Sample thickness affects contrast and measured shape in TEM images and in electron tomograms.

We investigated the effect of nanoparticle (NP) image broadening and its contrast change dependence on a support matrix thickness in a transmission electron microscope (TEM). We measured the effect of NP size and atomic number on its image broadening. Based on the experimental TEM images we generated tomograms of NPs on four types of support matrix. The measured shape aspect ratio of the NPs in such tomograms depends on the geometry of the support matrix. For example, the aspect ratio of 6 nm NP placed on a thin film with window-frame support is 1.14, while the aspect ratio of 6 nm NP on a rod-shaped support with 910 nm diameter is 1.67 in a tomogram.

Iron phosphide nanocrystals as an air-stable heterogeneous catalyst for liquid-phase nitrile hydrogenation.

Iron-based heterogeneous catalysts are ideal metal catalysts owing to their abundance and low-toxicity. However, conventional iron nanoparticle catalysts exhibit extremely low activity in liquid-phase reactions and lack air stability. Previous attempts to encapsulate iron nanoparticles in shell materials toward air stability improvement were offset by the low activity of the iron nanoparticles. To overcome the trade-off between activity and stability in conventional iron nanoparticle catalysts, we developed air-stable iron phosphide nanocrystal catalysts. The iron phosphide nanocrystal exhibits high activity for liquid-phase nitrile hydrogenation, whereas the conventional iron nanoparticles demonstrate no activity. Furthermore, the air stability of the iron phosphide nanocrystal allows facile immobilization on appropriate supports, wherein TiO2 enhances the activity. The resulting TiO2-supported iron phosphide nanocrystal successfully converts various nitriles to primary amines and demonstrates high reusability. The development of air-stable and active iron phosphide nanocrystal catalysts significantly expands the application scope of iron catalysts.

MRI-MECH: mechanics-informed MRI to estimate esophageal health.

Dynamic magnetic resonance imaging (MRI) is a popular medical imaging technique that generates image sequences of the flow of a contrast material inside tissues and organs. However, its application to imaging bolus movement through the esophagus has only been demonstrated in few feasibility studies and is relatively unexplored. In this work, we present a computational framework called mechanics-informed MRI (MRI-MECH) that enhances that capability, thereby increasing the applicability of dynamic MRI for diagnosing esophageal disorders. Pineapple juice was used as the swallowed contrast material for the dynamic MRI, and the MRI image sequence was used as input to the MRI-MECH. The MRI-MECH modeled the esophagus as a flexible one-dimensional tube, and the elastic tube walls followed a linear tube law. Flow through the esophagus was governed by one-dimensional mass and momentum conservation equations. These equations were solved using a physics-informed neural network. The physics-informed neural network minimized the difference between the measurements from the MRI and model predictions and ensured that the physics of the fluid flow problem was always followed. MRI-MECH calculated the fluid velocity and pressure during esophageal transit and estimated the mechanical health of the esophagus by calculating wall stiffness and active relaxation. Additionally, MRI-MECH predicted missing information about the lower esophageal sphincter during the emptying process, demonstrating its applicability to scenarios with missing data or poor image resolution. In addition to potentially improving clinical decisions based on quantitative estimates of the mechanical health of the esophagus, MRI-MECH can also be adapted for application to other medical imaging modalities to enhance their functionality.

Low-aberration ExB deflector optics for scanning electron microscopy.

