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All-solid-state Li/S cells with high safety and high capacity were fabricated using a sulfur composite electrode prepared by mechanically milling S, P2S5 and a conductive additive (Ketjen black). The cells with 50 wt% sulfur content in the composite electrode showed a high reversible capacity of 942 mA h (g-sulfur)−1 at a constant current density of 0.64 mA cm−2 (0.1C). The discharge–charge mechanism of the high-capacity sulfur composite electrode without electrolytes was investigated. XRD and NMR measurements showed that amorphous P2S5+x species, where sulfur chains bridged phosphorus atoms, were produced in the as-milled composite electrode. Mixing of the amorphous P2S5+x and Ketjen black in the submicron order was indicated from the FE-SEM observation and EDX mapping of the electrode. XRD and TEM measurements of the sulfur electrodes before and after the discharge–charge processes indicated that the compounds in the electrodes remained in the amorphous state during these processes. XPS measurement showed that cleavages and associations of the disulfide bonds occurred in the amorphous compounds during the discharge–charge processes. A novel discharge–charge mechanism with an atomic-level dispersion of a sulfur redox part in an ion conductive part was proposed for the high-capacity sulfur electrode. [ABSTRACT FROM AUTHOR]

We investigated the structural phase transition of the Ba 1 − x Sr x Al 2 O 4 solid-solution system ( x ⩾ 0.6 ) via in situ powder X-ray diffraction and transmission electron microscopy. The sequence of structural phase transitions P 6 3 22 ↔ P 6 3 ( 3 a p ) ↔ P 2 1 occurs in a composition window of x =0.8–1.0. Ba substitution suppresses the P6 3 intermediate and low-temperature P2 1 phases, which disappear at x =0.7 and 0.6, respectively. The P2 1 phase boundary exhibits first-order characteristics, at which the cell parameters change discontinuously and the cell volume slightly contracts as the temperature increases. In the P2 1 phase, unstable twin walls are observed; the shapes and the crystal axes of each twin domain change as the temperature increases. This instability can be attributed to the latent instabilities that both the BaAl 2 O 4 and SrAl 2 O 4 compounds possess. [ABSTRACT FROM AUTHOR]

In the ferroelectric mixed-oxide system Ba(Ti1−xZrx)O3(BTZ), an increase in Zr content results in the crossover from the ferroelectric MA-type state with monoclinic symmetry to the relaxor state around x = 0.28. As a result of the crossover, BTZ is identified as the relaxor for x > 0.28. To understand the nature of the relaxor in BTZ, direct observations of the paraelectric (PE), MA, and relaxor states for 0.17 ≤ x ≤ 0.40 was carried out between 400 K and 87 K by transmission electron microscopy with the help of the failure of Friedel's law. The observations indicated that polar nanometer-sized regions with <110>PEand <001>PEcomponents were separately observed in the PE state above bothTcandTm, which are, respectively, a transition temperature of the direct (PE→MA) transition and a maximum temperature of the real dielectric permittivity for the relaxor. During cooling from the paraelectric state aboveTmin the relaxor, in the relaxor state below it, <001>PC-component regions locally formed a 180° domain structure, together with no coalescence of <110>PCregions. It is thus understood that the MA-to-relaxor crossover is characterized by the complete suppression of the coalescence of polar nanometer-sized regions with <110>PEcomponents. The relaxor state belowTmfor 0.29 ≤ x ≤ 0.40 could be, as a result, identified as an assembly of polar nanometer-sized domains, presumably with monoclinic symmetry. [ABSTRACT FROM AUTHOR]

