Anionic Sublattices in Halide Solid Electrolytes: A Case Study with the High-Pressure Phase of Li3ScCl6.

The Li3MX6 compounds (M=Sc, Y, In; X=Cl, Br) are known as promising ionic conductors due to their compatibility with typical metal oxide cathode materials. In this study, we have successfully synthesized γ-Li3ScCl6 using high pressure for the first time in this family. Structural analysis revealed that the high-pressure polymorph crystallizes in the polar and chiral space group P63mc with hexagonal close-packing (hcp) of anions, unlike the ambient-pressure α-Li3ScCl6 and its spinel analog with cubic closed packing (ccp) of anions. Investigation of the known Li3MX6 family further revealed that the cation/anion radius ratio, rM/rX, is the factor that determines which anion sublattice is formed and that in γ-Li3ScCl6, the difference in compressibility between Sc and Cl exceeds the ccp rM/rX threshold under pressure, enabling the ccp-to-hcp conversion. Electrochemical tests of γ-Li3ScCl6 demonstrate improved electrochemical reduction stability. These findings open up new avenues and design principles for lithium solid electrolytes, enabling routes for materials exploration and tuning electrochemical stability without compositional changes or the use of coatings.

Key Role of Interfacial Cobalt Segregation in Stable Low-Resistance Composite Oxygen-Reducing Electrodes.

The development of efficient and stable oxygen-reducing electrodes is challenging but vital for the production of efficient electrochemical cells. Composite electrodes composed of mixed ionic-electronic conducting La1-xSrxCo1-yFeyO3-δ and ionic conducting doped CeO2 are considered promising components for solid oxide fuel cells. However, no consensus has been reached regarding the reasons of the good electrode performance, and inconsistent performance has been reported among various research groups. To mitigate the difficulties related to analyzing composite electrodes, this study applied three-terminal cathodic polarization to dense and nanoscale La0.6Sr0.4CoO3-δ-Ce0.8Sm0.2O1.9 (LSC-SDC) model electrodes. The critical factors determining the performance of the composite electrodes are the segregation of catalytic cobalt oxides to the electrolyte interfaces and the oxide-ion conducting paths provided by SDC. The addition of Co3O4 to the LSC-SDC electrode resulted in reduced LSC decomposition; thus, the interfacial and electrode resistances were low and stable. In the Co3O4-added LSC-SDC electrode under cathodic polarization, Co3O4 turned wurtzite-type CoO, which suggested that the Co3O4 addition suppressed the decomposition of LSC and, thus, the cathodic bias was maintained from the electrode surface to electrode-electrolyte interface. This study shows that cobalt oxide segregation behavior must be considered when discussing the performance of composite electrodes. Furthermore, by controlling the segregation process, microstructure, and phase evolution, stable low-resistance composite oxygen-reducing electrodes can be fabricated.

Levels of Toxic and Essential Elements and Associated Factors in the Hair of Japanese Young Children.

There is growing concern regarding the effects of toxic element exposure on the development of children. However, little is known about the level of toxic elements exposure in Japanese children. The purpose of this study was to assess the concentrations of multiple elements (aluminum, cadmium, lead, calcium, copper, iron, magnesium, sodium, zinc) in the hair of 118 Japanese young children and to explore the factors associated with their element levels. The element concentration was analyzed by ICP-MS, and children's food and water intake were assessed by the questionnaire. Results showed that there were no large differences between the level of elements in the hair of Japanese children and those of children in other developed countries. Girls had significantly higher levels of aluminum, copper, and iron (p = 0.000, 0.014, and 0.013, respectively), and boys had a higher level of sodium (p = 0.006). The levels of calcium, iron, magnesium, and sodium in nursery school children were significantly higher than those in kindergarten children (p = 0.024, 0.001, 0.046, and 0.029, respectively). Multiple regression analyses with controlling the confounding variables showed significant negative associations of frequency of yogurt intake with aluminum and lead levels (p = 0.015 and 0.037, respectively). When the children were divided into three groups based on the frequency of yoghurt consumption, viz. L (≤once a week), M (2 or 3 times a week), and H (≥4 to 6 times a week) group, the mean aluminum concentration (µg/g) in the L, M, and H groups was 11.06, 10.13, and 6.85, while the mean lead concentration (µg/g) was 1.76, 1.70, and 0.87, respectively. Our results suggested the validity of hair element concentrations as an exposure measure of essential elements and frequent yogurt intake as a viable measure for protecting children from toxic elements. However, these findings will need to be confirmed in more detailed studies with larger sample sizes in the future.

Quality improvement of gluten-free rice flour bread through the addition of high-temperature water during processing.

