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Frostbite occurs when the skin is exposed to localized low temperatures. The main causes of frostbite are thought to be direct cell injury due to freezing of cells and tissue ischemia due to abnormal blood circulation. However, the molecular mechanism of frostbite has not been elucidated. This study aims to explain the molecular dynamics of frostbite using a mouse frostbite model and keratinocyte cell culture. Comprehensive gene expression analysis performed on mouse skin samples revealed that β-catenin signaling is activated by frostbite. Immunohistochemistry showed nuclear translocation of β-catenin in the skin of frostbite model mice that was not observed in mice subjected to a mechanical skin damage model induced by tape stripping. Tissue hypoxia, as detected by pimonidazole staining, coexisted with nuclear expression of β-catenin. In keratinocyte cell cultures, nuclear translocation of β-catenin was induced by hypoxia, but not by low temperature. Hypoxia induced epithelial-mesenchymal transition - an important biological event in the healing process of skin - and in vitro wound-healing activity, both of which were suppressed by β-catenin inhibition. Our results suggest that during frostbite, impaired blood flow causes hypoxia, which in turn activates β-catenin that promotes keratinocyte motility and tissue repair.

Background Accidental hypothermia (AH) sometimes leads to coagulation disorder, especially in severe AH. We previously demonstrated that intrasplenic platelet activation caused aberrant hemostasis and thrombus formation after rewarming in a murine AH model. However, no study has focused on the appropriate management of platelets causing coagulation activation after rewarming of AH. We investigated whether or not recombinant soluble thrombomodulin (rTM) can suppress thrombosis formation after rewarming using a rat AH model. Methods Wistar rats were exposed to an ambient temperature of −20 °C under general anesthesia until their rectal temperature decreased to 26 °C. The Hypo group rats (n = 5) were immediately euthanized, while the Hypo/Re group (n = 5) and rTM group rats (n = 5), which were administered rTM (1 mg/kg) via the tail vein, were rewarmed until the rectal temperature returned to 34 °C and then euthanized 6 h later. Tissue and blood samples were collected from all rats for histopathological and coagulation analyses at euthanasia. Results There was no significant change in the D-dimer level in the Hypo group rats, while the D-dimer level was significantly elevated at 6 h after rewarming in the Hypo/Re group rats (P = 0.015), and histopathology detected both fibrin and platelets in the renal glomerulus. However, the rTM group rats did not show any elevation of the D-dimer levels at 6 h after rewarming, and no fibrin was noted on histopathology. Conclusions rTM may be useful as an appropriate anticoagulant in cases of aberrant hemostasis after rewarming of AH.

An asymptomatic 75-year-old woman was identified with a 40-mm-sized, round-shaped lesion beside the pulmonary artery on computed tomography (CT). Coronary angiography showed a coronary artery fistula (CAF) with an aneurysm branching from the left anterior descending artery toward the pulmonary artery. The CAF aneurysm (CAFA) was resected and coronary artery bypass graft surgery using the left internal thoracic artery was performed successfully. Pathological analysis revealed that medial depletion similar to segmental arterial mediolysis (SAM) may contribute to aneurysm formation.

Background Colchicine binds to intracellular tubulin and prevents mitosis. Colchicine is also used as an anti-inflammatory drug. Meanwhile, excess administration of medication or accidental ingestion of colchicine-containing plants can cause acute colchicine poisoning, which initially results in gastrointestinal effects that may be followed by multiorgan dysfunction. However, the mechanism of colchicine poisoning remains unclear, and there are no standard therapeutic strategies. Aims We focused on intestinal barrier function and attempted to reveal the underlying mechanism of colchicine poisoning using an animal model. Methods Colchicine was orally administered to C57Bl/6 mice. Then, we performed histopathological analysis, serum endotoxin assays, and intestinal permeability testing. Additionally, the LPS-TLR4 signaling inhibitor TAK-242 was intraperitoneally injected after colchicine administration to analyze the therapeutic effect. Results We observed villus height reduction and increased numbers of apoptotic cells in the gastrointestinal epithelium of colchicine-treated mice. Both intestinal permeability and serum endotoxin levels were higher in colchicine-treated mice than in control mice. Although colchicine-poisoned mice died within 25 h, those that also received TAK-242 treatment survived for more than 48 h. Conclusion Colchicine disrupted intestinal barrier function and caused endotoxin shock. Therapeutic inhibition of LPS-TLR4 signaling might be beneficial for treating acute colchicine poisoning.

