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Lithium-ion deintercalation/intercalation during charge/discharge processes is one of the essential reactions that occur in the layered cathodes of lithium-ion batteries, and the performance of the cathode can be expressed as the sum of the reactions that occur in the local area of the individual cathode particles. In this study, the spatial distributions of the chemical states present in prototypical layered LiCoO2 cathode particles were determined at different charging conditions using scanning transmission X-ray microscopy (STXM) with a spatial resolution of approximately 100 nm. The Co L3- and O K-edge X-ray absorption spectroscopy (XAS) spectra, extracted from the same area of the corresponding STXM images, at the initial state as well as after charging to 4.5 V demonstrate the spatial distribution of the chemical state changes depending on individual particles. In addition to the Co L3-edge XAS spectra, the O K-edge XAS spectra of the initial and charged LiCoO2 particles are different, indicating that both the Co and O sites participate in charge compensation during the charging process possibly through the hybridization between the Co 3d and O 2p orbitals. Furthermore, the element maps of both the Co and O sites, derived from the STXM stack images, reveal the spatial distribution of the chemical states inside individual particles after charging to 4.5 V. The element mapping analysis suggests that inhomogeneous reactions occur on the active particles and confirm the existence of non-active particles. The results of this study demonstrate that an STXM-based spatially resolved electronic structural analysis method is useful for understanding the charging and discharging of battery materials.
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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). The morphology of the organic carbon includes nanoglobules and diffuse carbon associated with phyllosilicate and carbonate minerals. Deuterium and/or nitrogen-15 enrichments indicate that the organic matter formed in a cold molecular cloud or the presolar nebula. The diversity of the organic matter indicates variable levels of aqueous alteration on Ryugu's parent body.
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We performed X-ray absorption studies for the electrolytes of a Ti-Mn redox flow battery (RFB) to understand the redox reaction of the Ti/Mn ions and formation of precipitates in charged catholyte, because suppression of the disproportionation reaction is a key to improve the cyclability of Ti-Mn RFB and enhance the energy density. Hard X-ray absorption spectroscopy with a high transmittance and soft X-ray absorption spectroscopy to directly observe the 3d orbitals were complementarily employed. Moreover, the Ti/Mn 3d electronic structure for each precipitate and solution in the charged catholyte was investigated by using scanning transmission X-ray microscopy: the valence of Mn in the precipitate is mostly attributed to 4+, and the solution includes only Mn2+ . This charge disproportionation reaction should occur after the Mn ions in the catholyte should be oxidized from Mn2+ to Mn3+ by charge.
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Electrólitos , Titanio , Espectroscopía de Absorción de Rayos X , Oxidación-ReducciónRESUMEN
Synchrotron-based X-ray spectroscopic and microscopic techniques are used to identify the origin of enhancement of the photoelectrochemical (PEC) properties of BiVO4 (BVO) that is coated on ZnO nanodendrites (hereafter referred to as BVO/ZnO). The atomic and electronic structures of core-shell BVO/ZnO nanodendrites have been well-characterized, and the heterojunction has been determined to favor the migration of charge carriers under the PEC condition. The variation of charge density between ZnO and BVO in core-shell BVO/ZnO nanodendrites with many unpaired O 2p-derived states at the interface forms interfacial oxygen defects and yields a band gap of approximately 2.6 eV in BVO/ZnO nanocomposites. Atomic structural distortions at the interface of BVO/ZnO nanodendrites, which support the fact that there are many interfacial oxygen defects, affect the O 2p-V 3d hybridization and reduce the crystal field energy 10Dq â¼2.1 eV. Such an interfacial atomic/electronic structure and band gap modulation increase the efficiency of absorption of solar light and electron-hole separation. This study provides evidence that the interfacial oxygen defects act as a trapping center and are critical for the charge transfer, retarding electron-hole recombination, and high absorption of visible light, which can result in favorable PEC properties of a nanostructured core-shell BVO/ZnO heterojunction. Insights into the local atomic and electronic structures of the BVO/ZnO heterojunction support the fabrication of semiconductor heterojunctions with optimal compositions and an optimal interface, which are sought to maximize solar light utilization and the transportation of charge carriers for PEC water splitting and related applications.
