Monodentate σ-Accepting Boron-Based Ligands Bearing Square-Planar Ni(0) Centers.

Transition metals are known to work as electron donors toward electron-accepting heavier-group-13 elements (Al, Ga, and In), called Z-type ligands. However, complexes with boron-based Z-type ligands are stable only in the presence of additional coordination units (the so-called "supported-ligand" strategy). Here, we report the synthesis and characterization of square-planar Ni(0) complexes that bear tris(perfluoroaryl)boranes as monodentate Z-type ligands, even though such coordination geometry has been traditionally associated with Ni(II) species based on the well-established ligand-field theory.

Rational partitioning of spectral feature space for effective clustering of massive spectral image data.

We have successfully proposed and demonstrated a clustering method that overcomes the "needle-in-a-haystack problem" (finding minuscule important regions from massive spectral image data sets). The needle-in-a-haystack problem is of central importance in the characterization of materials since in bulk materials, the properties of a very tiny region often dominate the entire function. To solve this problem, we propose that rational partitioning of the spectral feature space in which spectra are distributed, or defining of the decision boundaries for clustering, can be performed by focusing on the discrimination limit defined by the measurement noise and partitioning the space at intervals of this limit.

Variations of organic functional chemistry in carbonaceous matter from the asteroid 162173 Ryugu.

Primordial carbon delivered to the early earth by asteroids and meteorites provided a diverse source of extraterrestrial organics from pre-existing simple organic compounds, complex solar-irradiated macromolecules, and macromolecules from extended hydrothermal processing. Surface regolith collected by the Hayabusa2 spacecraft from the carbon-rich asteroid 162173 Ryugu present a unique opportunity to untangle the sources and processing history of carbonaceous matter. Here we show carbonaceous grains in Ryugu can be classified into three main populations defined by spectral shape: Highly aromatic (HA), Alkyl-Aromatic (AA), and IOM-like (IL).

Reversible Modulation of the Electronic and Spatial Environment around Ni(0) Centers Bearing Multifunctional Carbene Ligands with Triarylaluminum.

Designing and modulating the electronic and spatial environments surrounding metal centers is a crucial issue in a wide range of chemistry fields that use organometallic compounds. Herein, we demonstrate a Lewis-acid-mediated reversible expansion, contraction, and transformation of the spatial environment surrounding nickel(0) centers that bear -phosphine oxide-substituted -heterocyclic carbenes (henceforth referred to as (S)PoxIms). Reaction between tetrahedral (-κ-,-(S)PoxIm)Ni(CO) and Al(CF) smoothly afforded heterobimetallic Ni/Al species such as trigonal-planar {κ--Ni(CO)}(μ--(S)PoxIm){κ--Al(CF)} via a complexation-induced rotation of the -phosphine oxide moieties, while the addition of 4-dimethylaminopyridine resulted in the quantitative regeneration of the former Ni complexes.

Macromolecular organic matter in samples of the asteroid (162173) Ryugu.

Samples of the carbonaceous asteroid (162173) Ryugu were collected and brought to Earth by the Hayabusa2 spacecraft. We investigated the macromolecular organic matter in Ryugu samples and found that it contains aromatic and aliphatic carbon, ketone, and carboxyl functional groups. The spectroscopic features of the organic matter are consistent with those in chemically primitive carbonaceous chondrite meteorites that experienced parent-body aqueous alteration (reactions with liquid water).

Depolymerization of robust polyetheretherketone to regenerate monomer units using sulfur reagents.

Super engineering plastics, high-performance thermoplastic resins such as polyetheretherketone, and polyphenylene sulfide have been utilized in industries, owing to their high thermal stability and mechanical strength. However, their robustness hinders their depolymerization to produce monomers and low-weight molecules. Presently, chemical recycling for most super engineering plastics remains relatively unexplored.

Photoelectron shield for the first mirror of a soft X-ray beamline.

At a soft X-ray beamline with an undulator source, significant heat generation at the first-mirror chamber and light emission at the viewport were found, which can be explained by photoelectrons from the mirror. The chamber temperature increases up to approximately 50°C over a period of several hours. A photoelectron shield consisting of thin copper plates not only prevents the heat generation and light emission but also improves the pressure of the vacuum chamber, if a voltage of a few tens of V is applied to the shield.

Bent crystal Laue analyser combined with total reflection fluorescence X-ray absorption fine structure (BCLA + TRF-XAFS) and its application to surface studies.