Lead fluoride (PbF₂) is a promising electrode material for fluoride shuttle batteries (FSBs) owing to its high theoretical capacity (219 mAh g⁻¹). In this study, the discharge and charge capacities of a PbF₂ electrode were measured using a bis[2‐(2‐methoxyethoxy)ethyl] ether containing cesium fluoride and triphenylborane as an electrolyte. A high specific capacity was maintained during both the discharge and charge processes in the first cycle, but the capacity decreased from the first charge process to the following discharge process. To clarify the electrochemical reaction mechanism, the dissolution and change in the electronic state of Pb at the PbF2 electrode during the discharge and charge processes were evaluated via atomic absorption spectrometry (AAS) and X‐ray photoelectron spectroscopy (XPS). The results obtained from AAS and XPS indicated that Pb was formed during the discharge process. Conversely, the formation of PbF₂ and dissolution of Pb coexisted within the wide range of charge process. The PbF₂ could react in the following cycle, but the dissolved Pb was unable to contribute to the following discharge/charge reaction. Therefore, after the initial charge process, the capacity decreased., This article also appears in: Electro, Physical & Theoretical Chemistry

Fluoride shuttle battery (FSB) is a promising next-generation battery candidate. In the FSB, metal fluoride and organic solvent containing supporting electrolyte salt and anion acceptor were used as active material and electrolyte. In this study, using bis[2-(2-methoxyethoxy)ethyl] ether (tetraglyme: G4) containing cesium fluoride (CsF; 0.45 mol dm⁻³ or saturated) and triphenylboroxine (TPhBX; 0.50 mol dm⁻³) as electrolyte (CsF(0.45)–TPhBX(0.50)–G4 and CsF(sat.)–TPhBX(0.50)–G4), the electrochemical performance of bismuth fluoride (BiF₃) was assessed. Although the discharge and charge reactions of BiF₃ electrode proceeded in both electrolytes, the cycling performance of BiF₃ electrode in CsF(0.45)–TPhBX(0.50)–G4 was poorer than that in CsF(sat.)–TPhBX(0.50)–G4. The cause of differences in the electrochemical properties was investigated using atomic absorption spectrometry (AAS), X-ray photoelectron spectroscopy (XPS), and cross-sectional scanning electron microscopy (SEM)/energy dispersive X-ray spectroscopy (EDX). The AAS results indicate that the poor cycling performance with CsF(0.45)–TPhBX(0.50)–G4 was due to the dissolution of active material during charging. The XPS and cross-sectional SEM/EDX results indicate that the formation state of Bi, and the progress of electrolyte decomposition during discharging were affected by the CsF/TPhBX ratio in the electrolyte.

Bismuth fluoride (BiF3) is a promising positive electrode material for fluoride shuttle batteries (FSBs) owing to its high theoretical specific capacity (302 mA h g−1). However, it exhibits low practical capacity. The methods for preparing the electrode are known to have significant effects on battery performance. The mixture between BiF3 and carbon, BiF3/C, prepared by high energy ball milling method has been already approved in lithium ion batteries. With this method, a significant improvement over the discharge and charge capacities of the BiF3/C electrode has been achieved. In this work, for the first time, BiF3/C electrode has been used for FSB. Using BiF3/C electrode significantly increased the discharge and charge capacities. To confirm the progress of the discharge and charge reactions of BiF3/C electrode, the crystal structure of active materials and oxidation state of Bi for the BiF3/C electrode during discharging and charging has been investigated by X-ray diffraction and X-ray absorption fine structure. The results reveal that, with higher capacity values, discharge and charge reactions related to BiF3/C have been realized.

