Structural and optical characterization of nanoalloys mixing gold or silver with aluminium or indium: evolution under various reactive environments.

In this study, the atomic and chemical structure and the optical response of AxB1-x bimetallic nanoparticles (BNPs) combining gold or silver (A) with aluminium or indium (B) were investigated at various stoichiometries in order to examine if stable alloyed phases could exist and promote the emergence of localized surface plasmon resonance (LSPR) in the UV range. The structure and morphology of BNPs of a few nanometres, produced by laser vaporization, were analysed by transmission electron microscopy (TEM) and optical absorption measurements were performed on matrix-embedded BNPs. Information about the oxidation state of the BNPs can be inferred from a comparison between experimental optical spectra and Mie calculations in the dipolar approximation. The BNPs' internal structures were further investigated by additional characterization techniques. Firstly, in situ X-ray photoelectron spectroscopy provided information about the chemical state of the constituent elements and their evolution with time. Secondly, synchrotron-based X-ray scattering techniques were performed on Ag-Al BNPs in a wide-angle configuration under grazing incidence, giving complementary information about structural and morphological heterogeneities in the BNPs. Finally, the restructuring of the partially oxidized Au0.33Al0.67 BNPs annealed in a reducing atmosphere was also attempted by environmental TEM. The complementary techniques of characterization show that silver-based Ag-In and Ag-Al BNPs form metallic silver-rich alloyed cores surrounded by an indium or aluminium oxide shell. The initial LSPR is in the UV range for both systems, but the difference in the kinetics of oxidation between indium and aluminium involves less blue-shifted LSPR for Ag-Al BNPs. In the case of gold-based BNPs, we show evidence of ordered nanoalloys just after air exposure and the appearance of gold and indium (or aluminium) demixing during oxidation. The initial LSPR of Au-In BNPs is the one the most in the UV range among the four systems, with an LSPR peak centred at 254 nm, which may be a sign of the formation of the Au0.33In0.67 alloy. Nevertheless, strategies to preserve BNPs from oxidation have to be developed.

Study of Molecular-Level Dispersion of Pristine Graphene in Aqueous Media via Polyvinyl Alcohol Coil Physisorption.

Graphene has been widely used as a nanofiller in advanced electronic devices and nanocomposite materials to achieve enhanced electronic, mechanical, and barrier properties. Adequate polymers play the role of the composite matrix and can assist in the liquid-phase exfoliation of pristine graphene without any heavy chemical modification and the detriment of the properties of graphene. This stabilization mechanism is generally attributed to the steric forces formed between the polymer-adsorbed adsorbent. However, the key influence of the polymer concentration on the maximum graphene content in the colloidal solutions is still unclear. In this study, three different molar weights of water-soluble polyvinyl alcohol (PVA) were used for graphene dispersion. The influence of the PVA concentration on the graphene dispersion was systematically studied. Based on Flory's theory, we first proposed a model to describe the polymer adsorption process in the graphene/PVA/water ternary system in the "dilute" regime and simulated the adsorption-free energy changes during this transformation. This model is in good agreement with the experimental results and explains the critical polymer concentration, Cc, allowing the optimization of the graphene/polymer ratio. This fundamental understanding of polymer physisorption on 2D materials provides a simple method for producing nanocomposites with controlled nanosheet/polymer ratios and structures, which are of great interest for energy devices and biomaterials.

Superior Semicircular Canal Dehiscence by Superior Petrosal Sinus: Proposal for Classification.

