanoclusters on the surface depends strongly on the combination of the reduction potential of such species and appropriate band positions of their oxides. The latter prevented excessive self-recombination of the photogenerated charge carriers by the nanoclusters in Ni and Zn modification, which was probably the case in other metal modifications. Overall, only Ni modification had a positive effect on solar photoactivity in both oxidation and reduction reactions. [ABSTRACT FROM AUTHOR]

Conversion type materials, in particular metal fluorides, have emerged as attractive candidates for positive electrodes in next generation Li-ion batteries (LIBs). However, their practical use is being hindered by issues related to reversibility and large polarization. To minimize these issues, a few approaches enlisting the anionic network have been considered. We herein report the electrochemical properties of bismuth oxyborate Bi4B2O9 and show that this compound reacts with lithium via a conversion reaction leading to a sustained capacity of 140 mA h g−1 when cycled between 1.7 and 3.5 V vs. Li+/Li0 while having a surprisingly small polarization (∼300 mV) in the presence of solely 5% in weight of a carbon additive. These observations are rationalized in terms of charge transfer kinetics via complementary XRD, HRTEM and NMR measurements. This finding demonstrates that borate based conversion type materials display rapid charge transfer with limited carbon additives, hence offering a new strategy to improve their overall cycling efficiency. [ABSTRACT FROM AUTHOR]

Charge transfer at the semiconductor-electrolyte junction is one of the main challenges for further improvement of photoelectrochemical (PEC) water splitting cells due to the poor surface catalytic properties of most semiconductors for the water oxidation reaction. Here it is shown, for the first time, that a conformal and thin carbon nitride (CN) layer can efficiently extract holes from ZnO nanowires (NWs), leading to a great enhancement of both PEC performance and stability in alkaline solution. The conformal CN coating is acquired by using a new synthetic method which involves the deposition of small supramolecular assemblies on ZnO-NWs as a seeding layer for the CN growth. Detailed PEC characterization reveals that the CN facilitates the hole transfer from the ZnO-NWs to the electrolyte and acts as a protective shell, resulting in 3.5 times higher current densities and high external quantum efficiencies at 1.23 V versus RHE compared to the pristine ZnO-NWs. [ABSTRACT FROM AUTHOR]

This study explores the fine structural details of the boundaries between the growth micro-sectors in a ruby crystal grown hydrothermally on a nonsingularly oriented (011̅2̅) seed. The samples were examined using IR-spectroscopy and HRTEM-analysis, demonstrating that the interfaces of the micro-sectors serve as ‘traps’ for OH-groups often observed in grown crystals. Counter to what has previously been reported, a significant proportion of these OH-groups is incorporated into ruby crystals in an orderly manner, forming diaspore-like layers growing epitaxially on the corundum (011̅2) lattice planes. The tensions on the boundaries between the micro-sectors result in local increase of internal pressure, making the diaspore-like phase stable. The assumption is made that the mechanism discussed in the article can explain the occurrence of OH-groups in the structure of nominally anhydrous minerals, such as MgSiO3 (akimotoite) which is structurally similar to corundum. [ABSTRACT FROM AUTHOR]