In fluoride shuttle batteries (FSBs), the addition of an anion acceptor (AA) is required to dissolve the supporting electrolyte salt in an organic solvent. Based on theoretical calculations and practical experiments, the effectiveness of triphenylboroxine (TPhBX) as an AA for FSB was verified. Using an electrolyte with TPhBX as an AA, the specific capacities of the following two types of lead fluoride (PbF2) electrodes were evaluated: (i) PbF2 pulverized using a ball mill, (ii) pulverized PbF2 mixed with carbon using a ball mill. The experimental results indicate that mixing PbF2 with carbon using a ball mill increases the specific capacity of PbF2 electrode.

Objectives: To evaluate the ‘One Stretch’ exercise’s effect on improvements in low back pain (LBP), psychological factors, and fear avoidance in a large number of nurses.Methods: Between July 2015 ...

As a cathode material, Li1.2Ni0.2Mn0.6O2 delivers high discharge capacity at low C-rate but low discharge capacity at high C-rate. Furthermore, a large potential hysteresis occurs during charge and discharge, and the charge-discharge curves change shape during the charge-discharge cycling. Increasing nickel/manganese (Ni/Mn) ratio in Li1.2NiyMn0.8−yO2 improves discharge capacity at high C-rate, but it decreases discharge capacity at low C-rate. To accomplish high discharge capacity at both high and low C-rates, lithium/transition-metal (Li/TM) ratio in high-nickel-content material, namely, Li1.2Ni0.35Mn0.45O2, was adjusted. Cathode materials with varied lithium/transition-metal ratio (x), namely, Li1.2−xNi0.35+(0.35/0.8)xMn0.45+(0.45/0.8)xO2 (x = 0, 0.02, 0.04, 0.06, or 0.08), were prepared, and their electrochemical performances were evaluated. It was found that as x was decreased, discharge capacity first increased then decreased, and Li1.2−xNi0.35+(0.35/0.8)xMn0.45+(0.45/0.8)xO2 (x = 0.04), which can be described as Li1.16Ni0.37Mn0.47O2, was found to exhibit the highest discharge capacity. Accordingly, the electrochemical properties of Li1.16Ni0.37Mn0.47O2 were compared with those of a conventional lithium-rich layer-structured cathode material, namely, Li1.2Ni0.2Mn0.6O2. The rate performance of Li1.16Ni0.37Mn0.47O2 was higher than that of Li1.2Ni0.2Mn0.6O2. Furthermore, potential hysteresis and shape change of the charge-discharge curves for Li1.16Ni0.37Mn0.47O2 were smaller than those for Li1.2Ni0.2Mn0.6O2. It is thus concluded that changing the composition of the cathode material from Li1.2Ni0.2Mn0.6O2 to Li1.16Ni0.37Mn0.47O2 alleviates the drawbacks of lithium-rich layer-structured cathode material, namely, low rate performance, potential hysteresis, and shape change of charge-discharge curves.

For liquid-based fluoride shuttle batteries, electrolyte composed of organic solvent and supporting electrolyte salt is developed. To increase the solubility of supporting electrolyte salt in organic solvent, anion acceptors (triphenylboroxine or triphenylborane) are added. The addition of anion acceptor greatly increases the solubility of supporting electrolyte salt, and discharge-charge reaction of BiF₃ electrode is confirmed in the prepared electrolytes. A supporting electrolyte salt (Cesium fluoride (CsF)) dissolves sparingly in an organic solvent (bis[2-(2-methoxyethoxy)ethyl]ether (tetraglyme: G4)); however, the solubility of the CsF in the G4 is greatly increased by addition of an anion acceptor (triphenylboroxine or triphenylborane). Using the developed electrolyte for fluoride shuttle battery, discharge and charge reactions of a metal fluoride electrode can be progressed.