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Drug penetration in human skin ex vivo following a modification of skin barrier permeability is systematically investigated by scanning transmission X-ray microscopy. Element-selective excitation is used in the O 1s regime for probing quantitatively the penetration of topically applied rapamycin in different formulations with a spatial resolution reaching <75 nm. The data were analyzed by a comparison of two methods: (i) two-photon energies employing the Beer-Lambert law and (ii) a singular value decomposition approach making use of the full spectral information in each pixel of the X-ray micrographs. The latter approach yields local drug concentrations more reliably and sensitively probed than the former. The present results from both approaches indicate that rapamycin is not observed within the stratum corneum of nontreated skin ex vivo, providing evidence for the observation that this high-molecular-weight drug inefficiently penetrates intact skin. However, rapamycin is observed to penetrate more efficiently the stratum corneum when modifications of the skin barrier are induced by the topical pretreatment with the serine protease trypsin for variable time periods ranging from 2 to 16 h. After the longest exposure time to serine protease, the drug is even found in the viable epidermis. High-resolution micrographs indicate that the lipophilic drug preferably associates with corneocytes, while signals found in the intercellular lipid compartment were less pronounced. This result is discussed in comparison to previous work obtained from low-molecular-weight lipophilic drugs as well as polymer nanocarriers, which were found to penetrate the intact stratum corneum exclusively via the lipid layers between the corneocytes. Also, the role of the tight junction barrier in the stratum granulosum is briefly discussed with respect to modifications of the skin barrier induced by enhanced serine protease activity, a phenomenon of clinical relevance in a range of inflammatory skin disorders.
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Marine mussels efficiently adhere under wet conditions by precisely controlling the hierarchical structure of the adhesive plaque through sequential mussel foot protein secretion in the foot-tip cavity. Chemical analysis of the non-uniform mussel plaque morphology has been performed using spectromicroscopy; however, the mesoscopic morphology has not been elucidated yet because of the limited spatial resolution of conventional chemical imaging techniques. We investigated the chemical speciation in the non-uniform mussel plaque morphology employing scanning transmission soft X-ray spectromicroscopy (STXM). The high-spatial-resolution STXM chemical imaging with C 1s near-edge X-ray absorption fine structure yields the distribution of the hydroxy-substituted aromatic residues in the sub-micron scale non-uniform mussel plaque morphology. The matrix consists of a high-protein-density cured product containing a large number of hydroxy-substituted aromatic carbons, including tyrosine and 3,4-dihydroxyphenylalanine (Dopa), whereas the microdomains are poor-protein-density regions with a low aromatic residue relative content. The adhesive interface was covered with the matrix phase to ensure adhesion. The cuticle layer involves a moderate Dopa content, which appears to be optimized for the mechanical performance of the skin.
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Bivalvos , Dihidroxifenilalanina , Adhesivos , Animales , Tirosina , Rayos XRESUMEN
We have designed a new low-pass Fresnel zone plate (LPFZP) to extend soft x-ray absorption spectroscopy (XAS) to the lithium K absorption edge in a scanning transmission x-ray microscope (STXM). The performance of the LPFZP was evaluated in the STXM beamline at the UVSOR-III Synchrotron (Okazaki, Japan); the contribution of the higher-order harmonics is successfully suppressed to 0.1% of the fundamental energy, and a spatial resolution of 72 nm and an energy resolution (E/∆E) above 1000 are achieved as expected. XAS spectra of lithium are measured successfully in an electrode of a lithium-ion battery.
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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. Based on the dependence of the optical density ratio between C 1s â π* and 1s â σ* excitation on the polarization angle of the X-rays, the average two-dimensional orientation angle of the π orbital in each position in a natural spherical graphite sample was visualized.
