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A variety of multisegmented nanorods (NRs) composed of dense Au and porous Rh and Ru segments with lengths controlled down to ca. 10 nm are synthesized within porous anodic aluminum oxide membranes. Despite the high Rh and Ru porosity (i.e., ∼40%), the porous metal segments are able to efficiently couple with the longitudinal localized surface plasmon resonance (LSPR) of Au NRs. Finite-difference time-domain simulations show that the LSPR wavelength can be precisely tuned by adjusting the Rh and Ru porosity. Additionally, light absorption inside Rh and Ru segments and the surface electric field (E-field) at Rh and Ru can be independently and selectively enhanced by varying the position of the Rh and Ru segment within the Au NR. The ability to selectively control and decouple the generation of high-energy, surface hot electrons and low-energy, bulk hot electrons within photocatalytic metals such as Rh and Ru makes these bimetallic structures great platforms for fundamental studies in plasmonics and hot-electron science.

Vertically aligned silicon nanowire (VA-SiNW) arrays can significantly enhance light absorption and reduce light reflection for efficient light trapping. VA-SiNW arrays thus have the potential to improve solar cell design by providing reduced front-face reflection while allowing the fabrication of thin, flexible, and efficient silicon-based solar cells by lowering the required amount of silicon. Because their interaction with light is highly dependent on the array geometry, the ability to control the array morphology, functionality, and dimension offers many opportunities. Herein, after a short discussion about the remarkable optical properties of SiNW arrays, we report on our recent progress in using chemical and electrochemical methods to structure and pattern SiNW arrays in three dimensions, providing substrates with spatially controlled optical properties. Our approach is based on metal-assisted chemical etching (MACE) and three-dimensional electrochemical axial lithography (3DEAL), which are both affordable and large-scale wet-chemical methods that can provide a spatial resolution all the way down to the sub-5 nm range.

Developing simple, inexpensive, and environmentally benign approaches to integrate morphologically well-defined nanoscale building blocks into larger high surface area materials is a key challenge in materials design and processing. In this work, we investigate the fundamental surface phenomena between MgO and water (both adsorption and desorption) with particles prepared via a vapor-phase process (MgO nanocubes) and a modified aerogel process (MgO(111) nanosheets). Through these studies, we unravel a strategy to assemble individual MgO nanoparticles into extended faceted single-crystalline MgO nanosheets and nanorods with well-defined exposed surfaces and edges. This reorganization can be triggered by the presence of H2O vapor or bulk liquid water. Water adsorption and the progressive conversion of vapor-phase grown oxide particles into hydroxides give rise to either one-dimensional or two-dimensional (1D or 2D) structures of high dispersion and surface area. The resulting Mg(OH)2 lamella with a predominant (001) surface termination are well-suited precursor structures for their topotactic conversion into laterally extended and uniform MgO(111) grain surface configurations. To understand the potential of polar (111) surfaces for faceting and surface reconstruction effects associated with water desorption, we investigated the stability of MgO(111) nanosheets during vacuum annealing and electron beam exposure. The significant surface reconstruction of the MgO(111) surfaces observed shows that adsorbate-free (111)-terminated surfaces of unsupported MgO nanostructures reconstruct rather than remain as charged planes of either three-fold coordinated O2– ion or Mg2+ ions. Thus, here we demonstrate the role water can play in surface formation and reconstruction by bridging wet chemical and surface science inspired approaches., The organization of MgO nanocubes as primary building blocks can be achieved by materials contact with water and subsequent thermal treatment in a vacuum.

Gold nanoparticle/silicon composites are canonical substrates for sensing applications because of their geometry-dependent physicochemical properties and high sensing activity via surface-enhanced Raman spectroscopy (SERS). The self-assembly of gold nanoparticles (AuNPs) synthesized via wet-chemistry on functionalized flat silicon (Si) and vertically aligned Si nanowire (VA-SiNW) arrays is a simple and cost-effective approach to prepare such substrates. Herein, we report on the critical parameters that influence nanoparticle coverage, aggregation, and assembly sites in two- and three-dimensions to prepare substrates with homogeneous optical properties and SERS activity. We show that the degree of AuNP aggregation on flat Si depends on the silane used for the Si functionalization, while the AuNP coverage can be adjusted by the incubation time in the AuNP solution, both of which directly affect the substrate properties. In particular, we report the reproducible synthesis of nearly touching AuNP chain monolayers where the AuNPs are separated by nanoscale gaps, likely to be formed due to the capillary forces generated during the drying process. Such substrates, when used for SERS sensing, produce a uniform and large enhancement of the Raman signal due to the high density of hot spots that they provide. We also report the controlled self-assembly of AuNPs on VA-SiNW arrays, which can provide even higher Raman signal enhancement. The directed assembly of the AuNPs in specific regions of the SiNWs with a control over NP density and monolayer morphology (i.e., isolated vs nearly touching NPs) is demonstrated, together with its influence on the resulting SERS activity.