A bent crystal Laue analyser (BCLA) is an X-ray energy analyser used for fluorescence X-ray absorption fine-structure (XAFS) spectroscopy to separate the fluorescence X-ray emission line of a target atom from the elastic scattering X-rays and other fluorescence emission lines. Here, the feasibility of the BCLA for total reflection fluorescence XAFS (TRF-XAFS), which has a long X-ray footprint on the substrate surface owing to grazing incidence, was tested. The focal line of the BCLA was adjusted on the X-ray footprint and the XAFS signal for one monolayer of Pt deposited on a 60 nm Au film with high sensitivity was obtained.

Azimuthal-rotation sample holder for molecular orientation analysis.

In this study, an azimuthal-rotation sample holder compatible with scanning transmission X-ray microscopy was developed. This holder exhibits improvement in the accuracy of rotation angles and reduces the displacement of the rotation axes during azimuthal rotation by using a crossed roller bearing. To evaluate the performance of the holder, the authors investigated the dependence of the optical density around the C K-edge absorption of π-orbital-oriented domains in natural spherical graphite on the rotational angle by using linearly horizontally and vertically polarized undulator radiation.

An Another Protocol to Make Sulfur Embedded Ultrathin Sections of Extraterrestrial Small Samples.

Another protocol to make sulfur embedded ultrathin sections was developed for STXM-XANES, AFM-IR and TEM analyses of organic materials in small extraterrestrial samples. Polymerized liquid sulfur-instead of low-viscosity liquid sulfur-is the embedding media in this protocol. Due to high viscosity of the polymerized sulfur, the embedded samples stay near the surface of polymerized liquid sulfur, which facilitates trimming of glassy sulfur and ultramicrotomy of tiny embedded samples.

Nanoscale crack initiation and propagation in carbon fiber/epoxy composites using synchrotron: 3D image data.

Crack initiation and propagation in carbon fiber-reinforced plastic (CFRP) was observed under the application of an opening load using nanoscopic synchrotron radiation X-ray computed tomography (nanoscopic SR X-CT) at a high spatial resolution of ∼50 nm. Two datasets of reconstructed and segmented images were produced in typical regions, namely in the thin and thick epoxy regions where the resin thickness between the adjacent carbon fibers was small and large, respectively. This novel study presents the first non-destructive three-dimensional (3D) visualization of resin deformation behavior around crack tips, and provides a valuable and unique insight for the future design of CFRPs.

Nanoscopic origin of cracks in carbon fibre-reinforced plastic composites.

Voids and cracks can fatally degrade structural materials such as metals and ceramics but are tolerated in carbon fibre-reinforced plastic (CFRP) composites if monitored to prevent their growth to a critical size. Thus, the use of CFRPs as aeronautical structural materials requires an understanding of microscopic crack formation. However, this crack-formation mechanism remains unclear because experimental difficulties have hindered studies of relevant phenomena that occur before crack formation.

In situ TREXS Observation of Surface Reduction Reaction of NiO Film with ∼2 nm Surface Sensitivity.

X-ray absorption fine structure (XAFS) spectroscopy is one of the most widely used methods at synchrotron radiation facilities. XAFS gives us information on chemical states and local structures. Fundamentally, XAFS is bulk sensitive, not surface sensitive.

Finding Degradation Trigger Sites of Structural Materials for Airplanes Using X-Ray Microscopy.

Macroscopic properties of carbon fiber-reinforced plastic (CFRP) and environmental barrier coating (EBC), widely used for airplanes, can be deteriorated by local cracks or degradation ("trigger sites"). We have tried to find these trigger sites using x-ray microscopy (XM), which can provide the 2D or 3D images of the chemical states and microstructures. Crack initiation in CFRP was observed in a non-destructive manner in multi-scales (nm-mm).

A novel organic-rich meteoritic clast from the outer solar system.

The Zag meteorite which is a thermally-metamorphosed H ordinary chondrite contains a primitive xenolithic clast that was accreted to the parent asteroid after metamorphism. The cm-sized clast contains abundant large organic grains or aggregates up to 20 μm in phyllosilicate-rich matrix. Here we report organic and isotope analyses of a large (~10 μm) OM aggregate in the Zag clast.

Significant contribution of subseafloor microparticles to the global manganese budget.

Ferromanganese minerals are widely distributed in subseafloor sediments and on the seafloor in oceanic abyssal plains. Assessing their input, formation and preservation is important for understanding the global marine manganese cycle and associated trace elements. However, the extent of ferromanganese minerals buried in subseafloor sediments remains unclear.

Non-empirical identification of trigger sites in heterogeneous processes using persistent homology.