Recently, the reversible discharge and charge reaction of BiF3 electrode for fluoride shuttle battery (FSB) that can be used as a promising candidate for next-generation battery are observed using a liquid-based electrolyte. In this study, we investigate the electrochemical performance of PbF2 as an active material for the FSB. To increase the electronic conductivity, the PbF2 was mixed with carbon, and the composite material between PbF2 and carbon, PbF2/C, is formed. High discharge and charge capacities are obtained for PbF2/C during the first cycle. Although the discharge and charge capacities gradually decreased, the discharge and charge reactions occurred in the second and third cycles. To confirm the progress of the discharge and charge reactions, the crystal structure change of the active material during discharging and charging in the first and second cycles is evaluated using X-ray diffraction (XRD). From the XRD results, the formation of Pb and PbF2 during discharging and charging can be confirmed, indicating that the discharge (PbF2 + 2e− → Pb + 2F−) and charge (Pb + 2F− → PbF2 + 2e−) reactions progress in both the first and second cycles.

Inflammatory bowel disease (IBD), such as ulcerative colitis (UC) and Crohn’s disease (CD), is an intractable intestinal inflammation associated with the disruption of the intestinal mucosa. We previously demonstrated that Lactobacillus brevis-derived long-chain polyphosphate (poly P) improved the intestinal barrier function by the upregulation of cell adhesion and relieved intestinal inflammation, thereby exerting a curing effect on colitis in vitro, in vivo, and in an investigator-initiated clinical study of UC. However, how poly P improves mucosal defects induced by intestinal inflammation has not been elucidated. In this study, we detected the accumulation of platelets in inflamed tissues induced by poly P in a dextran sulfate sodium- (DSS-) induced colitis mouse model. A light transmission aggregometry analysis and scanning electron microscopy showed that poly P promoted the platelet aggregation. An SRB assay and ki-67 staining showed that the supernatant of poly P-treated platelet-rich plasma (PRP) increased intestinal epithelial cell growth. A wound healing assay showed that the supernatant of poly P-treated PRP, but not poly P itself, accelerated wound healing. A Western blotting analysis indicated that mitogen-activated protein kinase activation was induced by the supernatant of poly P-treated human PRP in the epithelial cells and its wound healing effect was significantly decreased by the inhibition of ERK signaling. These data suggested that platelet-derived mediators induced by poly P improved intestinal inflammation through the promotion of epithelial cell growth by the activation of the ERK signaling pathway. The mechanism is a novel host-microbe interaction through mammalian platelet-derived mediators induced by bacterial molecules.

Background Colorectal cancers develop through several pathways, including the adenoma–carcinoma sequence and colitis-associated carcinogenesis. An altered intestinal microflora has been reported to be associated with the development and progression of colorectal cancer via these pathways. We identified Lactobacillus casei-derived ferrichrome as a mediator of the bacterial anti-tumor effect of colorectal cancer cells through the upregulation of DDIT3. In this study, we investigated the anti-tumor effects of ferrichrome on precancerous conditions and cancer cells associated with sporadic as well as colitis-associated colorectal cancer. Methods SRB and MTT assays were performed to assess growth inhibition in vitro. Eighteen organoids were prepared from biopsy specimens obtained by colonoscopy. An AOM-DSS carcinogenesis model and xenograft model of colorectal cancer cells were generated for the assessment of the tumor suppressive effect of ferrichrome in vivo. Results Ferrichrome inhibited the cell growth of colorectal cancer cells in vitro and in in vivo xenograft models. Ferrichrome exerted a strong tumor-suppressive effect that was superior to that of currently available anti-tumor agents, including 5-FU and cisplatin, both in vitro and in vivo. The tumor-suppressive effect of the combination of ferrichrome and 5-FU was superior to that of single treatment with either drug. The tumor suppressive effects of ferrichrome were confirmed through the upregulation of DDIT3 in patient-derived organoids of adenoma and carcinoma. Ferrichrome inhibited the tumor progression in the AOM-DSS model while exhibiting no anti-inflammatory effect in the DSS-colitis model, suggesting that ferrichrome inhibited cancer cells, but not a precancerous condition, via the colitis-associated pathway. Conclusions Ferrichrome exerts a tumor suppressive effect on precancerous conditions and cancer cells associated with sporadic as well as colitis-associated colorectal cancer. The anti-tumor effect of ferrichrome was mediated by the upregulation of DDIT3, and was superior to that of 5-FU or cisplatin. These results suggest that Lactobacillus brevis-derived ferrichrome may be a candidate anti-tumor drug for the treatment of colorectal neoplasms.