The combination of metal-assisted chemical etching (MACE) and colloidal lithography allows for the affordable, large-scale and high-throughput synthesis of silicon nanowire (SiNW) arrays. However, many geometric parameters of these arrays are coupled and cannot be addressed individually using colloidal lithography. Despite recent advancements towards higher flexibility, SiNWs fabricated via colloidal lithography and MACE usually have circular, isotropic cross-sections inherited from the spherical templates. Here we report a facile technique to synthesize anisotropic SiNWs with tunable cross-sections via colloidal lithography and MACE. Metal films with an elliptical nanohole array can form from shadows of colloidal particles during thermal evaporation of the metal at tilted angles. The aspect ratio of these anisotropic holes can be conveniently controlled via the deposition angle. Consecutive MACE using these patterned substrates with or without prior removal of the templating spheres results in arrays of anisotropic SiNWs with either elliptical or crescent-shaped cross-sections, respectively. As a consequence of the anisotropy, long SiNWs with elliptical cross-sections preferentially collapse along their short axis, leading to a controlled bundling process and the creation of anisotropic surface topographies. These results demonstrate that a rich library of SiNW shapes and mesostructures can be prepared using simple spherical colloidal particles as masks., We demonstrate the design of silicon nanowire arrays with tunable elliptical cross-sections. Their anisotropic character of the individual pillars affords defined bending or bundling of the arrays.

Metal–silicon nanowire array photoelectrodes provide a promising architecture for water-splitting because they can afford high catalyst loading and decouple charge separation from the light absorption process. To further improve and understand these hybrid nanowire photoelectrodes, control of the catalyst amount and location within the wire array is required. Such a level of control is currently synthetically challenging to achieve. Here, we report the synthesis of cm2-sized hybrid silicon nanowire arrays with electrocatalytically active Ni–Mo and Pt patches placed at defined vertical locations within the individual nanowires. Our method is based on a modified three-dimensional electrochemical axial lithography (3DEAL), which combines metal-assisted chemical etching (MACE) to produce Si nanowires with spatially defined SiO2 protection layers to selectively cover and uncover specific areas within the nanowire arrays. This spatioselective SiO2 passivation yields nanowire arrays with well-defined exposed Si surfaces, with feature sizes down to 100 nm in the axial direction. Subsequent electrodeposition directs the growth of the metal catalysts at the exposed silicon surfaces. As a proof of concept, we report photoelectrocatalytic activity of the deposited catalysts for the hydrogen evolution reaction on p-type Si nanowire photocathodes. This demonstrates the functionality of these hybrid metal/Si nanowire arrays patterned via 3DEAL, which paves the way for investigations of the influence of three-dimensional geometrical parameters on the conversion efficiency of nanostructured photoelectrodes interfaced with metal catalysts.

The combination of metal-assisted chemical etching (MACE) with colloidal lithography has emerged as a simple and cost-effective approach to nanostructure silicon. It is especially efficient at synthesizing Si micro- and nanowire arrays using a catalytic metal mesh, which sinks into the silicon substrate during the etching process. The approach provides a precise control over the array geometry, without requiring expensive nanopatterning techniques. Although MACE is a high-throughput solution-based approach, achieving large-scale homogeneity can be challenging because of the instability of the metal catalyst when the experimental parameters are not set appropriately. Such instabilities can lead to metal film fracture, significantly damaging the substrate and thus compromising the nanowire array quality. Here, we report on the critical parameters that influence the stability of the metal catalyst layer for achieving large-scale homogeneous MACE: etchant composition, metal film thickness, adhesion layer thickness, nanowire diameter and pitch, metal film coverage, Si/Au/etchant interface length, and crystalline quality of the colloidal template (grain size and defects). Our results investigate the origin of the catalyst film fracture and reveal that MACE experiments should be optimized for each Si wire array geometry by keeping the etch rate below a certain threshold. We show that the Si/Au/etchant interface length also affects the etch rate and should thus be considered when optimizing the MACE experimental parameters. Finally, our results demonstrate that colloidal templates with small grain sizes (i.e.

In this research paper the microstructure of the magnesium AZ31B alloy is investigated after the application of a single monotonic compressive strain of −0.4%. A band of twinned grains is observed to form in the test bar approximately 10 mm wide, corresponding to the zone of highest plastic strain. The microstructure of this region is studied using electron backscatter diffraction and transmission electron microscopy (TEM). Twinning mode and fraction are reported along with a detailed analysis of precipitate phase and size distribution. Evidence is given for twin-precipitate interaction during the twin formation process. High resolution TEM and energy dispersive X-ray spectroscopy are used in conjunction with structural simulation software to identify the Al-Mn phase. A zinc shell is observed forming around precipitates, and this is related to zinc exclusion by the precipitating Al-Mn phase.