To suppress aberrations in the signal electron optics of a scanning electron microscope, we propose ExB deflector (deflector with superimposed electric and magnetic fields) optics that cancel the aberrations generated during large-angle deflection. This improves the resolution of the angle or position of the signal electrons on the sample surface, allowing them to be discriminately detected. The proposed optics consist of two ExB deflectors and a transfer system with two 4-f systems, or systems that have four times the focal length, placed between them. This configuration maintains the symmetry of the electron beam trajectory throughout the transfer system such that aberrations generated by the first ExB deflector are negated by the second. The effect of the proposed optics was confirmed using a ray-tracing simulation of the electron beam, and the aberration was reduced to at most one-tenth of that in the case with only one ExB deflector. Furthermore, as an example, we examined the implementation of the proposed ExB deflector optics to resolve the signal electron angle and found that the sample emission angle range of 80° can be resolved with an angular resolution of 1°. Therefore, the proposed ExB deflector optics can be applied to the signal electron optics of a scanning electron microscope to improve the resolution of the signal electrons.

Virtual disease landscape using mechanics-informed machine learning: Application to esophageal disorders.

Esophageal disorders are related to the mechanical properties and function of the esophageal wall. Therefore, to understand the underlying fundamental mechanisms behind various esophageal disorders, it is crucial to map mechanical behavior of the esophageal wall in terms of mechanics-based parameters corresponding to altered bolus transit and increased intrabolus pressure. We present a hybrid framework that combines fluid mechanics and machine learning to identify the underlying physics of various esophageal disorders (motility disorders, eosinophilic esophagitis, reflux disease, scleroderma esophagus) and maps them onto a parameter space which we call the virtual disease landscape (VDL). A one-dimensional inverse model processes the output from an esophageal diagnostic device called the functional lumen imaging probe (FLIP) to estimate the mechanical "health" of the esophagus by predicting a set of mechanics-based parameters such as esophageal wall stiffness, muscle contraction pattern and active relaxation of esophageal wall. The mechanics-based parameters were then used to train a neural network that consists of a variational autoencoder that generated a latent space and a side network that predicted mechanical work metrics for estimating esophagogastric junction motility. The latent vectors along with a set of discrete mechanics-based parameters define the VDL and formed clusters corresponding to specific esophageal disorders. The VDL not only distinguishes among disorders but also displayed disease progression over time. Finally, we demonstrated the clinical applicability of this framework for estimating the effectiveness of a treatment and tracking patients' condition after a treatment.

Interpretation of mean free path values derived from off-axis electron holography amplitude measurements.

In this work, we have explored the factors which govern mean free path values obtained from off-axis electron holography measurements. Firstly, we explore the topic from a theoretical perspective, and show that the mean amplitude reconstructed from off-axis holograms is due to the coherent portion of the direct, central object-transmitted beam only - it is not affected by the presence or absence of other scattered beams. Secondly, we present a detailed experimental study which compares mean free path values obtained from hologram sideband, centreband, EELS, and TEM measurements as a function of optical collection angle and energy-loss-filtering. These results confirm that the coherent portion of the direct beam defines the mean amplitude, and additionally show that the coherent portion corresponds to the conventional energy-filtered signal (with threshold 5 eV in this work). Finally, we present summary measurements from a selection of different materials, and compare the results against a simple electron scattering model. This study reinforces the claim that the mean amplitude is defined by the energy-filtered direct beam, and confirms that the contributions of elastic and inelastic scattering to the total mean free path are broadly in line with theoretical expectations for these different materials. These results in aggregate indicate that neither experimental collection angles nor enhanced sensitivity to low-loss phonon scattering affect the mean amplitude signal arising from off-axis holography reconstructions, nor the associated mean free path values which are derived from this mean amplitude.

Origin of spurious intensity in vacuum near sample edge in bright field TEM images.

Bright-field transmission electron microscope (BFTEM) images exhibit spurious image intensity in the vacuum near the sample edge. The spurious intensity gradually decreases with increasing distance from the sample edge. By taking into account angular and energy loss distribution of the scattered electrons and lens aberrations, the origin of the spurious intensity of BFTEM images can be explained. The spurious intensity extent and magnitude can be significantly reduced by using either electron energy filtering or a small collection semiangle.

Phosphorus-Alloying as a Powerful Method for Designing Highly Active and Durable Metal Nanoparticle Catalysts for the Deoxygenation of Sulfoxides: Ligand and Ensemble Effects of Phosphorus.