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Lignans are bioactive compounds that are especially abundant in the Norway spruce (Picea abies L. Karst.) knotwood. By combining a variety of chromatographic, spectroscopic and imaging techniques, we were able to quantify, qualify and localise the easily extractable lignans in the xylem tissue. The knotwood samples contained 15 different lignans according to the gas chromatography-mass spectrometry analysis. They comprised 16% of the knotwood dry weight and 82% of the acetone extract. The main lignans were found to be hydroxymatairesinols HMR1 and HMR2. Cryosectioned and resin-embedded ultrathin sections of the knotwood were analysed with scanning transmission X-ray microscopy (STXM). Cryosectioning was found to retain only lignan residues inside the cell lumina. In the resin-embedded samples, lignan was interpreted to be unevenly distributed inside the cell lumina, and partially confined in deposits which were either readily present in the lumina or formed when OsO4 used in staining reacted with the lignans. Furthermore, the multi-technique characterisation enabled us to obtain information on the chemical composition of the structural components of knotwood. A simple spectral analysis of the STXM data gave consistent results with the gas chromatographic methods about the relative amounts of cell wall components (lignin and polysaccharides). The STXM analysis also indicated that a torus of a bordered pit contained aromatic compounds, possibly lignin.
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Lignanos/análisis , Microscopía Electrónica de Transmisión de Rastreo/métodos , Picea/química , Espectrometría por Rayos X/métodos , Microtomografía por Rayos X/métodos , Lignanos/químicaRESUMEN
A sample holder for a suite of synchrotron radiation measurements on extraterrestrial materials, which are fragile and irregularly shaped, was developed using carbon nanotubes and polyimide. The holder enables investigation of such samples with multiple analytical instruments, which means that we can reduce the number of sample transfers between holders. The holder developed in our study also enables investigation of such samples without exposure to the terrestrial atmosphere, which contains abundant contaminants, such as water vapor and organic substances. The stability of the samples in the holder during the measurements and disturbance of the analysis result by the holder were evaluated, which showed that sample drift motion and image disturbance due to x-ray attenuation and scattering of the holder materials are insignificant.
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Organic-inorganic hybrid films were fabricated from cellulose nanofibrils (CNF) and nanosilica (5-30% wt) embedded in a chitosan (Chi) biopolymer matrix using a slow evaporation method. The self-standing films exhibited high strength and modulus up to 120 ± 5 MPa and 7.5 ± 0.4 GPa, respectively, which are remarkably high values for biopolymer/chitosan hybrids. Scanning electron microscopy showed that the nanosilica is formed of larger aggregates within the lamellar CNF network structure. This observation was further confirmed using synchrotron-based scanning transmission x-ray microscopy (STXM) with the capability to determine the spatial and chemical distribution analysis of the constituents of films. It is interesting that the thermal stability of the hybrid films improved as the nanosilica content increased. Furthermore, the nanosilica effectively filled the pores in the CNF network, thus decreasing the UV transmission and the visible light transmittance of the films.
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Soft X-ray microscopy was applied to study the quantitative distribution of DNA, RNA, histone, and proteins other than histone (represented by BSA) in mammalian cells, apoptotic nuclei, and a chromosome at spatial resolutions of 100 to 400 nm. The relative distribution of closely related molecules, such as DNA and RNA, was discriminated by the singular value decomposition (SVD) method using aXis2000 software. Quantities of nucleic acids and proteins were evaluated using characteristic absorption properties due to the 1sâ»π * transition of N=C in nucleic acids and amide in proteins, respectively, in the absorption spectra at the nitrogen K absorption edge. The results showed that DNA and histone were located in the nucleus. By contrast, RNA was clearly discriminated and found mainly in the cytoplasm. Interestingly, in a chromosome image, DNA and histone were found in the center, surrounded by RNA and proteins other than histone. The amount of DNA in the chromosome was estimated to be 0.73 pg, and the content of RNA, histone, and proteins other than histone, relative to DNA, was 0.48, 0.28, and 4.04, respectively. The method we present in this study could be a powerful approach for the quantitative molecular mapping of biological samples at high resolution.