Recently, there has been an increase in the demand for gluten-free bread due to health reasons. One of the flours used to produce gluten-free bread is rice flour; flour characteristics are very important for breadmaking. Although a study has shown that the addition of high-temperature water can improve the quality of rice flour bread, studies are yet to consider different rice properties. Therefore, the aim of this study was to investigate the effect of adding high-temperature water and rice flour characteristics on the quality of rice flour bread using six commercially available rice flours. The rice flours used in the sample had amylose content from 12.1% to 24.5%, damaged starch content from 2.4% to 5.5%, mode diameter from 16.3 to 63.3 µm, protein content from 5.4% to 6.1%, and moisture content in the range of 12.0%-15.0%. The results showed that regardless of the rice characteristics, breads prepared at the optimum watering temperature were puffier and softer than those prepared using cold water (5°C). For rice flours with similar particle size, the optimal water temperature and degree of gelatinization for breadmaking increased with rice flours with lower amylose content. Furthermore, the rheological properties of dough prepared at the optimum water addition temperature were stable, with loss modulus (G″) being dominant over the entire frequency range in the frequency sweep test. Since the water temperature added to the dough affects breadmaking properties more than the characteristics of the rice flour, adjusting the water temperature may enable the production of high-quality bread even with rice flour unsuitable for making. PRACTICAL APPLICATION: Presently, the addition of high-temperature water to rice flour has been shown to improve the bread quality. In this study, we investigated the effects of high-temperature water addition on the quality of rice flour bread using rice flour varieties with different flour characteristics. Even in rice flour with small particle size and low amylose content, which is not suitable for breadmaking, bread quality can be improved by adding hot water at around 70°C. This is a simple and practical method to improve the quality of gluten-free rice flour bread without adding thickeners.

Effect of the addition of high-temperature water on the properties of batter and bread made from gluten-free rice flour.

Increasing number of individuals worldwide are consuming gluten-free products, for example, bread, for health and other reasons. However, gluten-free products are currently expensive and/or their preparation involves the use of specialist machinery or food additives. In this study, we focused on the thickening effect of starch gelatinization and attempted to develop a novel method for gluten-free rice flour bread production without the use of additives. We aimed to determine the effect of adding high-temperature water to gluten-free rice flour on the properties of the resulting batter, primarily gelatinization. The water was tested at temperatures between 50 and 80°C, in 2°C increments. For comparison, control bread from gluten-free rice flour was made using cold (5°C) water. The addition of water at a temperature between 66 and 70°C significantly improved the specific volume and firmness of bread (p < 0.05, Dunnett's test; compared with control). Additionally, maintaining the gelatinization temperature of the bread batter for approximately 1-10 s and the degree of gelatinization of batter, approximately 5%-10%, were crucial for obtaining good-quality bread. Further, the addition of water at a temperature above 78°C adversely affected the bread-making properties. This simple method developed for making high-quality bread from gluten-free rice flour will make gluten-free bread products more widely available to and acceptable by the consumers. PRACTICAL APPLICATION: Currently, making high-quality bread from gluten-free rice flour involves the use of food additives or special rice flour. Here, we present a simple method for producing high-quality bread by manipulating the temperature of water added during the preparation of rice flour batter. We optimized the method by analyzing the gelatinization properties of the batter and determined the optimal water temperature suitable for bread making. This method yields high-quality gluten-free bread and is cost-effective and simple to implement.

Heat-Resistant Black Insulative Thin Films for Flat-Panel Displays in Al-Doped Ag-Fe-O Systems.

Multilayer antireflection (AR) coatings require a material with a large and constant absorption coefficient over the whole visible range and thermal stability. Coatings for use in touch panel displays are also required to be electrically insulative. In this study, 60 mol % Ag-40 mol % (Fe1-xAlx)-O (x = 0, 0.25, 0.50, 0.75, and 1.0) thin films are prepared by pulsed laser deposition, and their optical properties, electric resistance, and thermal stability are clarified by combining the experimental data and density functional theory (DFT) calculations. Over the visible range, large and constant absorption coefficients are obtained for all compositions. The standard deviations of the absorption coefficients of the x = 0.75 and 1.0 samples are found to be smaller than those of conventional materials like graphite and CrOx. High sheet resistance (Rsheet > 107 Ω·sq-1) is also confirmed. It is determined that nanometer-sized Ag dispersed into a matrix, which was confirmed to be ionic Ag in the matrix phase, is responsible for the absorption at a shorter visible light range and insulative nature even at high Ag content. The films with high Al content are stable up to 500 °C. The potential of these black insulative Ag-Al-Fe-O thin films for use as black AR coatings is confirmed by optical simulations with multilayer stacks.