Macroscopic phenomena, such as fracture, corrosion, and degradation of materials, are associated with various reactions which progress heterogeneously. Thus, material properties are generally determined not by their averaged characteristics but by specific features in heterogeneity (or 'trigger sites') of phases, chemical states, etc., where the key reactions that dictate macroscopic properties initiate and propagate.

Organic matter in extraterrestrial water-bearing salt crystals.

Direct evidence of complex prebiotic chemistry from a water-rich world in the outer solar system is provided by the 4.5-billion-year-old halite crystals hosted in the Zag and Monahans (1998) meteorites. This study offers the first comprehensive organic analysis of the soluble and insoluble organic compounds found in the millimeter-sized halite crystals containing brine inclusions and sheds light on the nature and activity of aqueous fluids on a primitive parent body.

Comparison of Solid-Water Partitions of Radiocesium in River Waters in Fukushima and Chernobyl Areas.

Adsorption of radiocesium (RCs) on particulate matters in aquatic environment is important to understand its mobility and bioavailability. We here focused on factors controlling partition of RCs on particulate matters and sediments in Kuchibuto (Fukushima) and Pripyat (Chernobyl) Rivers, though RCs level in water was much smaller than WHO guideline. Moreover, Cs speciation and organic matter-clay mineral interaction were studied: (i) extended X-ray absorption fine structure showed that the contribution of outer-sphere complex of Cs on particulate matters is larger in Chernobyl than in Fukushima and (ii) scanning transmission X-ray microscope revealed larger association of humic substances and clay minerals in Chernobyl partly due to high [Ca] in the Pripyat River.

Spatially Resolved Distribution of Fe Species around Microbes at the Submicron Scale in Natural Bacteriogenic Iron Oxides.

Natural bacteriogenic iron oxides (BIOS) were investigated using local-analyzable synchrotron-based scanning transmission X-ray microscopy (STXM) with a submicron-scale resolution. Cell, cell sheath interface (EPS), and sheath in the BIOS were clearly depicted using C-, N-, and O- near edge X-ray absorption fine structure (NEXAFS) obtained through STXM measurements. Fe-NEXAFS obtained from different regions of BIOS indicated that the most dominant iron mineral species was ferrihydrite.

Tellurium Distribution and Speciation in Contaminated Soils from Abandoned Mine Tailings: Comparison with Selenium.

The distribution and chemical species of tellurium (Te) in contaminated soil were determined by a combination of microfocused X-ray fluorescence (μ-XRF), X-ray diffraction (μ-XRD), and X-ray absorption fine structure (μ-XAFS) techniques. Results showed that Te was present as a mixture of Te(VI) and Te(IV) species, while selenium (Se) was predominantly present in the form of Se(IV) in the soil contaminated by abandoned mine tailings. In the contaminated soil, Fe(III) hydroxides were the host phases for Se(IV), Te(IV), and Te(VI), but Te(IV) could be also retained by illite.

Nonvortical Rashba Spin Structure on a Surface with C_{1h} Symmetry.

A totally anisotropic peculiar Rashba-Bychkov (RB) splitting of electronic bands was found on the Tl/Si(110)-(1×1) surface with C_{1h} symmetry by angle- and spin-resolved photoelectron spectroscopy and first-principles theoretical calculation. The constant energy contour of the upper branch of the RB split band has a warped elliptical shape centered at a k point located between Γ[over ¯] and the edge of the surface Brillouin zone, i.e.

One-dimensional metallic surface states of Pt-induced atomic nanowires on Ge(0 0 1).

Surface states of platinum-induced atomic nanowires on a germanium (0 0 1) surface, which shows a structural phase transition at 80 K, were studied by angle-resolved photoelectron spectroscopy (ARPES). We observed four one-dimensional metallic surface states, among which, two bands were reported in our previous study (Yaji et al 2013 Phys. Rev.

Direct Detection of Fe(II) in Extracellular Polymeric Substances (EPS) at the Mineral-Microbe Interface in Bacterial Pyrite Leaching.

We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface.

Enhanced orbital magnetic moments in magnetic heterostructures with interface perpendicular magnetic anisotropy.

We have studied the magnetic layer thickness dependence of the orbital magnetic moment in magnetic heterostructures to identify contributions from interfaces. Three different heterostructures, Ta/CoFeB/MgO, Pt/Co/AlOx and Pt/Co/Pt, which possess significant interface contribution to the perpendicular magnetic anisotropy, are studied as model systems. X-ray magnetic circular dichroism spectroscopy is used to evaluate the relative orbital moment, i.