We investigated the crystal structures and dielectric properties of an improper ferroelectric Ba1−xSrxAl2O4 (x≤0.1) and revealed that suppressing the condensation of the M-point soft mode involves the emergence of a "fluctuating" state. In the low-Sr-concentration region of x≤0.06, crystals exhibit a ferroelectric phase transition at TC from a paraelectric phase with a space group P6322 (PE phase) to a low-temperature ferroelectric phase with a P63 structure with doubled a and b axes (FE phase). Additionally, the temperature dependence of the dielectric constant ɛ′ exhibits a peak at TC. As x increases, TC decreases substantially, and the peak at TC becomes small. For x≥0.07, the peak is barely noticeable and becomes an anomaly at T*≈200 K, indicating that the system possesses another state (FL state) below the T*. The PE phase has been reported to possess two energetically competing soft modes at the M and K points. Electron diffraction (ED) experiments revealed that the superlattice reflections of the FE phase become diffuse scatterings originating from the M-point soft mode as the FE-FL boundary is approached. The K-point soft mode disappears in the FL state, whereas the M-point soft mode survives and fluctuates without condensation. Dark-field (DF) images revealed that the M-point soft mode exhibits coherent motion in nanodomains with sizes of approximately 10 nm in the FL state. The emergence of the FL state is ascribed to enhanced vibration of the AlO4 tetrahedra resulting from the substitution of Sr, which has a smaller ionic radius than Ba. [ABSTRACT FROM AUTHOR]

We studied the physical properties of hollandite titanates, BaxTi8O16+δ, which have double chains of edgesharing TiO6 octahedra with d electrons in the t2g states. We found that there is an electronic phase transition at ~220 K, at which various properties exhibit anomalies. This phase transition is characterized by a modulation in the TiO6 chains and a spectral weight transfer of over 2 eV in the optical conductivity spectrum, which are presumably caused by charge and orbital ordering of the Ti t2g electrons. [ABSTRACT FROM AUTHOR]

Synchrotron x-ray diffraction experiments were performed on the network compounds Ba1-xSrxAl2O4 at temperatures between 15 and 800 K. The ferroelectric phase of the parent BaAl2O4 is largely suppressed by substituting a small amount of Sr for Ba and disappears for x≥0.1. Structural refinements reveal that the isotropic atomic displacement parameter Biso in the bridging oxygen atom is largely independent of temperature and retains an anomalously large value in the adjacent paraelectric phase even at the lowest temperature. The Biso systematically increases as x increases, exhibiting an especially large value for x=0.5. According to previous electron diffraction experiments for Ba1-xSrxAl2O4 with x≥0.1, strong thermal diffuse scattering occurs at two reciprocal points relating to two distinct soft modes at the M and K points over a wide range of temperatures below 800 K [Y. Ishii et al., Sci. Rep. 6, 19154 (2016)]. Although the latter mode disappears at approximately 200 K, the former does not condense, at least down to 100 K. The anomalously large Biso observed in this study is ascribed to these soft modes existing in a wide temperature range. [ABSTRACT FROM AUTHOR]

No studies have focused on the trajectory of the average relative dose intensity (ARDI) during cycles of first-line chemotherapy for patients with diffuse large B-cell lymphoma. To evaluate the impact of attenuating ARDI during cycles on overall survival, we conducted a multi-centre, longitudinal, observational retrospective study. A total of 307 analysable patients were enrolled. Multivariate Cox hazards modelling with restricted cubic spline models revealed prognostic benefits of higher ARDI up to, but not after, cycle 6. According to group-based trajectory modelling, patients were classified into five groups depending on the pattern of ARDI changes. Among these, two groups in which ARDI had fallen significantly to less than 50% by cycles 4-6 displayed significantly poorer prognosis, despite increased ARDI in the second half of the treatment period (log-rank p = 0.02). The Geriatric Nutritional Risk Index offered significant prediction of unfavourable ARDI changes (odds ratio 2.540, 95% confidence interval 1.020-6.310; p = 0.044). Up to cycle 6, maintenance of ARDI in all cycles (but particularly in the early cycles) is important for prognosis. Malnutrition is a significant factor that lets patients trace patterns of ARDI changes during cycles of chemotherapy associated with untoward prognosis.