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Núcleo Celular/metabolismo , Cromosomas de los Mamíferos/genética , ADN/metabolismo , Histonas/metabolismo , Mamíferos/metabolismo , Microscopía/métodos , ARN/metabolismo , Animales , Células CHO , Cricetinae , Cricetulus , Células HeLa , Humanos , Albúmina Sérica Bovina/metabolismo , Rayos XRESUMEN
Soft X-ray spectromicroscopy was applied to study the distribution of DNA and RNA in a mammalian cell at the spatial resolution of 400ânm. The relative distribution of DNA and RNA was examined by the SVD (singular value decomposition) method in aXis2000 program using combined full spectra of DNA and RNA at the absorption edge regions of carbon, nitrogen and oxygen. The absorption of nucleic acid was evaluated using 1s-π* transitions in the NEXAFS spectra at the nitrogen K absorption edge and distributed to DNA and RNA according to the relative level obtained above. The present results revealed the usefulness of the SVD method to discriminate closely related molecules such as DNA and RNA.
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Técnicas Citológicas/métodos , ADN/análisis , Microscopía/métodos , ARN/análisis , Espectroscopía de Absorción de Rayos X/métodos , Algoritmos , Animales , Células CHO , Cricetulus , Imagen MolecularRESUMEN
The fabrication of multidimensional organometallic halide perovskite via a low-pressure vapor-assisted solution process is demonstrated for the first time. Phenyl ethyl-ammonium iodide (PEAI)-doped lead iodide (PbI2 ) is first spin-coated onto the substrate and subsequently reacts with methyl-ammonium iodide (MAI) vapor in a low-pressure heating oven. The doping ratio of PEAI in MAI-vapor-treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV-vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI2 ratio, which suggests the coexistence of low-dimensional perovskite (PEA2 MAn-1 Pbn I3n+1 ) with various values of n after vapor reaction. The dimensionality of the as-fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI2 ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI-containing perovskite grain is presumably formed around the MAPbI3 perovskite grain to benefit MAPbI3 grain growth. The device employing perovskite with PEAI/PbI2 = 0.05 achieves a champion power conversion efficiency of 19.10% with an open-circuit voltage of 1.08 V, a current density of 21.91 mA cm-2 , and a remarkable fill factor of 80.36%.
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Compuestos de Calcio/química , Óxidos/química , Titanio/química , Energía SolarRESUMEN
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. Fe(II)- and/or Fe(III)-acidic polysaccharides accompanied ferrihydrite near the cell and EPS regions. Our STXM/NEXAFS analysis showed that Fe species change continuously between the cell, EPS, and sheath under several 10-nm scales.
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Bacterias , Compuestos Férricos/análisis , Hierro , Sincrotrones , Espectroscopía de Absorción de Rayos XRESUMEN
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. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution.
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Acidithiobacillus/metabolismo , Biopolímeros/química , Biopolímeros/metabolismo , Microbiología Ambiental , Hierro/análisis , Sulfuros/metabolismo , Microanálisis por Sonda Electrónica , Hierro/metabolismo , Microscopía Electrónica de Transmisión de Rastreo , Oxidación-ReducciónRESUMEN
Efforts have been made to elucidate the origin of d(0) magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.