Ambient water condenses readily on metal oxides, which can lead to water film formation and water-mediated reactions at the oxide surface. Similar to bulk water, thin water films with thicknesses below 10 molecular layers can modify the oxide surface chemical reactivity and stability. However, due to the confinement of mass transport at the oxide surface, these processes do not proceed exactly as they do in bulk liquid water. In this review article, we will present selected examples from our group and others’ that illustrate the rich interaction of MgO and TiO2 nanostructures with thin water films. We will show that these condensed water films can induce significant chemical, structural, and microstructural transformations of metal oxide nanostructures such as dissolution/precipitation, morphological changes, crystallization, and self-assembly in the solid state.

We report on a quick, simple, and cost-effective solution-phase approach to prepare centimeter-sized morphology-graded vertically aligned Si nanowire arrays. Gradients in the nanowire diameter and shape are encoded through the macroscale substrate via a “dip-etching” approach, where the substrate is removed from a KOH etching solution at a constant rate, while morphological control at the nanowire level is achieved via sequential metal-assisted chemical etching and KOH etching steps. This combined approach provides control over light absorption and reflection within the nanowire arrays at both the macroscale and nanoscale, as shown by UV–vis spectroscopy and numerical three-dimensional finite-difference time-domain simulations. Macroscale morphology gradients yield arrays with gradually changing optical properties. Nanoscale morphology control is demonstrated by synthesizing arrays of bisegmented nanowires, where the nanowires are composed of two distinct segments with independently controlled lengths and diameters. Such nanowires are important to tailor light–matter interactions in functional devices, especially by maximizing light absorption at specific wavelengths and locations within the nanowires.

Measuring the dimensions and number density of nanoparticles dispersed in a solid matrix is usually accomplished via transmission electron microscopy (TEM) which suffers from high cost, low throughput, and small analytical volume. In comparison, scanning backscattered electron microscopy is inexpensive, requires little sample preparation, and allows for the analysis of large sample areas. However, the information depth is usually not known precisely and depends on several factors such as the composition of the nanoparticles and the matrix as well as the size of the nanoparticles, hindering the reconstruction of the actual size distribution and three-dimensional number density. Here we present a method to estimate the information depth for spherical nanoparticles of different sizes in order to accurately determine size distribution and number density. The approach is based on Monte Carlo simulation of electron trajectories in the material and analysis of the obtained backscattered electron signal-to-noise-ratio. Our experimental results are compared to those obtained via TEM and good agreement is demonstrated; this shows that TEM can be replaced by scanning electron microscopy for studying nanocomposites in many cases.

[Background] Activity retention upon enzyme adsorption on inorganic nanostructures depends on different system parameters such as structure and composition of the support, composition of the medium as well as enzyme loading. Qualitative and quantitative characterization work, which aims at an elucidation of the microscopic details governing enzymatic activity, requires well-defined model systems., [Results] Vapor phase-grown and thermally processed anatase TiO2 nanoparticle powders were transformed into aqueous particle dispersions and characterized by dynamic light scattering and laser Doppler electrophoresis. Addition of β-galactosidase (β-gal) to these dispersions leads to complete enzyme adsorption and the generation of β-gal/TiO2 heteroaggregates. For low enzyme loadings (~4% of the theoretical monolayer coverage) we observed a dramatic activity loss in enzymatic activity by a factor of 60–100 in comparison to that of the free enzyme in solution. Parallel ATR-IR-spectroscopic characterization of β-gal/TiO2 heteroaggregates reveals an adsorption-induced decrease of the β-sheet content and the formation of random structures leading to the deterioration of the active site., [Conclusions] The study underlines that robust qualitative and quantitative statements about enzyme adsorption and activity retention require the use of model systems such as anatase TiO2 nanoparticle agglomerates featuring well-defined structural and compositional properties., This work was financially supported by the University of Salzburg within the Allergy-Cancer-BioNano (ACBN) Research initiative.

As part of an ongoing effort to develop novel, highly active and stable Pt-free catalysts for the oxygen reduction reaction (ORR), we here report the synthesis, structural characteristics and electrochemical/electrocatalytic properties of novel core-shell composite materials, consisting of a spherical nitrided carbon core and a tantalum (oxy)nitride shell. The (nitrided) carbon core is supposed to improve the electrical conductivity of the material and the (oxy)nitride shell is intended to protect the core against electrochemical corrosion. Spherical core-shell TaOxNy@CmNn composite particles were synthesized by sol-gel deposition of tantalum oxide on preformed carbon spheres, which were prepared by hydrothermal carbonization of glucose and subsequent nitriding in ammonia vapor at different temperatures (700 °C − 1150 °C). The influence of the nitriding temperature on the structure and phase composition of the resulting composite particles was evaluated, employing a variety of techniques, including electron microscopy (SEM, TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), elemental analysis, thermogravimetric analysis (TGA), IR spectroscopy and N2 sorption measurements, and correlated with changes in the electrochemical/electrocatalytic behavior. These core-shell composite materials show a significantly improved ORR activity compared to pure tantalum (oxy)nitrides, in particular upon nitriding at 1000 °C, while the selectivity for the 4-electron pathway to H2O still requires improvement. The physical origin of the high activity of these materials and contributions from different phases are discussed.