All-solid-state lithium-sulfur (Li/S) batteries are promising next-generation energy-storage devices owing to their high capacities and long cycle lives. The Li 2 S active material used in the positive electrode has a high theoretical capacity; consequently, nanocomposites composed of Li 2 S, solid electrolytes, and conductive carbon can be used to fabricate high-energy-density batteries. Moreover, the active material should be constructed with both micro- and nanoscale ion-conduction pathways to ensure high power. Herein, a Li 2 S-Li 2 O-LiI positive electrode is developed in which the active material is dispersed in an amorphous matrix. Li 2 S-Li 2 O-LiI exhibits high charge-discharge capacities and a high specific capacity of 998 mAh g -1 at a 2 C rate and 25 °C. X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy observation suggest that Li 2 O-LiI provides nanoscale ion-conduction pathways during cycling that activate Li 2 S and deliver large capacities; it also exhibits an appropriate onset oxidation voltage for high capacity. Furthermore, a cell with a high areal capacity of 10.6 mAh cm -2 is demonstrated to successfully operate at 25 °C using a Li 2 S-Li 2 O-LiI positive electrode. This study represents a major step toward the commercialization of all-solid-state Li/S batteries., (© 2023 Wiley-VCH GmbH.)

Soft magnetic materials have low coercive fields and high permeability. Recently, nanocrystalline alloys obtained using annealing amorphous alloys have attracted much interest since nanocrystalline alloys with small grain sizes of tens of nanometers exhibit low coercive fields comparable to that of amorphous alloys. Since nanocrystalline soft magnetic materials attain remarkable soft magnetic properties by controlling the grain size, the crystal grains' microstructure has a substantial influence on the soft magnetic properties. In this research, we examined the magnetic properties of Fe-Si-B-P-Cu nanocrystalline soft magnetic alloys obtained by annealing amorphous alloys. During crystallization, the observation findings reveal the correlation between the generated microstructures and soft magnetic properties., (© The Author(s) 2022. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Coating the surface of the cathode active material of all-solid-state batteries with sulfide-based solid electrolytes is key for improving and enhancing the battery performance. Although lithium niobate (LiNbO 3 ) is one of the most representative coating materials, its low durability at a highly charged potential and high temperature is an impediment to the realization of high-performance all-solid-state batteries. In this study, we developed new hybrid coating materials consisting of lithium niobate (Li-Nb-O) and lithium phosphate (Li-P-O) and investigated the influence of the ratio of P/(Nb + P) on the durability performance. The cathode half-cells, using a sulfide-based solid electrolyte Li 6 PS 5 Cl/cathode active material, LiNi 0.5 Co 0.2 Mn 0.3 O 2 , coated with the new hybrid coating materials of LiP x Nb 1- x O 3 ( x = 0-1), were exposed to harsh conditions (60 °C and 4.55 V vs Li/Li + ) for 120 h as a degradation test. P substitution resulted in higher durability and lower interfacial resistance. In particular, the hybrid coating with x = 0.5 performed better, in terms of capacity retention and interfacial resistance, than those with other compositions of niobate and phosphate. The coated cathode active materials were analyzed using various analytical techniques such as scanning electron microscopy/energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy (XAS) to elucidate the improvement mechanism. Moreover, the degraded cathodes were observed using time-of-flight secondary-ion mass spectrometry, TEM/electron diffraction, and XAS. These analyses revealed that the Nb-O-P coordination in the hybrid coating material captured O by P. The coordination suppressed the release of O from the coating layer as a decomposition side reaction to realize a higher durability than that of LiNbO 3 .

Interfacial engineering of sulfide-based solid electrolyte/lithium-transition-metal oxide active materials in all-solid-state battery cathodes is vital for cell performance parameters, such as high-rate charge/discharge, long lifetime, and wide temperature range. A typical interfacial engineering method is the surface coating of the cathode active material with a buffer layer, such as LiNbO 3 . However, cell performance reportedly degrades under harsh environments even with a LiNbO 3 coating, such as high temperatures and high cathode potentials. Therefore, we investigated the interfacial degradation mechanism focusing on the solid electrolyte side for half cells employing the cathode mixture of argyrodite-type Li 6 PS 5 Cl/LiNbO 3 -coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 exposed at 60 °C and 4.25 and 4.55 V vs Li/Li + using transmission electron microscopy/electron diffraction (TEM/ED) and X-ray absorption spectroscopy (XAS). The TEM/ED results indicated that the ED pattern of the argyrodite structure disappeared and changed to an amorphous phase as the cells degraded. Moreover, the crystal phases of LiCl and Li 2 S appeared simultaneously. Finally, XAS analysis confirmed the decrease in the PS 4 units of the argyrodite structure and the increase in local P-S-P domains with delithiation from the interfacial solid electrolyte, corresponding to the TEM/ED results. In addition, the formation of P-O bonds was confirmed during degradation at higher cathode potentials, such as 4.55 V vs Li/Li + . These results indicate that the degradation of this interfacial region determines the cell performance.