Attenuation of the secondary injury of spinal cord injury (SCI) can suppress the spread of spinal cord tissue damage, possibly resulting in spinal cord sparing that can improve functional prognoses. Granulocyte colony-stimulating factor (G-CSF) is a haematological cytokine commonly used to treat neutropenia. Previous reports have shown that G-CSF promotes functional recovery in rodent models of SCI. Based on preclinical results, we conducted early phase clinical trials, showing safety/feasibility and suggestive efficacy. These lines of evidence demonstrate that G-CSF might have therapeutic benefits for acute SCI in humans. To confirm this efficacy and to obtain strong evidence for pharmaceutical approval of G-CSF therapy for SCI, we conducted a phase 3 clinical trial designed as a prospective, randomized, double-blinded and placebo-controlled comparative trial. The current trial included cervical SCI [severity of American Spinal Injury Association (ASIA) Impairment Scale (AIS) B or C] within 48 h after injury. Patients are randomly assigned to G-CSF and placebo groups. The G-CSF group was administered 400 μg/m2/day × 5 days of G-CSF in normal saline via intravenous infusion for five consecutive days. The placebo group was similarly administered a placebo. Allocation was concealed between blinded evaluators of efficacy/safety and those for laboratory data, as G-CSF markedly increases white blood cell counts that can reveal patient treatment. Efficacy and safety were evaluated by blinded observer. Our primary end point was changes in ASIA motor scores from baseline to 3 months after drug administration. Each group includes 44 patients (88 total patients). Our protocol was approved by the Pharmaceuticals and Medical Device Agency in Japan and this trial is funded by the Center for Clinical Trials, Japan Medical Association. There was no significant difference in the primary end point between the G-CSF and the placebo control groups. In contrast, one of the secondary end points showed that the ASIA motor score 6 months (P = 0.062) and 1 year (P = 0.073) after drug administration tend to be higher in the G-CSF group compared with the placebo control group. Moreover, in patients aged over 65 years old, motor recovery 6 months after drug administration showed a strong trend towards a better recovery in the G-CSF treated group (P = 0.056) compared with the control group. The present trial failed to show a significant effect of G-CSF in primary end point although the subanalyses of the present trial suggested potential G-CSF benefits for specific population., Koda et al. present the results of a randomized phase 3 trial comparing granulocyte colony-stimulating factor versus placebo in patients with acute spinal cord injury. While the primary endpoint was not met, a sub-analysis revealed a trend towards superior efficacy of G-CSF versus placebo in an elderly population.

The oncogenic properties of heterogeneous nuclear ribonucleoprotein H1 (hnRNP H1) have been reported, although the tumor-promoting mechanism remains unclear. We herein report the mechanism underlying colorectal cancer cell progression mediated by hnRNP H1. The growth of colorectal cancer cells was suppressed by hnRNP H1 downregulation. A terminal deoxynucleotidyl transferase dUTP nick-end labeling assay revealed the anti-apoptotic effect of hnRNP H1 in colorectal cancer cells. An RNA immunoprecipitation assay revealed that hnRNP H1 bound to sphingosine-1-phosphate lyase 1 (SGPL1). Reverse transcription-polymerase chain reaction revealed the high expression of hnRNP H1 mRNA in colorectal cancer cells and Spearman&rsquo, s rank correlation coefficient showed a strong positive correlation between hnRNP H1 mRNA and SGPL1 mRNA. An siRNA of hnRNP H1 decreased SGPL1 mRNA expression in colorectal cancer cells, but not in non-tumorous cells. These findings suggested that hnRNP H1 increased SGPL1 mRNA expression specifically in cancer cells through direct binding. Targeted knockdown of hnRNP H1 or SGPL1 with siRNAs upregulated p53 phosphorylation and p53-associated molecules, resulting in cell growth inhibition, while hnRNP H1 upregulated the mRNA of SGPL1 and inhibited p53 activation, thereby promoting tumor cell growth. This is a novel mechanism underlying colorectal cancer cell progression mediated by hnRNP H1&ndash, SGPL1 mRNA stabilization.