OBJECTIVES: This study aimed to present 3 different clinical stages in patients presenting with superior semicircular canal dehiscence (SSCD) by the superior petrosal sinus (SPS). A specific 3-class classification based on clinical, radiological, and audio-vestibular arguments is proposed. MATERIALS AND METHODS: We retrospectively compared clinical and radiological findings in 3 patients with different degrees of audio-vestibular dysfunction in whom the imagery evocated the diagnosis of SSCD by SPS. Imaging sensitivity was improved by combining inner ear high-resolution computed tomography (HRCT) scan and magnetic resonance imaging in fusion, allowing us to compare and corroborate clinical and audio-vestibular findings in each case with the imagery. RESULTS: HRCT and 3T inner ear fusion imaging highlighted a direct contact and/or compression between SPS and the membranous superior semicircular canal (SSC). We propose a new classification of SSCD by SPS. Class "A" corresponds to an HRCT image with a "cookie bite" and thin bone still covering the SSC. Class "B" corresponds to a "cookie bite" image with confirmed contact between the SPS wall and the membranous SSC in MRI labyrinthine sequences. Class "C" type corresponds to a "cookie bite" image, contact, and obvious compression of the membranous SSC by SPS on MRI sequences. CONCLUSION: Anatomical systematization is needed for daily practice. This classification of SSCD by SPS would contribute to a better understanding of the wide variety and variability in the occurrence and onset of symptoms.

Highly ductile amorphous oxide at room temperature and high strain rate.

Oxide glasses are an integral part of the modern world, but their usefulness can be limited by their characteristic brittleness at room temperature. We show that amorphous aluminum oxide can permanently deform without fracture at room temperature and high strain rate by a viscous creep mechanism. These thin-films can reach flow stress at room temperature and can flow plastically up to a total elongation of 100%, provided that the material is dense and free of geometrical flaws. Our study demonstrates a much higher ductility for an amorphous oxide at low temperature than previous observations. This discovery may facilitate the realization of damage-tolerant glass materials that contribute in new ways, with the potential to improve the mechanical resistance and reliability of applications such as electronic devices and batteries.

Electroactive Area from Porous Oxide Films Loaded with Silver Nanoparticles: Electrochemical and Electron Tomography Observations.

Electrochemical studies of nanomaterial-based electrodes have been widely developed for catalyst and energy-harvesting applications. The evolution of these electrodes over time and their efficiency have been extensively studied and analyzed in order to optimize their performance. However, the electrochemical responses of electrodes are rarely studied in terms of the position of the active species within these electrodes. In this paper, we highlight that the spatial location of silver nanoparticles (NPs) embedded inside semiconductive porous films, TiO2 or Fe2O3, is crucial for the electrochemical response. In fact, by using cycling voltammetry and electron tomography experiments, we show the existence of an "electroactive area", corresponding to a reduced thickness of the sample in close vicinity to a fluorine-doped tin oxide substrate where most of the electrochemical responses originate. Our results demonstrate that, for a film thickness of several hundred nanometers, only less than 30 nm close to the substrate responds electrochemically. However, cyclic voltammetry empties the electroactive area of silver NPs. Therefore, application of chronoamperometry coupled to irradiation allowed regeneration of this area thanks to an increased diffusion of silver species. In this paper, we also show the significant diffusion of silver species within the film during electrochemical experiments, a phenomenon even increased by irradiation. These results are therefore an important step that shows the importance of the localization of active species within a porous film and help in understanding and increasing the durability of nanomaterial-based electrodes.

Multimodal Biosensing on Paper-Based Platform Fabricated by Plasmonic Calligraphy Using Gold Nanobypiramids Ink.