Introduction Invasive fungal infections have been attracting attention as significant fatal complications in patients with febrile neutropenia (FN) who undergo intensive chemotherapy or hematopoietic stem cell transplantation to treat hematological malignancies. Although clinical trials are already underway in other countries, evidence supporting the use of caspofungin (CAS) in FN patients in Japan is still insufficient. Methods A retrospective study of patients treated with CAS for FN associated with hematological diseases between April 2015 and March 2018 was conducted to determine the treatment efficacy and safety. The study was conducted as a multicenter collaboration, and the data of 52 patients who met all of the inclusion criteria were analyzed. A five-composite-endpoint method was used, and the treatment was judged to be effective when all five endpoints (defervescence during neutropenia; no breakthrough fungal infections; resolution of baseline fungal infections; a survival for seven days or more after the completion of therapy; and no discontinuation of therapy due to side effects or invalidity) were met. Results The efficacy rate was 53.8% (28/52), which is close to the average reported efficacy rate. Adverse events included liver dysfunction and electrolyte abnormalities, but no renal dysfunction or serious events were seen. Conclusion These results suggest that the use of CAS in FN patients with hematological diseases is effective and well-tolerated, and we believe that the use of CAS could become a significant treatment in Japan.

The rational design principle of highly active catalysts for the oxygen evolution reaction (OER) is desired because of its versatility for energy-conversion applications. Postspinel-structured oxides, Ca B 2 O 4 ( B = Cr 3+ , Mn 3+ , and Fe 3+ ), have exhibited higher OER activities than nominally isoelectronic conventional counterparts of perovskite oxides La B O 3 and spinel oxides Zn B 2 O 4 . Electrochemical impedance spectroscopy reveals that the higher OER activities for Ca B 2 O 4 series are attributed to the lower charge-transfer resistances. A density-functional-theory calculation proposes a novel mechanism associated with lattice oxygen pairing with adsorbed oxygen, demonstrating the lowest theoretical OER overpotential than other mechanisms examined in this study. This finding proposes a structure-driven design of electrocatalysts associated with a novel OER mechanism., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Sulfide-based solid electrolytes (SEs) exhibiting high ionic conductivity are indispensable battery materials for next-generation all-solid-state batteries. However, sulfide-based SEs have a major drawback in their low chemical stability in air. When exposed to H2O or O2 gas, toxic H2S is generated, and their ionic conductivity considerably declines. However, their degradation mechanism caused by air exposure has not been understood yet. To clarify the degradation process, in this study, we developed a transmission electron microscope (TEM) system to evaluate the air stability of battery materials. Using a vacuum transfer double-tilt TEM holder with a gas-flow system, the in situ observation of the degradation process was conducted for a sulfide-based Li4SnS4 glass ceramic under an air-flow environment. Consequently, electron diffraction (ED) patterns and TEM images could clearly capture morphological changes and the amorphization process caused by air exposure. Moreover, based on the analysis of ED patterns, it is observed that Li4SnS4 is likely to decompose because of the reaction with H2O in air. Therefore, this airtight and air-flow TEM system should be effective in clarifying the process of the deterioration of sulfur-based SEs during exposure to air., (© The Author(s) 2021. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Because of the heterogeneity among older patients with diffuse large B-cell lymphoma (DLBCL), the establishment of an easy-to-use geriatric assessment tool is an unmet need. We verified the impact of the Geriatric 8 (G8) on treatment stratification and overall survival (OS). We conducted a retrospective, multicentre analysis of older patients (≥65 years) with DLBCL. The primary endpoint was OS. The total average relative dose intensity (tARDI) was defined as the average delivered dose intensity divided by the planned dose intensity through all cycles. A total of 451 patients were diagnosed with DLBCL from 2007 to 2017, and 388 patients received standard regimens. A multivariate Cox model confirmed that the G8 was a significant predictor of OS (hazard ratio 0·88, 95% confidence interval 0·828-0·935). A Cox model with restricted cubic spline showed a linear association between the G8 and the mortality risk. The G8 had a significant impact on OS in elderly patients with DLBCL. The upper limit of tARDI for standard regimens to improve OS might be appropriate at ≥80% for patients with high G8 scores and 60% for patients with low G8 scores. However, the standard regimens should be given to all patients regardless of the G8 score to improve OS., (© 2021 British Society for Haematology and John Wiley & Sons Ltd.)