The modification of metal nanoparticles (NPs) by incorporating additional metals is a key technique for developing novel catalysts. However, the effects of incorporating nonmetals into metal NPs have not been widely explored, particularly in the field of organic synthesis. In this study, we demonstrate that phosphorus (P)-alloying significantly increases the activity of precious metal NPs for the deoxygenation of sulfoxides into sulfides. In particular, ruthenium phosphide NPs exhibit an excellent catalytic activity and high durability against sulfur-poisoning, outperforming conventional catalysts. Various sulfoxides, including drug intermediates, were deoxygenated to sulfides with excellent yields. Detailed investigations into the structure-activity relationship revealed that P-alloying plays a dual role: it establishes a ligand effect on the electron transfer from Ru to P, facilitating the production of active hydrogen species, and has an ensemble effect on the formation of the Ru-P bond, preventing strong coordination with sulfide products. These effects combine to increase the catalytic performance of ruthenium phosphide NPs. These results demonstrate that P-alloying is an efficient method to improve the metal NP catalysis for diverse organic synthesis.

Single-Crystal Cobalt Phosphide Nanorods as a High-Performance Catalyst for Reductive Amination of Carbonyl Compounds.

The development of metal phosphide catalysts for organic synthesis is still in its early stages. Herein, we report the successful synthesis of single-crystal cobalt phosphide nanorods (Co2P NRs) containing coordinatively unsaturated Co-Co active sites, which serve as a new class of air-stable, highly active, and reusable heterogeneous catalysts for the reductive amination of carbonyl compounds. The Co2P NR catalyst showed high activity for the transformation of a broad range of carbonyl compounds to their corresponding primary amines using an aqueous ammonia solution or ammonium acetate as a green amination reagent at 1 bar of H2 pressure; these conditions are far milder than previously reported. The air stability and high activity of the Co2P NRs is noteworthy, as conventional Co catalysts are air-sensitive (pyrophorous) and show no activity for this transformation under mild conditions. P-alloying is therefore of considerable importance for nanoengineering air-stable and highly active non-noble-metal catalysts for organic synthesis.

A nickel phosphide nanoalloy catalyst for the C-3 alkylation of oxindoles with alcohols.

Although transition metal phosphides are well studied as electrocatalysts and hydrotreating catalysts, the application of metal phosphides in organic synthesis is rare, and cooperative catalysis between metal phosphides and supports remains unexplored. Herein, we report that a cerium dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/CeO2) efficiently promoted the C-3 alkylation of oxindoles with alcohols without any additives through the borrowing hydrogen methodology. Oxindoles were alkylated with various alcohols to provide the corresponding C-3 alkylated oxindoles in high yields. This is the first catalytic system for the C-3 alkylation of oxindoles with alcohols using a non-precious metal-based heterogeneous catalyst. The catalytic activity of nano-Ni2P/CeO2 was comparable to that reported for precious metal-based catalysts. Moreover, nano-Ni2P/CeO2 was easily recoverable and reusable without any significant loss of activity. Control experiments revealed that the Ni2P nanoalloy and the CeO2 support functioned cooperatively, leading to a high catalytic performance.

Quasi-static 3D structure of graphene ripple measured using aberration-corrected TEM.

Free-standing graphene has a three-dimensional (3D) structure, called a ripple, rather than a perfect two-dimensional (2D) crystal. Since theoretical calculations suggest that a ripple strongly influences various fundamental physicochemical properties of graphene, it is important to clarify the ripple structure quantitatively in experiments. This paper proposes a new method of measuring the 3D atomic structure of a ripple by using aberration-corrected transmission electron microscopy (TEM). The method utilizes the fact that the 2D contrast of a TEM image is sensitive to the height of a six-membered ring. The proposed method is experimentally applied to a monolayer graphene, and the 3D atomic arrangements of consecutively acquired TEM images are reconstructed. In that experiment, the specimen is found to be moving upward. Furthermore, the atomic arrangement can be approximated as a composite of two structures consisting of a 3D ripple and a 2D plane. The ripple is represented as a superposition of sinusoidal waves, with their wave vectors coinciding with the specific direction of the six-membered ring. The time dependences of the height and lateral size of the ripple are also measured.