In this work, we design new plasmonic paper-based nanoplatforms with interesting capabilities in terms of sensitivity, efficiency, and reproducibility for promoting multimodal biodetection via Localized Surface Plasmon Resonance (LSPR), Surface Enhanced Raman Spectroscopy (SERS), and Metal Enhanced Fluorescence (MEF). To succeed, we exploit the unique optical properties of gold nanobipyramids (AuBPs) deposited onto the cellulose fibers via plasmonic calligraphy using a commercial pen. The first step of the biosensing protocol was to precisely graft the previously chemically-formed p-aminothiophenol@Biotin system, as active recognition element for target streptavidin detection, onto the plasmonic nanoplatform. The specific capture of the target protein was successfully demonstrated using three complementary sensing techniques. As a result, while the LSPR based sensing capabilities of the nanoplatform were proved by successive 13-18 nm red shifts of the longitudinal LSPR associated with the change of the surface RI after each step. By employing the ultrasensitive SERS technique, we were able to indirectly confirm the molecular identification of the biotin-streptavidin interaction due to the protein fingerprint bands assigned to amide I, amide III, and Trp vibrations. Additionally, the formed biotin-streptavidin complex acted as a spacer to ensure an optimal distance between the AuBP surface and the Alexa 680 fluorophore for achieving a 2-fold fluorescence emission enhancement of streptavidin@Alexa 680 on the biotinylated nanoplatform compared to the same complex on bare paper (near the plasmonic lines), implementing thus a novel MEF sensing nanoplatform. Finally, by integrating multiple LSPR, SERS, and MEF nanosensors with multiplex capability into a single flexible and portable plasmonic nanoplatform, we could overcome important limits in the field of portable point-of-care diagnostics.

Shape-selective synthesis of nanoceria for degradation of paraoxon as a chemical warfare simulant.

Repeated attacks using organophosphorus compounds, in military conflicts or terrorist acts, necessitate developing inexpensive and readily available decontamination systems. Nanosized cerium oxide is a suitable candidate, acting as a heterogeneous catalyst for the degradation of organophosphorus compounds such as VX agent or sarin. However, the reaction mechanism of the phosphatase mimetic activity of CeO2 nanoparticles is not fully described. Adsorption, surface-promoted hydrolysis, and desorption cycles strongly depend on the physico-chemical characteristics of the facets. In this study, CeO2 nanoparticles with different shapes were elaborated by hydrothermal synthesis. Nano-octahedra, nanocubes, or nanorods were selectively obtained under different conditions (temperature, concentration and nature of the precursors). The degradation activity according to the crystal faces was evaluated in vitro by measuring the degradation kinetics of paraoxon organophosphate in the presence of CeO2 nanoparticles. The results show an influence of both specific surface area and crystal faces of the nanoparticles, with higher activity for {111} facets compared to {100} facets at 32 °C. The relative activity between the facets is ascribed to the adsorption probability, assuming coordination between the phosphoryl oxygen and cerium atoms, but also to the surface density of the Ce doublets with relevant spacing for phosphatase mimetic activity.

Electron Tomography of Plasmonic Au Nanoparticles Dispersed in a TiO2 Dielectric Matrix.

Plasmonic Au nanoparticles (AuNPs) embedded into a TiO2 dielectric matrix were analyzed by combining two-dimensional and three-dimensional electron microscopy techniques. The preparation method was reactive magnetron sputtering, followed by thermal annealing treatments at 400 and 600 °C. The goal was to assess the nanostructural characteristics and correlate them with the optical properties of the AuNPs, particularly the localized surface plasmon resonance (LSPR) behavior. High-angle annular dark field-scanning transmission electron microscopy results showed the presence of small-sized AuNPs (quantum size regime) in the as-deposited Au-TiO2 film, resulting in a negligible LSPR response. The in-vacuum thermal annealing at 400 °C induced the formation of intermediate-sized nanoparticles (NPs), in the range of 10-40 nm, which led to the appearance of a well-defined LSPR band, positioned at 636 nm. Electron tomography revealed that most of the NPs are small-sized and are embedded into the TiO2 matrix, whereas the larger NPs are located at the surface. Annealing at 600 °C promotes a bimodal size distribution with intermediate-sized NPs embedded in the matrix and big-sized NPs, up to 100 nm, appearing at the surface. The latter are responsible for a broadening and a redshift, to 645 nm, in the LSPR band because of increase of scattering-to-absorption ratio. Beyond differentiating and quantifying the surface and embedded NPs, electron tomography also provided the identification of "hot-spots". The presence of NPs at the surface, individual or in dimers, permits adsorption sites for LSPR sensing and for surface-enhanced spectroscopies, such as surface-enhanced Raman scattering.