Background: The management of severe adverse events (AEs) is important in safely and effectively providing chemotherapy to older adults with diffuse large B-cell lymphoma (DLBCL). However, reports on simple and DLBCL-specific predictive models for treatment-related toxicity in elderly individuals are scarce. The aim of this study was to examine the usefulness of Geriatric 8 (G8) in predicting treatment-related severe AEs, nonhematological toxicity, and febrile neutropenia in older adults with DLBCL in real-world practice., Materials and Methods: We conducted a multicenter, retrospective study on 398 consecutive patients with DLBCL (aged ≥65 years) who received standard therapy at three centers in Japan (University of Fukui Hospital, the Fukui Prefectural Hospital, and the Japanese Red Cross Fukui Hospital), between 2007 and 2017., Result: Multivariate logistic analysis demonstrated that the G8 score was an independent predictive factor for severe AEs. Moreover, a logistic regression model with restricted cubic spline showed a nonlinear association between the incidence of severe AEs and the G8 score. According to receiver operating characteristic analysis, the most discriminative cutoff value of the G8 for the incidence of severe AEs was 11, with an area under the curve value of 0.670. AEs occurred most often in the first course of chemotherapy and decreased as the course progressed., Conclusion: The G8 score, an easy-to-use geriatric assessment tool, can be a useful prediction model of treatment-related severe AEs during standard therapy in older adults with DLBCL., Implications for Practice: In older patients with diffuse large B-cell lymphoma (DLBCL), to accurately predict the risk of severe adverse events (AEs) in advance is essential for safe and effective treatment. This study demonstrated that the Geriatric 8 score, a simple and established geriatric assessment tool, indicated a high predictive ability for occurrence of therapy-related severe AEs in elderly patients with DLBCL who were treated with standard treatment., (© 2020 AlphaMed Press.)

Reflecting the increasing risk in elderly patients with diffuse large B cell lymphoma (DLBCL), prognostic predictors other than the International Prognostic Index have attracted more attention. This study presents the first analysis of the prognostic utility of the Geriatric Nutritional Risk Index (GNRI) in combination with the Charlson Comorbidity Index (CCI) for overall survival (OS) in elderly DLBCL patients. A multicentre retrospective was conducted on a cohort of 451 patients (≥65 years). The GNRI and CCI were independent predictors in a multivariate Cox proportional hazard model. There was a nonlinear correlation between the GNRI and OS in a Cox model with restricted cubic spline. Multivariate receiver operating characteristic curves showed a significant improvement in prediction accuracy when the GNRI was added to CCI. Adding the GNRI to CCI yielded a significant category-free net reclassification improvement (0·556; 95% CI: 0·378-0·736, P < 0·001) and integrated discrimination improvement (0·094; 95% CI: 0·067-0·122, P < 0·001). The decision curve analysis demonstrated the clinical net benefit associated with the adoption of the GNRI. The GNRI was not only a predictor of OS but also remarkably improved the prognosis prediction accuracy when incorporated with the CCI, having the ability to stratify the prognosis of elderly DLBCL patients., (© 2020 British Society for Haematology and John Wiley & Sons Ltd.)