In the automotive industry Al-Mg-Si alloys are often chosen for high strength extruded profiles. However, the production of such profiles can be challenging for high alloy contents. Among several processing steps, the homogenization heat treatment before extrusion is readily accessible to modifications to improve high temperature formability. In this work, the influence of five different homogenization variants on the flow stress of AA6082 at elevated temperatures was assessed by compression testing in a deformation dilatometer at 450 °C, 480 °C, and 510 °C. The observed differences in flow stress were interpreted with regards to the microstructure. Samples from billets homogenized at higher soak temperatures exhibited lower hot flow stresses in subsequent dilatometer testing, indicating better processability. Since the decrease in flow stress is approximately constant at all test temperatures, it is suggested that it is due to a lower number density of relatively temperature-stable α-Al(Mn,Fe)Si dispersoids formed during homogenization at higher temperatures; these dispersoids are stable at all three test temperatures. In contrast, the influence of a cooling rate variation was relatively minor and diminishes at higher test temperatures since Mg-Si precipitates – whose size and number density is affected by changes of the cooling rate – are less stable at the higher test temperatures.

Wasserdampf kann die Form und Anordnung von Nanopartikeln entscheidend beeinflussen. Inwieweit dies fur die Steuerung der Struktur und Eigenschaften von Nanomaterialien nutzbar ist, wurde bislang allerdings kaum erforscht. Hier wird uber die durch Wasserdampf ausgeloste Selbstorganisation von MgO-Nanowurfeln in regelmasig versetzte eindimensionale Anordnungen berichtet. Diese Transformation erfolgt uber eine anfangliche geordnete Anlagerung der MgO-Wurfel, hat die Bildung von langlichen Mg(OH)2-Strukturen zum Zwischenzustand und endet mit der Ruckumwandlung in Stapel aus versetzt gestuften MgO-Nanowurfeln. Mittels Ab-initio-Modellierung konnten die durch Hydratisierung und Hydroxylierung bedingten Anderungen der Energie der Wurfeloberflachen als Ausloser und Triebkraft fur die ungewohnliche, gestufte Anordnung der Wurfel identifiziert werden. Diese Selbstorganisation von Metalloxid-Nanopartikeln auserhalb einer flussigen Umgebungsphase bietet einen neuen Ansatz zur Steuerung keramischer Mikrostrukturen und sowie eine Moglichkeit zur Uberprufung oberflachenwissenschaftlicher Konzepte.

Characterization of Mg-Si precipitates is crucial for optimizing the homogenization heat treatment of Al-Mg-Si alloys. Although sample preparation is key for high quality scanning electron microscopy imaging, most common methods lead to dealloying of Mg-Si precipitates. In this article we systematically evaluate different sample preparation methods: mechanical polishing, etching with various reagents, and electropolishing using different electrolytes. We demonstrate that the use of a nitric acid and methanol electrolyte for electropolishing a homogenized Al-Mg-Si alloy prevents the dissolution of Mg-Si precipitates, resulting in micrographs of higher quality. This preparation method is investigated in depth and the obtained scanning electron microscopy images are compared with transmission electron micrographs: the shape and size of Mg-Si precipitates appear very similar in either method. The scanning electron micrographs allow proper identification and measurement of the Mg-Si phases including needles with lengths of roughly 200 nm. These needles are β″ precipitates as confirmed by high resolution transmission electron microscopy.

Particle/particle interfaces play a crucial role in the functionality and performance of nanocrystalline materials such as mesoporous metal oxide electrodes. Defects at these interfaces are known to impede charge separation via slow-down of transport and increase of charge recombination, but can be passivated via electrochemical doping (i.e., incorporation of electron/proton pairs), leading to transient but large enhancement of photoelectrode performance. Although this process is technologically very relevant, it is still poorly understood. Here we report on the electrochemical characterization and the theoretical modeling of electron traps in nanocrystalline rutile TiO2 films. Significant changes in the electrochemical response of porous films consisting of a random network of TiO2 particles are observed upon the electrochemical accumulation of electron/proton pairs. The reversible shift of a capacitive peak in the voltammetric profile of the electrode is assigned to an energetic modification of trap sta...