Hydride-based antiperovskites with soft anionic sublattices as fast alkali ionic conductors.

Most solid-state materials are composed of p-block anions, only in recent years the introduction of hydride anions (1s2) in oxides (e.g., SrVO2H, BaTi(O,H)3) has allowed the discovery of various interesting properties. Here we exploit the large polarizability of hydride anions (H-) together with chalcogenide (Ch2-) anions to construct a family of antiperovskites with soft anionic sublattices. The M3HCh antiperovskites (M = Li, Na) adopt the ideal cubic structure except orthorhombic Na3HS, despite the large variation in sizes of M and Ch. This unconventional robustness of cubic phase mainly originates from the large size-flexibility of the H- anion. Theoretical and experimental studies reveal low migration barriers for Li+/Na+ transport and high ionic conductivity, possibly promoted by a soft phonon mode associated with the rotational motion of HM6 octahedra in their cubic forms. Aliovalent substitution to create vacancies has further enhanced ionic conductivities of this series of antiperovskites, resulting in Na2.9H(Se0.9I0.1) achieving a high conductivity of ~1 × 10-4 S/cm (100 °C).

Children's Hair Mercury Concentrations and Seafood Consumption in Five Regions of Japan.

Exposure to methylmercury (MeHg) during the foetal and postnatal periods is known to have adverse effects on children's development. However, little attention has been paid to MeHg exposure during early childhood in Japan. To examine the regional differences in MeHg exposure and seafood consumption and the association between MeHg exposure and seafood consumption and dental metal restorations, we measured the total mercury (T-Hg) concentration in hair as an MeHg exposure index, and using questionnaires, we measured the frequency and amount of seafood consumption and the presence of dental metal restorations in 118 children aged 3-6 years in five regions of Japan. The arithmetic and geometric means of the T-Hg concentrations in hair were 1.03 and 0.87 ppm, respectively, and approximately 40% of the children exceeded the United States Environmental Protection Agency recommendation of 1.0 ppm. Significant regional differences in the hair T-Hg concentrations were found among the five regions, and the regional differences were consistent with the traditional regional patterns of eating fatty fish. According to the regression analysis, the consumption of fatty fish, particularly tuna/swordfish, had a significant effect on hair T-Hg concentrations, whereas age, sex, the materials used for dental metal restorations, and other types of seafood or fish/shellfish had no significant effects.

Effects of Grilling on Total Polyphenol Content and Antioxidant Capacity of Eggplant (Solanum melongena L.).

Cooking can change the polyphenol contents of eggplant. This study elucidated the effects of grilling on total polyphenol content (TPC), antioxidant capacity, and the inner structures of eggplant. After identical hollowing, cylindrical eggplant samples were prepared and were then grilled until their center temperatures (CT) respectively reached 50, 65, 75, 85, and 95 °C. Chemical assays and observations of the inner structures clarified that TPC and 1, 1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity decreased as CT increased when CT was below 65 °C. Results also showed that TPC and DPPH radical scavenging activity increased as CT increased when CT was between 65 °C and 95 °C. For CT 65 °C, the samples retained polyphenol oxidase (PPO) activity up to 40% of the raw state activity. The 3 grilled eggplant models, chlorogenic acid, chlorogenic acid-sugar and chlorogenic acid-amino acid model, yielded results showing that phenol functional groups on chlorogenic acid were thermally stable and that phenol functional groups on chlorogenic acid reacted neither with sugar nor with amino acids. Results show that PPO activity is a primary reason for the decrease of the 2 indices. Optical microscopic and scanning electron microscopic observations revealed collapsed cells and inter-tissue cracks around the surface area for CT 85 and 95 °C. Scanning electron microscopic observations clarified that intercellular bonds for CT 85 and 95 °C became thinner than those for CT 75 °C around the middle area. The phenomena explained above are reasons for the increase of TPC and DPPH radical scavenging activity.

Li-Ion Conductivity and Phase Stability of Ca-Doped LiBH4 under High Pressure.

