Kinetic analysis of silicon-lithium alloying reaction in silicon single crystal using soft X-ray absorption spectroscopy.

Silicon has been considered to be one of the most promising anode active materials for next-generation lithium-ion batteries due to its large theoretical capacity (4200 mA h g-1, Li22Si5). However, silicon anodes suffer from degradation due to large volume expansion and contraction. To control the ideal particle morphology, an experimental method is required to analyze anisotropic diffusion and surface reaction phenomena. This study investigates the anisotropy of the silicon-lithium alloying reaction using electrochemical measurements and Si K-edge X-ray absorption spectroscopy on silicon single crystals. During the electrochemical reduction process in lithium-ion battery systems, the continuous formation of solid electrolyte interphase (SEI) films prevents the achievement of steady-state conditions. Instead, the physical contact between silicon single crystals and lithium metals can prevent the effect of SEI formation. The apparent diffusion coefficient and the surface reaction coefficient are determined from the progress of the alloying reaction analyzed by X-ray absorption spectroscopy. While the apparent diffusion coefficients show no clear anisotropy, the apparent surface reaction coefficient of Si (100) is more significant than that of Si (111). This finding indicates that the surface reaction of silicon governs the anisotropy of practical lithium alloying reaction for silicon anodes.

Two-Phase Reaction Mechanism for Fluorination and Defluorination in Fluoride-Shuttle Batteries: A First-Principles Study.

Fluoride-shuttle batteries (FSBs), which are based on fluoride-ion transfer, have attracted attention because of their high theoretical energy densities. The fluorination and defluorination reactions at the electrodes are the possible rate-determining steps in FSBs, and understanding the mechanism is important to achieve smooth charge/discharge. In this study, we discuss the thermodynamically favored pathways for the fluorination and defluorination reactions and compare the reactions through the solid-solution and two-phase-coexistent states by density functional theory (DFT) calculations. The free energies of the solid-solution and two-phase states approximate the energies calculated by DFT, and their accuracy was validated by comparison with experimental formation enthalpies and free energies. The relative formation enthalpies of typical, transition, and relativistic metal (Tl, Pb, and Bi) fluorides are well reproduced by DFT calculations within 0.1, 0.2, and 0.4 eV, respectively. We also show that the reaction pathway can be determined by comparing the formation enthalpies of the metal fluoride H, a fluorine vacancy HV, and an interstitial fluorine defect HI from the simple selection rule. The enthalpy relation of HI > H > -HV observed in all the calculations strongly suggests that fluorination and defluorination in FSB electrodes occur by a two-phase reaction. This fluorination and defluorination mechanism will be useful to clarify the rate-determining step in FSBs.

Evolution of Reactions of a Fluoride Shuttle Battery at the Surfaces of BiF3 Microclusters Studied by In†Situ Raman Microscopy.

Fluoride shuttle batteries (FSBs), which utilize defluorination of metal fluorides and fluorination of the resultant metals, are expected to have high energy densities. In situ Raman microscopy was conducted during FSB reactions of a nearly-2D cluster of orthorhombic BiF3 microparticles partly embedded in a gold-plated film (o-BiF3 /gold). At a high overpotential, defluorination of the surface of an o-BiF3 particle (or cluster) was almost completed within approximately 120 s. At a low over potential, defluorination proceeded from the contours of the cluster that was in contact with the gold to the center of the cluster, suggesting that the rate-limiting process was electronic diffusion. Conversely, fluorination proceeded uniformly at the surface of the cluster to form BiF3 with a cubic structure (c-BiF3 ). The results will lead to the establishment of a strategy for efficient use of active materials with low electronic and ionic conductivities.

Interface structure between tetraglyme and graphite.

Clarification of the details of the interface structure between liquids and solids is crucial for understanding the fundamental processes of physical functions. Herein, we investigate the structure of the interface between tetraglyme and graphite and propose a model for the interface structure based on the observation of frequency-modulation atomic force microscopy in liquids. The ordering and distorted adsorption of tetraglyme on graphite were observed. It is found that tetraglyme stably adsorbs on graphite. Density functional theory calculations supported the adsorption structure. In the liquid phase, there is a layered structure of the molecular distribution with an average distance of 0.60 nm between layers.