Obtaining 3D Chemical Maps by Energy Filtered Transmission Electron Microscopy Tomography.

Energy filtered transmission electron microscopy tomography (EFTEM tomography) can provide three-dimensional (3D) chemical maps of materials at a nanometric scale. EFTEM tomography can separate chemical elements that are very difficult to distinguish using other imaging techniques. The experimental protocol described here shows how to create 3D chemical maps to understand the chemical distribution and morphology of a material. Sample preparation steps for data segmentation are presented. This protocol permits the 3D distribution analysis of chemical elements in a nanometric sample. However, it should be noted that currently, the 3D chemical maps can only be generated for samples that are not beam sensitive, since the recording of filtered images requires long exposure times to an intense electron beam. The protocol was applied to quantify the chemical distribution of the components of two different heterogeneous catalyst supports. In the first study, the chemical distribution of aluminum and titanium in titania-alumina supports was analyzed. The samples were prepared using the swing-pH method. In the second, the chemical distribution of aluminum and silicon in silica-alumina supports that were prepared using the sol-powder and mechanical mixture methods was examined.

Evaluation of noise and blur effects with SIRT-FISTA-TV reconstruction algorithm: Application to fast environmental transmission electron tomography.

Fast tomography in Environmental Transmission Electron Microscopy (ETEM) is of a great interest for in situ experiments where it allows to observe 3D real-time evolution of nanomaterials under operating conditions. In this context, we are working on speeding up the acquisition step to a few seconds mainly with applications on nanocatalysts. In order to accomplish such rapid acquisitions of the required tilt series of projections, a modern 4K high-speed camera is used, that can capture up to 100 images per second in a 2K binning mode. However, due to the fast rotation of the sample during the tilt procedure, noise and blur effects may occur in many projections which in turn would lead to poor quality reconstructions. Blurred projections make classical reconstruction algorithms inappropriate and require the use of prior information. In this work, a regularized algebraic reconstruction algorithm named SIRT-FISTA-TV is proposed. The performance of this algorithm using blurred data is studied by means of a numerical blur introduced into simulated images series to mimic possible mechanical instabilities/drifts during fast acquisitions. We also present reconstruction results from noisy data to show the robustness of the algorithm to noise. Finally, we show reconstructions with experimental datasets and we demonstrate the interest of fast tomography with an ultra-fast acquisition performed under environmental conditions, i.e. gas and temperature, in the ETEM. Compared to classically used SIRT and SART approaches, our proposed SIRT-FISTA-TV reconstruction algorithm provides higher quality tomograms allowing easier segmentation of the reconstructed volume for a better final processing and analysis.

The core contribution of transmission electron microscopy to functional nanomaterials engineering.

Research on nanomaterials and nanostructured materials is burgeoning because their numerous and versatile applications contribute to solve societal needs in the domain of medicine, energy, environment and STICs. Optimizing their properties requires in-depth analysis of their structural, morphological and chemical features at the nanoscale. In a transmission electron microscope (TEM), combining tomography with electron energy loss spectroscopy and high-magnification imaging in high-angle annular dark-field mode provides access to all features of the same object. Today, TEM experiments in three dimensions are paramount to solve tough structural problems associated with nanoscale matter. This approach allowed a thorough morphological description of silica fibers. Moreover, quantitative analysis of the mesoporous network of binary metal oxide prepared by template-assisted spray-drying was performed, and the homogeneity of amino functionalized metal-organic frameworks was assessed. Besides, the morphology and internal structure of metal phosphide nanoparticles was deciphered, providing a milestone for understanding phase segregation at the nanoscale. By extrapolating to larger classes of materials, from soft matter to hard metals and/or ceramics, this approach allows probing small volumes and uncovering materials characteristics and properties at two or three dimensions. Altogether, this feature article aims at providing (nano)materials scientists with a representative set of examples that illustrates the capabilities of modern TEM and tomography, which can be transposed to their own research.