The effect of Ca doping on the Li-ion conductivity and phase stability of the rock-salt-type LiBH4 phase emerging under high pressures in the range of gigapascals has been investigated. In situ electrochemical measurements under high pressure were performed using a cubic-anvil-type apparatus. Ca doping drastically enhanced the ionic conductivity of the rock-salt-type phase: the ionic conductivity of undoped and 5 mol %Ca-doped LiBH4 was 2.2 × 10-4 and 1.4 × 10-2 S·cm-1 under 4.0 GPa at 220 °C, respectively. The activation volume of LiBH4-5 mol %Ca(BH4)2, at 3.2 cm3·mol-1, was comparable to that of other fast ionic conductors, such as lithium titanate and NASICONs. Moreover, Ca-doped LiBH4 showed lithium plating-stripping behavior in a cyclic voltammogram. These results indicate that the conductivity enhancement by Ca doping can be attributed to the formation of a LiBH4-Ca(BH4)2 solid solution; however, the solid solution decomposed into the orthorhombic LiBH4 phase and the orthorhombic Ca(BH4)2 phase after unloading the high pressure.

Exceptional superionic conductivity in disordered sodium decahydro-closo-decaborate.

Na2 B10 H10 exhibits exceptional superionic conductivity above ca. 360 K (e.g., ca. 0.01 S cm(-1) at 383 K) concomitant with its transition from an ordered monoclinic structure to a face-centered-cubic arrangement of orientationally disordered B10 H10 (2-) anions harboring a vacancy-rich Na(+) cation sublattice. This discovery represents a major advancement for solid-state Na(+) fast-ion conduction at technologically relevant device temperatures.

(45)Sc NMR spectroscopy and first-principles calculation on the symmetry of ScO6 polyhedra in BaO-Sc2O3-based oxides.

The correlation between the local structure and the electric-field gradient at the Sc site in ScO6 polyhedra in Sc2O3, Ba3Sc4O9 and BaSc2O4 was investigated by means of (45)Sc NMR spectroscopy and DFT calculations. The electric-field gradient at the nucleus as determined experimentally and by calculations is compared using the quadrupolar coupling constant, CQ, around chemically and crystallographically distinct Sc sites in Sc-containing compounds. With CQ as the NMR parameter, the results obtained from the DFT calculation were in good agreement with the NMR measurements. The increase in the CQ values with the standard deviation of the O-O bond length surrounding Sc indicates that CQ is affected by the distribution of the six nearest neighboring O atoms around Sc. This study suggests that CQ plays an important role as an indicator of the local structure around ions, and that a combined complementary approach using both NMR spectroscopy and DFT calculation can be used along with diffraction techniques to provide a detailed understanding of crystal structures.

Antioxidant activities of two sericin proteins extracted from cocoon of silkworm (Bombyx mori) measured by DPPH, chemiluminescence, ORAC and ESR methods.

Recent efforts have focused on the use of sericin proteins extracted from cocoons of silkworm as a healthy food source for human consumption. In this study, we focused on the antioxidative properties of sericin proteins. The antioxidative properties were measured in sericin proteins extracted from the shell of the cocoon, designated hereafter as white sericin protein and yellow-green sericin protein, as well as bread without sericin protein and bread to which white sericin powder had been added using four measurement methods: 1,1-Diphenyl-2-picrylhydrazyl (DPPH), chemiluminescence, oxygen radical absorbance capacity (ORAC) and electron spin resonance (ESR). High antioxidative properties of sericin proteins were indicated by all four methods. A comparison of the two types of sericin proteins revealed that yellow-green sericin protein exhibited high antioxidative properties as indicated by the DPPH, chemiluminescence and ORAC methods. By contrast, a higher antioxidative property was determined in white sericin protein by the ESR method. Consequently, our findings confirmed that sericin proteins have antioxidative properties against multiple radicals. In addition, the antioxidative property of bread was enhanced by the addition of sericin powder to the bread. Therefore, findings of this study suggest that sericin proteins may be efficiently used as beneficial food for human health.

Sodium superionic conduction in Na2B12H12.

Impedance measurements indicate that Na2B12H12 exhibits dramatic Na(+) conductivity (on the order of 0.1 S cm(-1)) above its order-disorder phase-transition at ≈529 K, rivaling that of current, solid-state, ceramic-based, Na-battery electrolytes. Superionicity may be aided by the large size, quasispherical shape, and high rotational mobility of the B12H12(2-) anions.

Near-infrared spectroscopic assessment of contamination level of sewage.

We examined the use of near infrared (NIR) spectroscopy as a rapid technique for the evaluation of sewage quality. Influent water samples, primary sedimentation tank water samples, and final effluent water samples were collected from sewage treatment facilities in Nagoya, Japan and their NIR spectra obtained. Partial least squares (PLS) models for total phosphate (TP), total nitrogen (TN), biochemical oxygen demand (BOD), total organic carbon (TOC), and turbidity of sewage water were constructed from the NIR data. The models provided good correlation between measurements obtained conventionally and those predicted from spectroscopy. Spectral variation induced by background interference in samples affected accuracy. Loading plots and score plots derived from PLS regression analysis resolved the background interference and allowed highly accurate predictions. Spectral variation induced by contamination in the sewage was a main predictor of sewage quality. These results show that NIR spectroscopy shows potential for in-line, non-destructive measurement of sewage quality.