An all-solid-state lithium battery using inorganic solid electrolytes requires safety assurance and improved energy density, both of which are issues in large-scale applications of lithium-ion batteries. Utilization of high-capacity lithium-excess electrode materials is effective for the further increase in energy density. However, they have never been applied to all-solid-state batteries. Operational difficulty of all-solid-state batteries using them generally lies in the construction of the electrode-electrolyte interface. By the amorphization of Li 2 RuO 3 as a lithium-excess model material with Li 2 SO 4 , here, we have first demonstrated a reversible oxygen redox reaction in all-solid-state batteries. Amorphous nature of the Li 2 RuO 3 -Li 2 SO 4 matrix enables inclusion of active material with high conductivity and ductility for achieving favorable interfaces with charge transfer capabilities, leading to the stable operation of all-solid-state batteries., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

The performances of next generation all-solid-state batteries might be improved by using multi-valent cation doped Li 6 PS 5 Cl solid electrolytes. This study provided solid electrolytes at room temperature using planetary ball milling without heat treatment. Li 6 PS 5 Cl was doped with a variety of multivalent cations, where an electrolyte comprising 98% Li 6 PS 5 Cl with 2% YCl 3 doping exhibited an ionic conductivity (13 mS cm -1 ) five times higher than pure Li 6 PS 5 Cl (2.6 mS cm -1 ) at 50 °C. However, this difference in ionic conductivity at room temperature was slight. No peak shifts were observed, including in the synchrotron XRD measurements, and the electron diffraction patterns of the nano-crystallites ( ca. 10-30 nm) detected using TEM exhibited neither peak shifts nor new peaks. The doping element remained at the grain boundary, likely lowering the grain boundary resistance. These results are expected to offer insights for the development of other lithium-ion conductors for use in all-solid-state batteries., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Varicella zoster virus (VZV) infection sometimes result in visceral disseminated VZV infection (VD-VZV), which is a fulminant disease featured by abdominal pain and the absence of skin lesions, particularly occurs in the immunosuppressive patients. Brachial plexus neuritis (BPN) is another rare type of VZV infection usually appears without blisters. Few diagnostic images of both VD-VZV and BPN-VZV have been reported. A 25-year-old woman receiving allogeneic hematopoietic stem cell transplantation (HSCT) for acute myeloid leukemia. Unexplained severe pain in the left upper extremity followed by severe stomachache, liver dysfunction and unconsciousness appeared on day 344 post-HSCT. Computed tomography (CT) showed left brachial plexus hypertrophy and edematous changes to the hepatoduodenal ligament, fluorodeoxyglucose positron emission tomography (FDG-PET) showed increased uptake in both lesions. Intravenous acyclovir therapy was started and successfully resolved all symptoms. Several days later, blisters appeared all over the body and positive VZV DNA from blood using polymerase chain reaction test was obtained. FDG-PET and CT may offer supportive findings for detecting or diagnosing blister-less VZV infectious diseases., (Copyright © 2019 Japanese Society of Chemotherapy and The Japanese Association for Infectious Diseases. Published by Elsevier Ltd. All rights reserved.)

Liquid-phase synthesis is a useful technique for preparing argyrodite sulfide-based solid electrolytes, and the synthesis conditions such as heat treatment strongly affect the conductivity. Because the understanding of structural changes reveals crucial information about their properties, it is necessary to evaluate this change during heat treatment to determine the factors that affect the conductivity. In this study, X-ray diffraction measurements and transmission electron microscope observations reveal the effects of heat treatment on the crystallinities and ionic conductivities in the synthesis process of argyrodite electrolytes with tetrahydrofuran and ethanol. The amorphous material is in the main phase when heated at low temperatures below 200 °C and exhibits relatively low conductivities of ca. 2 × 10 -4 S cm -1 despite precipitation of the argyrodite crystals. As the heat treatment temperature increases, the ratio of argyrodite crystals increases, involving nucleation and grain growth, leading to high conductivities of over 10 -3 S cm -1 . It is critical to control the ratio of the amorphous and crystal phases to achieve high conductivities in the synthesis of argyrodite electrolytes via liquid-phase processing., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Lithium-ion batteries are widely used as a power source for portable equipment. However, the use of highly flammable organic solvents in the liquid electrolyte component in these batteries presents a serious safety concern. In this study, the thermal stability of battery cathodes comprising LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) and LiPF 6 -based electrolyte solutions have been investigated using transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) methods. Ex situ TEM measurements revealed that significant structural change occurred in the charged NMC composite after heating at a temperature above the exothermal peaks. It was found that LiF nanocrystallites precipitated in LiPF 6 and that a number of nanoscale stacking faults developed in the [Formula: see text] layered structure of NMC. The results suggested that the decomposition reaction of LiPF 6 and the structural change of NMC were directly associated with the exothermic reaction in the liquid electrolyte-based NMC electrode composite.