Receptor-based fluorescent sensors are the representative tool for quantitative detection of target ligands. The high substrate-selectivity originated from biomacromolecule receptor is one of the advantages of this tool, but a laborious trial and error is usually required to construct sensors showing satisfactory fluorescence intensity changes without diminishing the function of parent receptor. Ribonucleopeptide (RNP) provides a scaffold of fluorescent sensors to improve such issues. RNP receptors for the ligand of interest are constructed by applying in vitro selection for RNA-derived RNP library. Simple modification of the N-terminal of peptide in RNP by an appropriate fluorophore converts the RNP receptor into the fluorescent sensor with retaining the affinity and selectivity for the substrate. In this chapter, we introduce the protocols for construction of fluorescent RNP sensors through selection from a library of fluorophore-modified RNP complex or by a structure-based modular design. Furthermore, we describe the application of covalently linked RNP sensors for simultaneous detection of multiple ligands.

We have developed a fluoride shuttle battery (FSB) which is a promising candidate for the next-generation high-energy-density secondary batteries. Using the bis [2-(2-methoxyethoxy) ethyl] ether (tetraglyme: G4) solvent containing 0.45 mol dm−3 cesium fluoride (CsF) and 0.5 mol dm−3 fluorobis (2,4,6-trimethylphenyl) borane (FBTMPhB) as an electrolyte for FSB, we have successfully conducted the discharge (BiF3 + 3e− → Bi + 3F−) and charge (Bi + 3F− → BiF3 + 3e−) reactions for a BiF3 electrode; however, the discharge and charge capacities significantly decreased during cycling. Atomic absorption spectrometry results indicated that, in addition to the formation of BiF3, dissolution of Bi (Bi → Bi3+ + 3e−) occurred during the charge process. The dissolution of Bi indicated that the active material was lost from the electrode, which decreased the capacity during cycling. An increased CsF/FBTMPhB ratio in the electrolyte was found to suppress the dissolution of Bi during the charge process and, therefore, improve the cycling performance.

The potential in each state of charge (SOC) during charging of Li1.2Ni0.13Mn0.54Co0.13O2 is higher than that during discharging. In other words, the potential hysteresis occurs between charging and discharging. Furthermore, the potential in each SOC changes according to the charge-discharge operating conditions, indicating that the charge-discharge reaction mechanism is also affected. To clarify the effect of charge-discharge operating conditions on the electrochemical reaction, Li1.2Ni0.13Mn0.54Co0.13O2 was charged and discharged under various charge-discharge operating ranges, and open-circuit potential (OCP), crystal structure, and oxidation states of the transition metals were evaluated by electrochemical measurement, X-ray diffraction (XRD), and X-ray absorption fine structure (XAFS). These results indicate that OCP, lattice parameters, and oxidation states of the transition metals of Li1.2Ni0.13Mn0.54Co0.13O2 in each SOC are not constant. The XRD results indicate that two phases, namely, LiNi0.33Mn0.33Co0.33O2-like and Li2MnO3-like, exist in Li1.2Ni0.13Mn0.54Co0.13O2. For the LiNi0.33Mn0.33Co0.33O2-like phase, the relationship between OCP, lattice parameters, and oxidation states of the transition metals in each SOC is not affected by the charge-discharge operating conditions, indicating that extraction and insertion of lithium ions for the LiNi0.33Mn0.33Co0.33O2-like phase progresses at almost the same potential. Although the extraction and insertion of lithium ions for the Li2MnO3-like phase progresses at almost the same potential in the low-SOC region, the OCP and lattice parameter in each SOC in the high-SOC region are not constant. Therefore, the extraction of lithium ions from the Li2MnO3-like phase in the high-SOC region causes the potential hysteresis of Li1.2Ni0.13Mn0.54Co0.13O2.