Wave field reconstruction and phase imaging by electron diffractive imaging.

In electron diffractive imaging, the phase image of a sample is reconstructed from its diffraction intensity through iterative calculations. The principle of this method is based on the Fourier transform relation between the real-space wave field transmitted by the sample and its Fraunhofer diffraction wave field. Since Gerchberg's experimental work in 1972, various advancements have been achieved, which have substantially improved the quality of the reconstructed phase images and extended the applicable range of the method. In this review article, the principle of diffractive imaging, various experimental processes using electron beams and application to specific samples are explained in detail.

Ni2 P Nanoalloy as an Air-Stable and Versatile Hydrogenation Catalyst in Water: P-Alloying Strategy for Designing Smart Catalysts.

Non-noble metal-based hydrogenation catalysts have limited practical applications because they exhibit low activity, require harsh reaction conditions, and are unstable in air. To overcome these limitations, herein we propose the alloying of non-noble metal nanoparticles with phosphorus as a promising strategy for developing smart catalysts that exhibit both excellent activity and air stability. We synthesized a novel nickel phosphide nanoalloy (nano-Ni2 P) with coordinatively unsaturated Ni active sites. Unlike conventional air-unstable non-noble metal catalysts, nano-Ni2 P retained its metallic nature in air, and exhibited a high activity for the hydrogenation of various substrates with polar functional groups, such as aldehydes, ketones, nitriles, and nitroarenes to the desired products in excellent yields in water. Furthermore, the used nano-Ni2 P catalyst was easy to handle in air and could be reused without pretreatment, providing a simple and clean catalyst system for general hydrogenation reactions.

Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2 pressure.

Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2.

Progress in environmental high-voltage transmission electron microscopy for nanomaterials.

A new environmental high-voltage transmission electron microscope (E-HVEM) was developed by Nagoya University in collaboration with JEOL Ltd. An open-type environmental cell was employed to enable in-situ observations of chemical reactions on catalyst particles as well as mechanical deformation in gaseous conditions. One of the reasons for success was the application of high-voltage transmission electron microscopy to environmental (in-situ) observations in the gas atmosphere because of high transmission of electrons through gas layers and thick samples. Knock-on damages to samples by high-energy electrons were carefully considered. In this paper, we describe the detailed design of the E-HVEM, recent developments and various applications. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.

A cobalt phosphide catalyst for the hydrogenation of nitriles.

The study of metal phosphide catalysts for organic synthesis is rare. We present, for the first time, a well-defined nano-cobalt phosphide (nano-Co2P) that can serve as a new class of catalysts for the hydrogenation of nitriles to primary amines. While earth-abundant metal catalysts for nitrile hydrogenation generally suffer from air-instability (pyrophoricity), low activity and the need for harsh reaction conditions, nano-Co2P shows both air-stability and remarkably high activity for the hydrogenation of valeronitrile with an excellent turnover number exceeding 58000, which is over 20- to 500-fold greater than that of those previously reported. Moreover, nano-Co2P efficiently promotes the hydrogenation of a wide range of nitriles, which include di- and tetra-nitriles, to the corresponding primary amines even under just 1 bar of H2 pressure, far milder than the conventional reaction conditions. Detailed spectroscopic studies reveal that the high performance of nano-Co2P is attributed to its air-stable metallic nature and the increase of the d-electron density of Co near the Fermi level by the phosphidation of Co, which thus leads to the accelerated activation of both nitrile and H2. Such a phosphidation provides a promising method for the design of an advanced catalyst with high activity and stability in highly efficient and environmentally benign hydrogenations.