Sulfide-based all-solid-state lithium batteries are a next-generation power source composed of the inorganic solid electrolytes which are incombustible and have high ionic conductivity. Positive electrode composites comprising LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) and 75Li 2 S·25P 2 S 5 (LPS) glass electrolytes exhibit excellent charge-discharge cycle performance and are promising candidates for realizing all-solid-state batteries. The thermal stabilities of NMC-LPS composites have been investigated by transmission electron microscopy (TEM), which indicated that an exothermal reaction could be attributed to the crystallization of the LPS glass. To further understand the origin of the exothermic reaction, in this study, the precipitated crystalline phase of LPS glass in the NMC-LPS composite was examined. In situ TEM observations revealed that the β-Li 3 PS 4 precipitated at approximately 200 °C, and then Li 4 P 2 S 6 and Li 2 S precipitated at approximately 400 °C. Because the Li 4 P 2 S 6 and Li 2 S crystalline phases do not precipitate in the single LPS glass, the interfacial contact between LPS and NMC has a significant influence on both the LPS crystallization behavior and the exothermal reaction in the NMC-LPS composites.

In general, the ionic conductivity of sulfide glasses decreases with their crystallization, although it increases for a few sulphide glasses owing to the crystallization of a highly conductive new phase (e.g., Li 7 P 3 S 11 : 70Li 2 S-30P 2 S 5 ). We found that the ionic conductivity of 75Li 2 S-25P 2 S 5 sulfide glass, which consists of glassy and crystalline phases, is improved by optimizing the conditions of the heat treatment, i.e., annealing. A different mechanism of high ionic conductivity from the conventional mechanism is expected in the glassy phase. Here, we report the glassy structure of 75Li 2 S-25P 2 S 5 immediately before the crystallization by using the differential pair distribution function (d-PDF) analysis of high-energy X-ray diffraction. Even though the ionic conductivity increases during the optimum annealing, the d-PDF analysis indicated that the glassy structure undergoes no structural change in the sulfide glass-ceramic electrolyte at a crystallinity of 33.1%. We observed the formation of a nanocrystalline phase in the X-ray and electron diffraction patterns before the crystallization, which means that Bragg peaks were deformed. Thus, the ionic conductivity in the mixture of glassy and crystalline phases is improved by the coexistence of the nanocrystalline phase.

There are two types of solid electrolytes which has been recently expected to be applied to all-solid-state batteries. One is the glasses characterized by an amorphous state. The other is the glass ceramics containing crystalline in an amorphous matrix. However, the non-crystalline state of glasses and glass ceramics is still an open question. It has been anticipated that sea-island and core-shell structures including crystalline nanoparticles have been proposed as candidate models for glass ceramics. Nevertheless, no direct observation has been conducted so far. Here we report the non-crystalline state of Li 2 S-P 2 S 5 glasses and glass ceramics, and the crystallization behavior of the glasses during heating via direct transmission electron microscopy (TEM) observation. High resolution TEM images clearly revealed the presence of crystalline nanoparticles in an amorphous region. Eventually we suggest that the precipitation and connection of crystalline nanoparticles in an amorphous matrix are key to achieving high ionic conductivity.