Background The JOA (Japan Orthopaedic Association) score has been a standard outcome measure to evaluate cervical myelopathy in Japan. Despite its reliability and convenience, there can be a rating bias in the JOA score. The current study was conducted to delineate the rater's bias of the JOA score by comparing it with a new objective outcome measure. Methods Two hundred and thirty four operative candidates with cervical myelopathy were included in the study. The patients were divided into four groups according to the surgeon (92 patients in group A, 60 patients in group B, 38 patients in group C and 44 patients in group D). Each patient's preoperative JOA score was exclusively recorded by the surgeon himself, while JOACMEQ (Japanese Orthopaedic Association Cervical Myelopathy Evaluation Questionnaire) was recorded by each patient. Disease severity, the most important prognostic factor, was equalized between patient groups by a special statistical method called inverse-probability weighting (IPW). To define similarity of the two groups, Cohen's d was used. Results After the adjustment, the differences of the JOA score were only 0.1 between groups A and D and 0 between groups B and C. The values of Cohen's d were also very small both between groups A and D (3%), and between groups B and C (0.3%). The averaged JOA scores of groups A and D were higher by 0.4–0.8 than those of groups B and C, while the averaged JOA scores were almost the same both between groups A and D, and between groups B and C. Surgeons A and D had the same tendency to give higher JOA scores than surgeons B and C did. Conclusions The current study confirmed there is a definite rater's bias in the JOA score. JOACMEQ is to be applied as a more reliable outcome measure to evaluate myelopathy patients.

Two electrochemical reactions are possible in regard to Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 (0.5Li 2 MnO 3 −0.5LiNi 0.33 Mn 0.33 Co 0.33 O 2 ), viz, Li 2 MnO 3 -like and LiNi 0.33 Mn 0.33 Co 0.33 O 2 -like reactions. The open circuit potential (OCP) and changes in crystal structure during the charge-discharge process of Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 were investigated to clarify the mechanism responsible for the two reactions. Li 2 MnO 3 and LiNi 0.33 Mn 0.33 Co 0.33 O 2 were separately prepared for the investigation, and the OCPs and crystal structures in these cathodes were measured and then compared with those for Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 . The results obtained using X-ray diffraction (XRD) indicated that two phases existed in Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 . The changes in crystal structure of the two phases during the charge-discharge process were similar to those in Li 2 MnO 3 and LiNi 0.33 Mn 0.33 Co 0.33 O 2 . This indicated that two phases, viz, Li 2 MnO 3 -like and LiNi 0.33 Mn 0.33 Co 0.33 O 2 -like, existed in Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 . Li 2 MnO 3 -like, LiNi 0.33 Mn 0.33 Co 0.33 O 2 -like, and Li 2 MnO 3 -like phases were found to contribute mainly to electrochemical reactions in the low, middle, and high state of charge (SOC) ranges during the charge process from the results obtained using XRD and electrochemical measurements carried out on Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 . In contrast, the Li 2 MnO 3 -like and LiNi 0.33 Mn 0.33 Co 0.33 O 2 -like phases mainly contributed to electrochemical reactions in the low and high SOC ranges during the discharge process. Furthermore, the high polarization and potential decay during the charge-discharge cycling of Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 were mainly attributed to the Li 2 MnO 3 -like phase.

The effect of chemical treatment using (NH4)2SO4 on the electrochemical properties of Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.25Mn0.55O2 was investigated. The treatment was effective in improving the Coulombic efficiency and discharge capacity of a Li1.2Ni0.2Mn0.6O2 cathode, but treatment with too much (NH4)2SO4 degraded the cathode's electrochemical performance. The effect of (NH4)2SO4 treatment on the charge-discharge reaction mechanism of Li1.2Ni0.2Mn0.6O2 was investigated by evaluating reaction potential, particle configuration, and oxidation state of transition metal. The experimental results indicated that the changes in the electrochemical performance of the treated cathodes were attributed to the changes in the surface state and of the element contributing to the redox reaction. Treatment with an appropriate amount of (NH4)2SO4 also improved the electrochemical performance of the high-nickel-content lithium-rich layer-structured cathode material Li1.2Ni0.25Mn0.55O2.