The most frequently studied functionalities of porous WO3 particle systems—namely their electrochromic and photocatalytic properties—are intimately related to the wanted or unwanted action of defects in the material. Here, we report on the generation and action of three types of defects in WO3 electrodes: solid/solid interfaces between adjacent particle aggregates, defects generated in situ upon photoinduced electron accumulation, and defects resulting from tungsten bronze formation. Depending on the degree of aggregate interconnection, we observe a beneficial, albeit transient, effect of charge accumulation on the photoelectrocatalytic activity of the thin films, giving rise to an almost threefold increase in photocurrent. The dynamic change of thin film properties associated with this doping process is tracked by a combined spectroscopic and electrochemical approach, which allows the beneficial and detrimental effects of defects to be resolved on the electrochemical potential scale.

Health is a multi-dimensional concept, capturing how people feel and function. The broad concept of Active and Healthy Ageing was proposed by the World Health Organisation (WHO) as the process of optimizing opportunities for health to enhance quality of life as people age. It applies to both individuals and population groups. A universal Active and Healthy Ageing definition is not available and it may differ depending on the purpose of the definition and/or the questions raised. While the European Innovation Partnership on Active and Healthy Ageing (EIP on AHA) has had a major impact, a definition of Active and Healthy Ageing is urgently needed. A meeting was organised in Montpellier, France, October 20-21, 2014 as the annual conference of the EIP on AHA Reference Site MACVIA-LR (Contre les Maladies Chroniques pour un Vieillissement Actif en Languedoc Roussillon) to propose an operational definition of Active and Healthy Ageing including tools that may be used for this. The current paper describes the rationale and the process by which the aims of the meeting will be reached. Health is a multi-dimensional concept, capturing how people feel and function. The broad concept of Active and Healthy Ageing was proposed by the World Health Organisation (WHO) as the process of optimizing opportunities for health to enhance quality of life as people age. It applies to both individuals and population groups. A universal Active and Healthy Ageing definition is not available and it may differ depending on the purpose of the definition and/or the questions raised. While the European Innovation Partnership on Active and Healthy Ageing (EIP on AHA) has had a major impact, a definition of Active and Healthy Ageing is urgently needed. A meeting was organised in Montpellier, France, October 20-21, 2014 as the annual conference of the EIP on AHA Reference Site MACVIA-LR (Contre les Maladies Chroniques pour un Vieillissement Actif en Languedoc Roussillon) to propose an operational definition of Active and Healthy Ageing including tools that may be used for this. The current paper describes the rationale and the process by which the aims of the meeting will be reached.

BACKGROUND: Multimorbidity in allergic airway diseases is well known, but no data exist about the daily dynamics of symptoms and their impact on work. To better understand this, we aimed to assess the presence and control of daily allergic multimorbidity (asthma, conjunctivitis, rhinitis) and its impact on work productivity using a mobile technology, the Allergy Diary. METHODS: We undertook a 1-year prospective observational study in which 4 210 users and 32 585 days were monitored in 19 countries. Five visual analogue scales (VAS) assessed the daily burden of the disease (i.e., global evaluation, nose, eyes, asthma and work). Visual analogue scale levels

We report a template-based technique for the preparation of solution-dispersible nanorings composed of Au, Ag, Pt, Ni, and Pd with control over outer diameter (60-400 nm), inner diameter (25-230 nm), and height (40 nm to a few microns). Systematic and independent control of these parameters enables fine-tuning of the three characteristic localized surface plasmon resonance modes of Au nanorings and the resulting solution-based extinction spectra from the visible to the near-infrared. This synthetic approach provides a new pathway for solution-based investigations of surfaces with negative curvature.

The optical and electrical properties of heterogeneous nanowires are profoundly related to their composition and nanoscale architecture. However, the intrinsic constraints of conventional synthetic and lithographic techniques have limited the types of multi-compositional nanowire that can be created and studied in the laboratory. Here, we report a high-throughput technique that can be used to prepare coaxial nanowires with sub-10 nm control over the architectural parameters in both axial and radial dimensions. The method, termed coaxial lithography (COAL), relies on templated electrochemical synthesis and can create coaxial nanowires composed of combinations of metals, metal oxides, metal chalcogenides and conjugated polymers. To illustrate the possibilities of the technique, a core/shell semiconductor nanowire with an embedded plasmonic nanoring was synthesized--a structure that cannot be prepared by any previously known method--and its plasmon-excitation-dependent optoelectronic properties were characterized.

Surface-enhanced Raman scattering (SERS) is a versatile spectroscopic technique that suffers from reproducibility issues and usually requires complex substrate fabrication processes. In this article, we report the use of a simple mass production technology based on Blu-ray disc manufacturing technology to prepare large area SERS substrates (∼40 mm2) with a high degree of homogeneity (±7% variation in Raman signal) and enhancement factor of ∼6 × 106. An industrial high throughput injection molding process was used to generate periodic microstructured polymer substrates coated with a thin Ag film. A short chemical etching step produces a highly dense layer of Ag nanoparticles at the polymer surface, which leads to a large and reproducible Raman signal. Finite difference time domain simulations and cathodoluminescence mapping experiments suggest that the sample microstructure is responsible for the generation of SERS active nanostructures around the microwells. Comparison with commercial SERS substrates demo...