Complex hydrides with (BH(4))(-) and (NH(2))(-) anions as new lithium fast-ion conductors.

Some of the authors have reported that a complex hydride, Li(BH(4)), with the (BH(4))(-) anion exhibits lithium fast-ion conduction (more than 1 x 10(-3) S/cm) accompanied by the structural transition at approximately 390 K for the first time in 30 years since the conduction in Li(2)(NH) was reported in 1979. Here we report another conceptual study and remarkable results of Li(2)(BH(4))(NH(2)) and Li(4)(BH(4))(NH(2))(3) combined with the (BH(4))(-) and (NH(2))(-) anions showing ion conductivities 4 orders of magnitude higher than that for Li(BH(4)) at RT, due to being provided with new occupation sites for Li(+) ions. Both Li(2)(BH(4))(NH(2)) and Li(4)(BH(4))(NH(2))(3) exhibit a lithium fast-ion conductivity of 2 x 10(-4) S/cm at RT, and the activation energy for conduction in Li(4)(BH(4))(NH(2))(3) is evaluated to be 0.26 eV, less than half those in Li(2)(BH(4))(NH(2)) and Li(BH(4)). This study not only demonstrates an important direction in which to search for higher ion conductivity in complex hydrides but also greatly increases the material variations of solid electrolytes.

Halide-stabilized LiBH4, a room-temperature lithium fast-ion conductor.

Solid state lithium conductors are attracting much attention for their potential applications to solid-state batteries and supercapacitors of high energy density to overcome safety issues and irreversible capacity loss of the currently commercialized ones. Recently, we discovered a new class of lithium super ionic conductors based on lithium borohydride (LiBH(4)). LiBH(4) was found to have conductivity as high as 10(-2) Scm(-1) accompanied by orthorhombic to hexagonal phase transition above 115 degrees C. Polarization to the lithium metal electrode was shown to be extremely low, providing a versatile anode interface for the battery application. However, the high transition temperature of the superionic phase has limited its applications. Here we show that a chemical modification of LiBH(4) can stabilize the superionic phase even below room temperature. By doping of lithium halides, high conductivity can be obtained at room temperature. Both XRD and NMR confirmed room-temperature stabilization of superionic phase for LiI-doped LiBH(4). The electrochemical measurements showed a great advantage of this material as an extremely lightweight lithium electrolyte for batteries of high energy density. This material will open alternative opportunities for the development of solid ionic conductors other than previously known lithium conductors.

Preparation of Ultrafine Fe-Pt Alloy and Au Nanoparticle Colloids by KrF Excimer Laser Solution Photolysis.

We prepared ultrafine Fe-Pt alloy nanoparticle colloids by UV laser solution photolysis (KrF excimer laser of 248 nm wavelength) using precursors of methanol solutions into which iron and platinum complexes were dissolved together with PVP dispersant to prevent aggregations. From TEM observations, the Fe-Pt nanoparticles were found to be composed of disordered FCC A1 phase with average diameters of 0.5-3 nm regardless of the preparation conditions. Higher iron compositions of nanoparticles require irradiations of higher laser pulse energies typically more than 350 mJ, which is considered to be due to the difficulty in dissociation of Fe(III) acetylacetonate compared with Pt(II) acetylacetonate. Au colloid preparation by the same method was also attempted, resulting in Au nanoparticle colloids with over 10 times larger diameters than the Fe-Pt nanoparticles and UV-visible absorption peaks around 530 nm that originate from the surface plasmon resonance. Differences between the Fe-Pt and Au nanoparticles prepared by the KrF excimer laser solution photolysis are also discussed.

Changes in the radical-scavenging activity of sliced red and green cabbages during storage.

Vegetables are rich source of antioxidative components such as ascorbic acid and polyphenols, which scavenge free radicals and reactive oxygen species and prevent life-style related diseases. In this work, the changes of radical-scavenging activity in shredded red and green cabbage leaves during storage were determined as well as ascorbic acid and polyphenol contents. Shredded cabbage leaves were stored at 10 degrees C for 7 days in the presence or absence of oxygen. Radical-scavenging activity, ascorbic acid content, and polyphenol content of shredded cabbage leaves remained for 7 days in the presence and absence of oxygen. These results demonstrate that the radical-scavenging activity, ascorbic acid, and polyphenols are stable in shredded cabbage leaves and that oxygen does not affect the activity and active components.