Characteristic microglial features in patients with hereditary diffuse leukoencephalopathy with spheroids.

OBJECTIVE: To clarify the histopathological alterations of microglia in the brains of patients with hereditary diffuse leukoencephalopathy with spheroids (HDLS) caused by mutations of the gene encoding the colony stimulating factor-1 receptor (CSF-1R). METHODS: We examined 5 autopsied brains and 1 biopsy specimen from a total of 6 patients with CSF-1R mutations. Detailed immunohistochemical, biochemical, and ultrastructural features of microglia were examined, and quantitative analyses were performed. RESULTS: In layers 3 to 4 of the frontal cortex in HDLS brains, microglia showed relatively uniform and delicate morphology, with thin and winding processes accompanying knotlike structures, and significantly smaller areas of Iba1 immunoreactivity and lower numbers of Iba1-positive cells were evident in comparison with control brains. On the other hand, in layers 5 to 6 and the underlying white matter, microglia were distributed unevenly; that is, in some areas they had accumulated densely, whereas in others they were scattered. Immunoblot analyses of microglia-associated proteins, including CD11b and DAP12, revealed that HDLS brains had significantly lower amounts of these proteins than diseased controls, although Ki-67-positive proliferative microglia were not reduced. Ultrastructurally, the microglial cytoplasm and processes in HDLS showed vesiculation of the rough endoplasmic reticulum and disaggregated polyribosomes, indicating depression of protein synthesis. On the other hand, macrophages were immunonegative for GLUT-5 or P2ry12, indicating that they were derived from bone marrow. INTERPRETATION: The pathogenesis of HDLS seems to be associated with microglial vulnerability and morphological alterations. Ann Neurol 2016;80:554-565.

Composition-dependent electrocatalytic activity of AuPd alloy nanoparticles prepared via simultaneous sputter deposition into an ionic liquid.

Homogeneously alloyed bimetallic particles of AuPd with an average size of ca. 2 nm were successfully prepared by simultaneous sputter deposition of Au and Pd in an ionic liquid in the absence of any additional stabilizing agents. The chemical composition of the AuPd alloy was tunable depending on the area fraction of Au plates in the Au-Pd binary targets for sputtering. The particles were immobilized on an HOPG surface by heat treatment along with the increase in the average size of particles from ca. 2 nm to ca. 7 nm. Ionic liquid species adsorbed on the as-prepared AuPd nanoparticle films on HOPG caused the prevention of electrocatalytic reactions, but repetition of potential sweep cycling in a basic aqueous solution removed the adsorbed ionic species, resulting in electrocatalytic oxidation of ethanol at the AuPd alloy nanoparticle-immobilized HOPG electrode. The electrocatalytic activity of AuPd nanoalloy particles varied upon changing the fraction of Au and Pd in the particles, and alloy particles having an Au fraction of ca. 0.61 exhibited the maximum activity against ethanol oxidation, being higher than the activity of the pure Pt surface.

New frontiers in materials science opened by ionic liquids.

Ionic liquids (ILs) including ambient-temperature molten salts, which exist in the liquid state even at room temperature, have a long research history. However, their applications were once limited because ILs were considered as highly moisture-sensitive solvents that should be handled in a glove box. After the first synthesis of moisture-stable ILs in 1992, their unique physicochemical properties became known in all scientific fields. ILs are composed solely of ions and exhibit several specific liquid-like properties, e.g., some ILs enable dissolution of insoluble bio-related materials and the use as tailor-made lubricants in industrial applications under extreme physicochemical conditions. Hybridization of ILs and other materials provides quasi-solid materials, which can be used to fabricate highly functional devices. ILs are also used as reaction media for electrochemical and chemical synthesis of nanomaterials. In addition, the negligible vapor pressure of ILs allows the fabrication of electrochemical devices that are operated under ambient conditions, and many liquid-vacuum technologies, such as X-ray photoelectron spectroscopy (XPS) analysis of liquids, electron microscopy of liquids, and sputtering and physical vapor deposition onto liquids. In this article, we review recent studies on ILs that are employed as functional advanced materials, advanced mediums for materials production, and components for preparing highly functional materials.