We report the isotropic etching of 2D and 3D polystyrene (PS) nanosphere hcp arrays using a benchtop O2 radio frequency plasma cleaner. Unexpectedly, this slow isotropic etching allows tuning of both particle diameter and shape. Due to a suppressed etching rate at the point of contact between the PS particles originating from their arrangement in 2D and 3D crystals, the spherical PS templates are converted into polyhedral structures with well-defined hexagonal cross sections in directions parallel and normal to the crystal c-axis. Additionally, we found that particles located at the edge (surface) of the hcp 2D (3D) crystals showed increased etch rates compared to those of the particles within the crystals. This indicates that 2D and 3D order affect how nanostructures chemically interact with their surroundings. This work also shows that the morphology of nanostructures periodically arranged in 2D and 3D supercrystals can be modified via gas-phase etching and programmed by the superlattice symmetry. To show the potential applications of this approach, we demonstrate the lithographic transfer of the PS template hexagonal cross section into Si substrates to generate Si nanowires with well-defined hexagonal cross sections using a combination of nanosphere lithography and metal-assisted chemical etching.

Particle/particle interfaces play a crucial role in the functionality and performance of nanocrystalline materials such as mesoporous metal oxide electrodes. Defects at these interfaces are known to impede charge separation via slow-down of transport and increase of charge recombination, but can be passivated via electrochemical doping (i.e., incorporation of electron/proton pairs), leading to transient but large enhancement of photoelectrode performance. Although this process is technologically very relevant, it is still poorly understood. Here we report on the electrochemical characterization and the theoretical modeling of electron traps in nanocrystalline rutile TiO2 films. Significant changes in the electrochemical response of porous films consisting of a random network of TiO2 particles are observed upon the electrochemical accumulation of electron/proton pairs. The reversible shift of a capacitive peak in the voltammetric profile of the electrode is assigned to an energetic modification of trap states at particle/particle interfaces. This hypothesis is supported by first-principles theoretical calculations on a TiO2 grain boundary, providing a simple model for particle/particle interfaces. In particular, it is shown how protons readily segregate to the grain boundary (being up to 0.6 eV more stable than in the TiO2 bulk), modifying its structure and electron-trapping properties. The presence of hydrogen at the grain boundary increases the average depth of traps while at the same time reducing their number compared to the undoped situation. This provides an explanation for the transient enhancement of the photoelectrocatalytic activity toward methanol photooxidation which is observed following electrochemical hydrogen doping of rutile TiO2 nanoparticle electrodes.

This educational paper aims to assist physics teachers in explaining the concepts and principles of material composition and deformation by describing how to perform a microscopy investigation of a deformed wrought magnesium alloy test piece. By examining the changes taking place at the different length scales from macro to nano it is possible to understand how changes in the microstructure influence the macroscopic appearance and properties. The microscopy techniques employed for the investigation of each length scale—light microscopy, scanning electron microscopy and transmission electron microscopy—are explained along with the procedures of specimen preparation. A background is given to help teachers explain the microstructure of magnesium, the role of magnesium alloys in modern industrial and technological contexts and the historical developments of microscopy. The paper can also be used to assist teachers in laboratory courses to describe the principles and methods of scientific experiment. The work is fully referenced and a reading list is included, making it suitable as a teaching resource for academic courses or for solo study.

The microstructure of heterogeneous nanowires plays a major role in determining their properties. For example, core-shell nanowires composed of optically active p- and n-type semiconductors have photovoltaic properties that are superior to their planar counterparts due to more efficient charge separation owing to the high interfacial surface area and relatively small distance required to separate electron-hole pairs. The limited combined use of polymer, core-shell, and plasmonic compositions in nanostructured materials highlights the lack of versatility in current synthetic techniques and emphasizes the need for new synthetic techniques to address unmet challenges facing the photovoltaic community. Here, we report the electrochemical synthesis of solution dispersible, multi-segmented nanowires in which metallic nanostructures are precisely interfaced with core-shell polymeric and inorganic semiconductor materials with nanometer scale resolution.

Water vapor is ubiquitous under ambient conditions and may alter the shape of nanoparticles. How to utilize water adsorption for nanomaterial functionality and structure formation, however, is a yet unexplored field. Herein, we report the use of water vapor to induce the self-organization of MgO nanocubes into regularly staggered one-dimensional structures. This transformation evolves via an initial alignment of the MgO cubes, the formation of intermediate elongated Mg(OH)2 structures, and their reconversion into MgO cubes arranged in staggered structures. Ab initio DFT modelling identifies surface-energy changes associated with the cube surface hydration and hydroxylation to promote the uncommon staggered stacked assembly of the cubes. This first observation of metal oxide nanoparticle self-organization occurring outside a bulk solution may pave novel routes for inducing texture in ceramics and represents a great test-bed for new surface-science concepts.