Three-dimensional chemistry of multiphase nanomaterials by energy-filtered transmission electron microscopy tomography.

A three-dimensional (3D) study of multiphase nanostructures by chemically selective electron tomography combining tomographic approach and energy-filtered imaging is reported. The implementation of this technique at the nanometer scale requires careful procedures for data acquisition, computing, and analysis. Based on the performances of modern transmission electron microscopy equipment and on developments in data processing, electron tomography in the energy-filtered imaging mode is shown to be a very appropriate analysis tool to provide 3D chemical maps at the nanoscale. Two examples highlight the usefulness of analytical electron tomography to investigate inhomogeneous 3D nanostructures, such as multiphase specimens or core-shell nanoparticles. The capability of discerning in a silica-alumina porous particle the two different components is illustrated. A quantitative analysis in the whole specimen and toward the pore surface is reported. This tool is shown to open new perspectives in catalysis by providing a way to characterize precisely 3D nanostructures from a chemical point of view.

3D-TEM investigation of the nanostructure of a δ-Al2O3 catalyst support decorated with Pd nanoparticles.

The electron tomography technique applied in a quantitative way allowed us to characterize a heterogeneous catalyst made of Pd nanoparticles deposited on a δ-Al(2)O(3) lamellar support. In the first step, high resolution tomographic experiments carried out on several typical areas of support have confirmed the hypothesis of formation of δ-Al(2)O(3) proposed in the literature by the coalescence of lateral facets of the γ-Al(2)O(3) precursor. A bimodal porosity was also observed in the arrangement of δ-Al(2)O(3) platelets. In the second step, the Pd nanoparticles were found preferentially anchored on the lateral facets of δ-Al(2)O(3) platelets or on the defects situated on their basal planes. From a general point of view, we have demonstrated once again that the electron tomography technique implemented with nanometre resolution provides unique insight into the structure, morphology and spatial arrangement of components in a complex 3D nanostructure.

Analytical electron tomography mapping of the SiC pore oxidation at the nanoscale.

Silicon carbide is a ceramic material that has been widely studied because of its potential applications, ranging from electronics to heterogeneous catalysis. Recently, a new type of SiC materials with a medium specific surface area and thermal conductivity, called ß-SiC, has attracted overgrowing interest as a new class of catalyst support in several catalytic reactions. A primary electron tomography study, performed in usual mode, has revealed a dual surface structure defined by two types of porosities made of networks of connected channels with sizes larger than 50 nm and ink-bottled pores with sizes spanning from 4 to 50 nm. Depending on the solvent nature, metal nanoparticles could be selectively deposited inside one of the two porosities, a fact that illustrates a selective wetting titration of the two types of surfaces by different liquids. The explaining hypothesis that has been put forward was that this selectivity against solvents is related to the pore surface oxidation degree of the two types of pores. A new technique of analytical electron tomography, where the series of projections used to reconstruct the volume of an object is recorded in energy filtered mode (EFTEM), has been implemented to map the pore oxidation state and to correlate it with the morphology and the accessibility of the porous network. Applied, for the first time, at a nanoscale resolution, this technique allowed us to obtain 3D elemental maps of different elements present in the analysed porous grains, in particular oxygen; we found thus that the interconnected channel pores are more rapidly oxidized than the ink-bottled ones. Alternatively, our study highlights the great interest of this method that opens the way for obtaining precise information on the chemical composition of a 3D surface at a nanometer scale.

An efficient strategy to drive nanoparticles into carbon nanotubes and the remarkable effect of confinement on their catalytic performance.

Are you in? Bimetallic PtRu nanoparticles have been selectively confined inside or deposited outside carbon nanotubes (see picture). The confined nanoparticles display significantly higher selectivity and catalytic activity in hydrogenation reactions.