Bifunctional electrocatalysts for oxygen evolution/reduction reaction (OER/ORR) are desirable for the development of energy conversion technologies. It is discovered that the manganese quadruple perovskites CaMn 7 O 12 and LaMn 7 O 12 show bifunctional catalysis in the OER/ORR. A possible origin of the high OER activity is the unique surface structure through corner-shared planar MnO 4 and octahedral MnO 6 units to promote direct OO bond formations., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Purpose: The Japan Prosthodontic Society (JPS) has proposed a new diagnostic nomenclature system (DNS), based on pathogenesis and etiology, to facilitate and improve prosthodontic treatment. This system specifies patient disability and the causative factor (i.e. "B (disability) caused by A (causative factor)"). The purpose of this study was to examine the reliability and validity of this DNS., Study Selection: The JPS Clinical Guideline Committee assessed mock patient charts and formulated disease names using the new DNS. Fifty validators, comprising prosthodontic specialists and dental residents, made diagnoses using the same patient charts. Reliability was evaluated as the consistency of the disease names among the validators, and validity was evaluated using the concordance rate of the disease names with the reference disease names., Results: Krippendorff's α was 0.378 among all validators, 0.370 among prosthodontic specialists, and 0.401 among dental hospital residents. Krippendorff's α for 10 validators (3 specialists and 7 residents) with higher concordance rates was 0.524. Two validators (1 specialist and 1 resident) with the highest concordance rates had a Krippendorff's α of 0.648. Common disease names had higher concordance rates, while uncommon disease names showed lower concordance rates. These rates did not show correlation with clinical experience of the validator or time taken to devise the disease name., Conclusions: High reliability was not found among all validators; however, validators with higher concordance rates showed better reliability. Furthermore, common disease names had higher concordance rates. These findings indicate that the new DNS for prosthodontic dentistry exhibits clinically acceptable reliability and validity., (Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Purpose: Dentists may encounter patients who present with a sense of a malocclusion but in whom no objective findings can be detected. For the patient who insists that there is occlusal discomfort, in the absence of evidence some dentists elect to perform an occlusal adjustment that not only fails to alleviate symptoms, and may, in fact, exacerbate the discomfort. The patient-dentist relationship is then likely compromised because of a lack of trust., Study Selection: In 2011, the Clinical Practice Guidelines Committee of the Japan Prosthodontic Society formulated guidelines for the management of occlusal discomfort. When formulating clinical practice guidelines, the committee bases their recommendations on information derived from scientific evidence. For "occlusal dysesthesia," however, there are an insufficient number of high-quality papers related to the subject. Therefore, a consensus meeting was convened by the Japan Prosthodontic Society to examine evidence in the Japanese- and English-language literature and generate a multi-center survey to create an appropriate appellation for this condition., Results: As a result of the consensus meeting and survey findings, this condition may be justifiably termed "occlusal discomfort syndrome.", Conclusions: The Japan Prosthodontics Society believes that identification of an umbrella term for occlusal discomfort might serve as a useful guide to formulating clinical practice guidelines in the future. This position paper represents summary findings in the literature combined with the results of a multicenter survey focused on dental occlusal treatment and the condition of patients who present with occlusal discomfort syndrome., (Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The structural fluctuation in hexagonal Ba(1-x)Sr(x)Al2O4 with a corner-sharing AlO4 tetrahedral network was characterized at various temperatures using transmission electron microscopy experiments. For x ≤ 0.05, soft modes of q ~ (1/2, 1/2, 0) and equivalent wave vectors condense at a transition temperature (TC) and form a superstructure with a cell volume of 2a × 2b × c. However, TC is largely suppressed by Sr-substitution, and disappears for x ≥ 0.1. Furthermore, the q ~ (1/2, 1/2, 0) soft mode deviates from the commensurate value as temperature decreases and survives in nanoscaled regions below ~200 K. These results strongly suggest the presence of a new quantum criticality induced by the soft mode. Two distinct soft modes were observed as honeycomb-type diffuse scatterings in the high-temperature region up to 800 K. This intrinsic structural instability is a unique characteristic of the framework compound and is responsible for this unusually fluctuating state.

The oxygen evolution reaction that occurs during water oxidation is of considerable importance as an essential energy conversion reaction for rechargeable metal-air batteries and direct solar water splitting. Cost-efficient ABO3 perovskites have been studied extensively because of their high activity for the oxygen evolution reaction; however, they lack stability, and an effective solution to this problem has not yet been demonstrated. Here we report that the Fe(4+)-based quadruple perovskite CaCu3Fe4O12 has high activity, which is comparable to or exceeding those of state-of-the-art catalysts such as Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) and the gold standard RuO2. The covalent bonding network incorporating multiple Cu(2+) and Fe(4+) transition metal ions significantly enhances the structural stability of CaCu3Fe4O12, which is key to achieving highly active long-life catalysts.