Additional file 1. IPCRG scaling up activities.

Physisorbed water originating from exposure to the ambient can have a strong impact on the structure and chemistry of oxide nanomaterials. The effect can be particularly pronounced when these oxides are in physical contact with a solid substrate such as the ones used for immobilization to perform electron or ion microscopy imaging. We used helium ion microscopy (HIM) and investigated morphological changes of vapor-phase-grown MgO cubes after vacuum annealing and pressing into foils of soft and high purity indium. The indium foils were either used as obtained or, for reference, subjected to vacuum drying. After four days of storage in the vacuum chamber of the microscope and at a base pressure of p < 10−7 mbar, we observed on these cubic particles the attack of residual physisorbed water molecules from the indium substrate. As a result, thin magnesium hydroxide layers spontaneously grew, giving rise to characteristic volume expansion effects, which depended on the size of the particles. Rounding of the originally sharp cube edges leads to a significant loss of the morphological definition specific to the MgO cubes. Comparison of different regions within one sample before and after exposure to liquid water reveals different transformation processes, such as the formation of Mg(OH)2 shells that act as diffusion barriers for MgO dissolution or the evolution of brucite nanosheets organized in characteristic flower-like microstructures. The findings underline the significant metastability of nanomaterials under both ambient and high-vacuum conditions and show the dramatic effect of ubiquitous water films during storage and characterization of oxide nanomaterials.

Ultrathin and flexible silica nanosheets, synthesized with gold nanorod dimers embedded uniformly throughout, can be dispersed in solution and deposited onto arbitrary surfaces. These novel materials conform and maintain the as-synthesized density of dimers, allowing them to be used reliably in labeling and detection applications.

The facile fabrication of free-standing conductive Au(0) and Ag(0) nanostructured monoliths via the chemical reduction of sheets composed respectively of AuCl(n-butylamine) nanofibers and aggregated AgCl nanocubes is reported. This preparation can be performed on a large scale (hundreds of milligrams) with high yield (>74%). The product sheets have large dimensions (several cm2), high conductivity (>1800 S m–1 for the Au(0) sheets), and large surface areas (2 m2 g–1 or 400 m2 mol–1 for the Au(0) sheets). The macroscopic structure of the Au(I) and Ag(I) sheets is preserved during the chemical reduction process. At the nanoscale the Au(I) fibers are converted into Au(0) ribbons and fibers, and the AgCl cubes are converted into porous Ag(0) cubes. The resulting porous metal sheets provide physically stable Au(0) and Ag(0) foams that are highly sought-after in catalysis, sensing, and electrocatalysis applications.

A template-based method for the fabrication of silver cyanide and polymer composite nanowires is described. Poly(styrene-alt-maleic anhydride) forms nanotubes in aqueous solution and acts as a template, guiding the growth of silver cyanide into long nanowires. The structures obtained can grow to several tens of micrometers in length and their diameter range from several to tens of nanometers. These AgCN nanowires can be reduced to metallic silver to form a high surface area Ag(0) nanowire array on a flexible nylon filter substrate.

The goal of this study was to examine the perceived usefulness and the perceived ease of use of a Hospital Information System (HIS) for the care staff. We administrated a questionnaire composed of open-end and closed questions. As results, the perceived usefulness and ease of use are correlated with medical occupations. Content analysis of open questions highlights three factors influencing these constructs: ergonomics, errors in the documenting process and insufficient compatibility with the medical department or the occupation. While the results are consistent with literature, they show medical occupations do not report the same low rate of perceived usefulness and of ease of use. The main explanation consists in the medical risk in the prescription process for anesthesiologists, surgeons and physicians.

International audience

For many applications, micro- and nanostructured materials show a strong correlation between their geometry and their function. We report here the interfacial precipitation of a copper/alkylamine complex to form Cu(OH)(2) nanofibers in a two-phase system (H(2)O/CH(2)Cl(2)). Their aggregation results in porous microbeads. This mesoscale aggregation is due to the formation of a water-in-oil (W/O) emulsion. The fibers formed at the H(2)O/CH(2)Cl(2) interface adsorb on the water droplet surface leading to spherical networks of Cu(OH)(2) fibers. Our preparation technique is rapid (less than 1 h) and benefits from the simplicity and the tunability of emulsions.To our knowledge, this is the first demonstration of the in situ synthesis of 1D nanostructures that self-assemble at both the surface and the inside of emulsion droplets. We report the successful control over the chemical nature of the synthesized material, its size, and morphology at both the mesoscale (completely hollow versus porous) and the nanoscale (nanoribbons versus nanofibers) by the addition of a short chain alcohol. The transformation of these materials into porous CuO spheres has several potential applications, including a demonstrated sensitive response to visible light (measured photocurrent/dark current ratio of 2.22).