Empirical determination of transmission attenuation curves in mass-thickness contrast TEM imaging.

The thickness dependence of electron transmission, observed as mass-thickness contrast in transmission electron microscopy (TEM) images, was precisely measured for polystyrene and amorphous carbon. In the early stages of transmission attenuation, a slight increase in the attenuation coefficient was observed, although a constant value is generally expected according to Beer's law. In contrast, as generally known as nonlinear behavior due to multiple scattering, the coefficient decreased during the intermediate stages. In the later stages, an asymptotic behavior in which the transmission approached a constant value was observed. Based on these results, a function containing three parameters was proposed to express the nonlinear transmission attenuation with increasing thickness. Results obtained using this new model and other previously proposed models were compared with experimental data measured over a wide range of conditions: acceleration voltage of 200-3000 kV, objective aperture radius of 0.85-30 nm-1, and thickness of 0.25-10 µm. It was confirmed that our model can well reproduce all of the measurements with a high degree of precision, while the other models were valid only under limited imaging conditions and/or for limited thickness ranges. Thus, a quantitative description of transmission attenuation under normal TEM observation conditions, that is, over a thickness range without physical absorption and a scattering angular range of a few degrees, is finally obtained after more than a century since early studies on ß-rays. Based on a simplified model of multiple scattering, the characteristic behavior of the attenuation curves is intuitively explained.

Precise method for measuring spatial coherence in TEM beams using Airy diffraction patterns.

We have developed a method to precisely measure spatial coherence in electron beams. The method does not require an electron biprism and can be implemented in existing analytical transmission electron microscopes equipped with a post-column energy filter. By fitting the Airy diffraction pattern of the selector aperture, various parameters such as geometric aberrations of the lens system and the point-spread function of the diffraction blurring are precisely determined. From the measurements of various beam diameters, components that are attributed to the partial spatial coherence are successfully separated from the point-spread functions. A linear relationship between the spatial coherence length and beam diameter is revealed, thus indicating that a wide range of coherence lengths can be determined by our proposed method as long as the coherence length remains >80% of the aperture diameter. A remarkable feature of this method is its ability to simultaneously determine diffraction blurring and lens aberrations. Possible applications of this method are also discussed.

Mild Hydrogenation of Amides to Amines over a Platinum-Vanadium Bimetallic Catalyst.

Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H2 and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H2 at 70 °C or 5 bar H2 at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.

Depth-resolution imaging of crystalline nanoclusters attached on and embedded in amorphous films using aberration-corrected TEM.

For observations of crystalline nanoclusters, the features and capabilities of depth-resolution imaging by aberration-corrected transmission electron microscopy (TEM) were investigated using image simulations and experiments for two types of samples. The first sample was gold clusters attached on an amorphous carbon film. The experimental through-focal series indicated that the focal plane for the cluster was shifted 3 nm from that for the supporting film. This difference is due to the depth-resolution imaging of the cluster and film, the mid-planes of which are separated by 3 nm along the depth direction (the electron incident direction). On the basis of this information, the three-dimensional configuration of the sample, such as the film thickness of 2 nm, was successfully illustrated. The second sample was a Zr66.7Ni33.3 metallic glass including a medium-range-order (MRO) structure, which was approximately considered to be a crystalline cluster with a diameter of 1.6 nm. In the experimental through-focal series, the lattice fringe of the MRO cluster was visible at limited focal conditions. Image simulations reproduced well the focal conditions and also indicated a structural condition for the visualization that the embedded cluster must be apart from the mid-plane of the matrix film. Similar to the case of the first sample, this result can be explained by the idea that the "effective focal planes" for the film and cluster are at different heights. This type of depth-resolution phase contrast imaging is possible only in aberration-corrected TEM and when the sample has a simple structure and is sufficiently thin for the kinematical scattering approximation.