Remarkable photoluminescence enhancement of ZnS-AgInS2 solid solution nanoparticles by post-synthesis treatment.

The photoluminescence intensity of ZnS-AgInS(2) solid solution nanoparticles was remarkably enhanced by increasing the heating temperature to 180 degrees C, above which the emission was simply diminished, while ZnS coating of the particles resulted in further enhancement of PL intensity, giving the highest quantum yield of ca. 80%.

Size control and immobilization of gold nanoparticles stabilized in an ionic liquid on glass substrates for plasmonic applications.

Gold (Au) nanoparticles were prepared by sputter deposition of Au metal in an ionic liquid (IL) of 1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF6). The size of Au nanoparticles was increased from 2.6 to 4.8 nm by heat treatment at 373 K. The nanoparticles uniformly dispersed in the IL were densely immobilized on a glass substrate surface modified with a silane coupling agent having an imidazole functional group by spreading the Au particle IL solution on the substrates, followed by heat treatment at 373 K. The optical property of the thus-obtained films was tunable by controlling the size of Au nanoparticles in the IL and the degree of immobilization. An intense localized surface plasmon resonance (LSPR) peak was observed in each Au particle film, and the wavelength of the LSPR peak could be controlled by changing the size of nanoparticles in the IL solution before immobilization. Photoexcitation of the LSPR peak caused enhancement of the photoluminescence of CdTe nanoparticles immobilized on Au nanoparticle films, probably due to the locally enhanced electric field formed around Au nanoparticles.

Hemifacial seizures due to ganglioglioma of cerebellum.

We present a male infant with hemifacial seizures refractory to antiepileptic medication. Hemifacial spasms around the left eye were frequent during wakefulness and sleep since birth. He also had mild psychomotor retardation. Magnetic resonance imaging (MRI) revealed a large tumor in the left middle cerebellar peduncle. Ictal single photon emission computed tomography (SPECT) and ictal (18)F-fluorodeoxyglucose [(18)F-FDG] positron emission tomography (PET) revealed hyperperfusion and hyper glucose metabolism at the tumor. Total removal of the tumor resulted in complete disappearance of hemifacial seizures and improved psychomotor development, indicating that the cerebellar tumor caused hemifacial seizures. A histopathological study confirmed that the tumor was a ganglioglioma. This case and the literature on similar cases indicated that this was a new epileptic syndrome originating in the cerebellum. Early diagnosis and early complete removal of the epileptogenic lesion should be recommended for this syndrome.

Candida albicans, Cryptococcus neoformans or Aspergillus fumigatus induces an antifungal activity in mouse serum, which is different from transferrin.

It has been reported that administration of Candida albicans into mouse induces an antifungal activity in serum, which has been identified as transferrin. In the present study, we show that not only C. albicans, but also other fungus such as Cryptococcus neoformans or Aspergillus fumigatus similarly can induce an antifungal activity in mouse serum. This antifungal activity was inhibited by the addition of ferrous ion, indicating that the growth inhibition of C. albicans was due to deficiency of ferrous ion, which may be caused by transferrin. Indeed, addition of transferrin in an in vitro assay system using RPMI1640 culture medium inhibited the growth of C. albicans, C. neoformans or A. fumigatus. However, when C. albicans was grown in RPMI1640 medium with 10% fetal bovine serum (FBS), transferrin was unable to inhibit the growth of C. albicans, in sharp contrast, when C. albicans treated mouse serum was added instead of FBS, the growth of the organism was inhibited. Similar results were obtained when C. neoformans or A. fumigatus was used. Taken together, the results suggest that antifungal activity induced by C. albicans, C. neoformans or A. fumigatus was not due to transferrin but likely due to other unknown serum proteins, which may cut off the source of iron for the growth of these fungi.

Stacked-structure-dependent photoelectrochemical properties of CdS nanoparticle/layered double hydroxide (LDH) nanosheet multilayer films prepared by layer-by-layer accumulation.