Using on-wire lithography, we studied the emission properties of nanostructures made of a polythiophene disk separated by fixed nanoscopic distances from a plasmonic gold nanorod. The intense plasmonic field generated by the nanorod modifies the shape of the polythiophene emission spectrum, and the strong distance dependence of this modulation forms the basis for a new type of “plasmophore ruler”. Simulations using the discrete dipole approximation (DDA) quantitatively support our experimental results. Importantly, this plasmophore ruler is independent of signal intensity and is effective up to 100 nm, which is more than two times larger than any reported value for rulers based on photoluminescence processes.

Background Patients with chronic inflammatory rheumatic disease have a greater risk of cardiovascular (CV) diseases. European recommendations of cardiology propose to classify patients with asymptomatic atheromatous plaques as high CV risk patients. New EULAR recommendations about CV risk management propose the use of supra-aortic vessel ultrasound for atheromatous plaques detection and total CV risk estimation. Moreover, EULAR-2015 recommendations suggest multiplying by a 1.5 factor the global CV risk for all patients with Rheumatoid Arthritis (RA) unlike 2010 recommendations. Objectives The objective of our study was to evaluate the impact of these new recommendations on CV management, especially on indication of statin use, in patients with RA in daily practice, in comparison to EULAR-2010 recommendations. Methods Total CV risk estimation included physical examination, glucidic and lipidic blood tests, supra-aortic and abdominal vessels ultrasound, echocardiography and global risk SCORE calculation. Heart-SCORE was multiplied according to EULAR-2010 (mSCORE2010) or EULAR-2015 (mSCORE2015) recommendations. For EULAR-2015 recommendations, patients with ultrasound carotid plaques were classified at high CV risk. LDL targets and immediate need of statin use were defined according to European cardiology recommendations with need of statin when LDL >0.7 g/L for patients at very high CV risk and >1 g/L for those at high risk. In moderate and low risk patients, statins are not immediately recommended. Results 157 RA patients underwent the screening with a mean disease duration of 13 (6–19) ± 9 years and mean age of 61 ± 11 years. 56/76 (73.7%) of patients classified as moderate risk with Heart-SCORE and 3/12 (25%) of patients with low risk had asymptomatic carotid plaques. Application of the EULAR 2010 recommendations should lead to immediate statin prescription in 42 patients (28%) whereas applications of the EULAR 2015 recommendations should lead to statin prescription in 92 (61%) patients. Conclusions In our experience, the use of carotid ultrasound to estimate total CV risk and thus to define LDL targets led to prescribe statins in 61% of patients with RA. Disclosure of Interest None declared

Aluminium extrudate used for safety parts in cars need to exhibit high yield strength and ductility, a combination that is not easily achieved. In this work, the mechanical properties and microstructure of profiles with a yield strength greater than 280MPa achieved by two different artificial ageing treatments were studied. Profiles from one of the heat treatments performed well in quasi-static compression testing while those from the other heat treatment clearly failed. The batch of profiles that failed showed higher uniform elongation in tensile testing but a lower reduction in area. However, the difference in bending angles in the three-point-bending test were not as pronounced. Microscopic investigation of polished sections and fracture surfaces revealed that failure is dominated by the fracture of intermetallic phases resulting in voids. The growth and coalescence of these voids is facilitated by another population of smaller voids within the matrix, presumably nucleating at secondary phases.

We describe x-ray photon correlation spectroscopy (XPCS) experiments tracking the motion of gold nanoparticles within solutions of high-molecular-weight polystyrene. Over displacements from nanometers to tens of nanometers, the particles undergo subdiffusive motion that is dictated by the temporal evolution of the entangled polymer mesh in the immediate vicinity of the particles. The results thus provide a novel microscopic dynamical characterization of this key structural property of polymers and more broadly demonstrate the capability of XPCS-based microrheology to interrogate heterogeneous mechanical environments in nanostructured soft materials.

The facile phase-transfer of large, water-soluble metal nanoparticles to nonpolar solvent is reported here. Thiol-terminated polystyrene (PS-SH) is ligand-exchanged onto water-soluble metal nanoparticles in single-phase acetone/water mixtures, generating a precipitate. The solvent is then removed and the particles are redissolved in nonpolar solvent. This approach is demonstrated for nanoparticles of different metal (Au and Ag), size (3 to100 nm), shape (spheres, rods, and wires, etc.), and leaving ligand (citrate, cetyltrimethylammonium bromide, poly(vinylpyrrolidone), and 4-dimethylaminopyridine. The resulting PS-SH-stabilized nanoparticles maintain their initial size and shape, and are highly stable. They are soluble in various organic solvents (toluene, benzene, chloroform, dichloromethane, and tetrahydrofuran), and can be readily dried, purified, and re-dissolved. This method makes possible the utilization of a full range of existing nanoparticle cores in nonpolar solvents with a single ligand. It provides access to numerous nanomaterials that cannot be obtained through direct synthesis in nonpolar solvent, and is expected to be of significant value in a number of applications.