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Nanoestructuras , Nanotecnología/métodos , Óxido de Zinc/química , Análisis de Fourier , Luminiscencia , Magnetismo , Nanocables , Oxígeno/química , Espectrofotometría , Propiedades de Superficie , Temperatura , Compuestos de Estaño/química , Espectroscopía de Absorción de Rayos X , Rayos XRESUMEN
Excess iron deposition in the liver is known to be hepatotoxic and may exacerbate liver injury. However, little is known about iron distribution in the lobule because of the lack of a highly sensitive detection method. The aim of this study is to determine iron distribution in the lobule of human liver by means of synchrotron radiation X-ray fluorescence (SRXRF) microscopy. Mapping of the trace elements was done with use of SRXRF microscopy and compared with the results of staining by Berlin blue and oxidative stress markers. Iron deposits were distributed predominantly in periportal hepatocytes in the normal liver in a decreasing gradient from the periportal area to the perivenous area. This distribution was consistent with the formation of oxidative stress markers, suggesting that hepatocytes in the periportal area may be predominantly primed by iron-induced free radical damage even in normal liver. On the other hand, iron deposits in the periportal area were more intense than those in the centrilobular area in both the liver with chronic hepatitis C and the cirrhotic liver. In conclusion, elemental mapping by SRXRF microscopy was a highly sensitive method for the detection and mapping of elements such as iron and copper in liver sections.
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Hepatocitos/metabolismo , Hierro/análisis , Microscopía Fluorescente/métodos , Espectrometría por Rayos X/métodos , Sincrotrones , Hepatitis C Crónica/metabolismo , Humanos , Hierro/metabolismo , Cirrosis Hepática/metabolismo , Microscopía Fluorescente/instrumentación , Sensibilidad y Especificidad , Espectrometría por Rayos X/instrumentaciónRESUMEN
The three-dimensional structure of scabies mites (Sarcoptes scabiei var. hominis) and keratin layers affected by crusted scabies lesions were obtained using X-ray computed tomography at sub-micrometer and micrometer resolution, respectively (X-ray micro-CT). Clear three-dimensional images including internal structure of scabies mites were obtained. Utilizing reconstructed micro-CT data, the sections of the capitulum (head part), digestive organs, and legs are shown. The reconstructed capitulum shows a jaw-like structure capable of penetrating the keratin layer of the skin. The tip of the forelegs of female scabies mites has a flat disk structure that may be used to grasp the skin surface. The keratin layer of a crusted scabies lesion spontaneously exfoliated from a patient was also reconstructed by the X-ray micro-CT technique. Extracted sections from CT data revealed a network structure of tunnels made by scabies mites with numerous larvae and eggs inside the tunnels.
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Sarcoptes scabiei/anatomía & histología , Escabiosis/patología , Piel/patología , Microtomografía por Rayos X , Animales , Femenino , Humanos , Imagenología Tridimensional , Escabiosis/parasitología , Piel/parasitologíaRESUMEN
PURPOSE: To determine whether glioma cells irradiated with a microplanar X-ray beam exert bystander effects. METHODS AND MATERIALS: Microplanar beam irradiation of glioma cells in vitro was done using the SPring-8 synchrotron radiation facility. The amount of DNA double-strand breaks (dsbs) was measured by the fluorescence intensity of phosphorylated H2AX or the number of 53BP1 foci. The dose distribution in a cell population exposed to a single microplanar beam was determined by the amount of phosphorylated H2AX-positive cells. Bystander effects were determined by counting the number of 53BP1 foci in nonirradiated cells treated with conditioned medium from cultures of irradiated cells. RESULTS: More DNA dsbs were detected in cells adjacent to an area irradiated by the single beam than in cells in distant, nonirradiated areas as a result of bystander effects caused by scattered X-rays and DNA dsbs. In support of this, more 53BP1 foci were observed in nonirradiated, conditioned medium-treated cells than in control cells (i.e., cells not treated with irradiation or conditioned medium). These results suggest that DNA dsbs were induced in nonirradiated cells by soluble factors in the culture medium. In addition, we observed cellular migration into areas irradiated with peak doses, suggesting that irradiated cells send signals that cause nonirradiated cells to migrate toward damaged cells. CONCLUSIONS: Bystander effects are produced by factors secreted as a result of slit-type microplanar X-ray beam irradiation.