Inorganic multilayer films were prepared by layer-by-layer accumulation of positively charged layered double hydroxide (LDH) nanosheets and negatively charged CdS nanoparticles of different sizes. Nanoparticles were densely immobilized on LDH sheets to form a monolayer without coalescence into larger particles. The absorbance and photoluminescence intensity of immobilized CdS particles were enlarged with an increase in the accumulation number of the film. Hybrid films produced by accumulation of both monolayers of CdS particles (diameter: 5 nm) and those of smaller CdS particles (2.1 nm) exhibited characteristic photoluminescence spectra indicating the efficient energy transfer of photogenerated excitons from nanoparticle layers of smaller CdS particles to those of larger ones. LDH/CdS multilayers deposited on an F-doped SnO(2) (FTO) electrode behaved as an n-type semiconductor photoelectrode in an acetonitrile solution regardless of the size of the CdS particles immobilized, but their efficiency for photocurrent generation was greatly dependent on the stacked structure of the films. Accumulation of CdS particles of 2.1 nm in diameter on pre-coated LDH/CdS layers of 5 nm-sized CdS particles on FTO remarkably enhanced the photocurrent intensity in comparison to that in the case of accumulation of these two kinds of CdS particles in the opposite sequence. These observations can be explained by photoinduced electron transfer and energy transfer along with the band gap gradient in the films.

Electrochemical deposition of gold frame structure on silver nanocubes.

Au-framed Ag nanocubes were prepared by site-selective electrochemical deposition of Au onto the edges and vertices of Ag nanocubes modified with a self-assembled monolayer (SAM) of 1-octanethiol, and further chemical etching of the Ag cubes used as a template produced Au nanoframes.

Photo-induced electron migrations in the nano-cavities of mesoporous silica sensitized by a cationic porphyrin dye.

Photo-induced redox reactions in a hybrid film of a cationic porphyrin dye (H2TMPyP) accommodated within a transparent mesoporous silica (MPS) film spin-coated on an FTO electrode have been investigated for such applications as the construction of efficient solar energy storage devices and novel light-stimulated sensors. In this system, anodic and cathodic photocurrents were observed under bias voltages of +0.3 V and -0.4 V, respectively. The action spectrum of the photocurrents corresponded well with the absorbance of the H2TMPyP molecules in the visible light region. Control experiments showed no photocurrents for the mesoporous silica without H2TMPyP. Our investigations showed that the H2TMPyP molecules function not only as a sensitizer but also as a mediator for electron migrations within mesoporous nano-cavities.

Photochemical shape control of cadmium sulfide nanorods coated with an amorphous silica thin layer.

The surface of cadmium sulfide nanorods was modified by 3-mercaptopropyltrimethoxysilane, followed by the hydrolysis of trimethoxysilyl groups to form a silica shell structure (SiO2/CdS[rod]). Size-selective photoetching was applied to SiO2/CdS[rod] to modify the size of the CdS rod core. The absorption spectra were blue-shifted by irradiation of monochromatic light, and finally absorption onset agreed with the wavelength of irradiation light. These facts indicated that CdS rod particles were photoetched to smaller ones until the irradiated photons were no longer absorbed by the photoetched particles and that the SiO2 shell layer surrounding the CdS rod core prevented coalescence between photoetched particles. Changes in the wavelength of irradiation light from 488 to 436 nm caused a decrease in rod width from 3.5 to 2.3 nm along with remarkable decrease in the length of rod from 14 to 4.2 nm, suggesting that the photoetching rate was dependent on the kind of crystal faces and that the photocorrosion reactions at the tips of the CdS rod, that is, on (001) and/or (001) faces, were faster than those on other faces that appeared on the sides of the rod. This technique enabled control of CdS rod shape by selecting the wavelength of irradiation light.

Self-assembly of ionic liquid (BMI-PF6)-stabilized gold nanoparticles on a silicon surface: chemical and structural aspects.

Ultrafine monodisperse gold nanoparticles (AuNPs) were synthesized by an elegant sputtering of gold onto 1- n-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF(6)) ionic liquid. It was found that the BMI-PF(6) supramolecular aggregates were loosely coordinated to the gold nanoparticles and were replaceable with thiol molecules. The self-assembly of BMI-PF(6)-stabilized AuNPs onto a (3-mercaptopropyl)trimethoxysilane (MPS)-functionalized silicon surface in 2D arrays, followed by dodecanethiol (DDT) treatment, have been demonstrated using X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and contact angle measurements. DDT treatment of tethered AuNPs revealed two types of interactions between AuNPs and the MPS-functionalized surface: (a) AuNPs anchor through Au-S chemisorption linkage resulting in strong immobilization and (b) some of the AuNPs are supported by physisorption, driven by BMI-PF(6). The attachment of these particles remains unchanged with sonication. The replacement of BMI-PF(6) aggregates from physisorbed AuNPs with DDT molecules advances the dilution of their interaction with the MPS-functionalized surface, and they subsequently detach from the silicon surface. The present finding is promising for the immobilization of ionic liquid-stabilized nanoparticles, which is very desirable for electronic and catalytic device fabrication. Additionally, these environmentally friendly AuNPs are expected to replace conventional citrate-stabilized AuNPs.

Single-step synthesis of gold-silver alloy nanoparticles in ionic liquids by a sputter deposition technique.

The simultaneous sputter deposition of gold and silver onto ionic liquids formed bimetallic alloy nanoparticles, which exhibited composition-sensitive surface plasmon resonance, the peak wavelength being red-shifted with an increase in the surface area of the gold foil targets sputtered.

Facile synthesis of ZnS-AgInS2 solid solution nanoparticles for a color-adjustable luminophore.

Nanoparticles of ZnS-AgInS2 solid solution (ZAIS) were synthesized by the thermal decomposition of (AgIn)xZn2(1-x)(S2CN(C2H5)2)4 precursors in a hot oleylamine solution. X-ray powder diffraction analyses revealed that the resulting nanoparticle powders were not a mixture of ZnS and AgInS2 but a ZnS-AgInS2 solid solution in which the fraction of ZnS was enlarged with a decrease in the value of x, that is, an increase in the content of Zn2+ in the precursors used. The energy gap of ZAIS nanoparticles could be controlled by the composition of solid solution. Intense emission was observed at room temperature, regardless of the kind of the particles, the peak wavelength of PL being blue-shifted from 720 to 540 nm with a decrease in the value of x. The highest quantum yield of ca. 24% was obtained for nanoparticles prepared with x = 0.86, which was much higher than the quantum yields reported for I-III-VI2-based semiconductor nanoparticles, such as CuInS2 and ZnS-CuInS2 solid solution.

Photocatalytic syntheses of azoxybenzene by visible light irradiation of silica-coated cadmium sulfide nanocomposites.

Photoirradiation (lambda= 436 nm) of a deaerated 2-propanol aqueous solution containing nitrobenzene and rhodium-loaded silica-coated cadmium sulfide nanoparticles produced azoxybenzene with relatively high selectivity (68%), the photocatalytic activity being enhanced with a decrease in the size of the semiconductor particle core.

Photochemical fine-tuning of luminescent color of cadmium selenide nanoparticles: fabricating a single-source multicolor luminophore.

Size-selective photoetching was applied to silica-coated cadmium selenide (SiO2/CdSe) nanoparticles to precisely control their photoluminescence properties. The absorption spectra of CdSe was blue-shifted by irradiation of monochromatic light, and finally, the absorption onset agreed with the wavelength of irradiation light, indicating that CdSe particles were photoetched to smaller ones until the irradiated photons were not absorbed by the photoetched particles and that the SiO2 shell layer surrounding the CdSe core prevented coalescence between the photoetched particles. Although as-prepared SiO2/CdSe did not exhibit photoluminescence, the application of size-selective photoetching to SiO2/CdSe resulted in the development of the band gap emission, with the degree being enhanced with progress of the photoetching. The peak wavelength of photoluminescence decreased with a decrease in the wavelength used for the photoetching, so that the luminescence color could be tuned between red and blue. Partial photoetching of SiO2/CdSe nanoparticle films produced intense band gap emission of CdSe at the photoetched area, while the remainder of the SiO2/CdSe films did not exhibit detectable photoluminescence, resulting in the formation of a clear photoluminescence image under UV irradiation. This technique makes it possible to produce a multicolored photoluminescence image by irradiation with monochromatic lights having various wavelengths using a single source material.