Background Pancreatic cancer is associated with an extremely poor prognosis, so new biomarkers that can detect the initial stages are urgently needed. The significance of serum microRNA (miR) levels in pancreatic neoplasm such as pancreatic cancer and intraductal papillary mucinous neoplasm (IPMN) diagnosis remains unclear. We herein evaluated the usefulness of miRs enclosed in serum exosomes (ExmiRs) as diagnostic markers. Methods The ExmiRs from patients with pancreatic cancer (n = 32) or IPMN (n = 29), and patients without neoplasms (controls; n = 22) were enriched using ExoQuick-TC™. The expression of ExmiRs was evaluated using a next-generation sequencing analysis, and the selected three miRs through this analysis were confirmed by a quantitative real-time polymerase chain reaction. Results The expression of ExmiR-191, ExmiR-21 and ExmiR-451a was significantly up-regulated in patients with pancreatic cancer and IPMN compared to the controls (p

The conversion-based BiF3 is a promising cathode material for lithium-ion batteries due to its high theoretical capacity (302 mAh g−1). Nanocomposites of BiF3 and carbon (BiF3/C) are known to improve the electrochemical performance by increasing the electronic conductivity of the electrode. Here we investigate the electrochemical performance of BiF3/C at high C-rates. In particular, we newly investigate the difference of high C-rate performance between discharge and charge reactions. The discharge and charge capacities in the first cycle were almost the same at 0.1 C. In contrast, the discharge capacity was higher than charge capacity at 10 C. Further, during cycling at 10 C, the charge capacity drastically decreased, but the discharge capacity remained high. The rate performance of the discharge reaction was higher than that of the charge reaction, especially after cycling.

A large potential hysteresis occurs between the charge and discharge reactions of Li 1.2 Ni x Mn 0.8− x O 2 ( x = 0.2). As the nickel content x was increased through x = 0.2, 0.3, and 0.4, the potential hysteresis was suppressed. The results obtained by X-ray absorption fine structure indicate that, for Li 1.2 Ni x Mn 0.8− x O 2 ( x = 0.2), the redox of the nickel, manganese, and oxygen contributed to the charge-discharge reactions. There was little difference in the redox potentials of nickel and manganese between the charge and discharge processes. In contrast, the redox potential of oxygen during the charge process was very different from that during the discharge process. This means that large potential hysteresis of Li 1.2 Ni x Mn 0.8− x O 2 ( x = 0.2) was mainly due to the progress of the reaction compensated by the redox of oxygen. As the nickel content x increased in Li 1.2 Ni x Mn 0.8− x O 2 ( x = 0.2, 0.3, and 0.4), the charge-discharge reactions compensated by the redox of nickel increased, but that of oxygen decreased. Therefore, for the lithium-rich layer-structured cathode material, the increased nickel/manganese ratio was effective in suppressing the potential hysteresis between the charge and discharge processes.

Understanding and controlling the mechanism of energy conversion related to the development of a sustainable society not only make our lives more convenient but also make them more meaningful and enrichens us. The physical properties at the interface between solid and liquid (solid/liquid interface) play a significant role in energy conversion. The solid/liquid interface is buried and spatially limited, and thus clarifying the physical properties at the interface at the atomic scale is challenging. In this review, we describe our achievements by using frequency modulation atomic force microscopy for studying the geometric structure, molecule distribution, and viscosity at the solid/liquid interface at the atomic scale.

Fluoride shuttle batteries (FSBs), which utilize F– ion migration in electrochemical reactions, have recently advanced in academic research as next-generation rechargeable batteries. Bismuth trifluoride (BiF3) and its relatives are expected to be promising positive electrode materials for FSBs because of their high theoretical capacity. Herein, the defluorination/fluorination reaction of a BaF2-doped BiF3, Bi0.8Ba0.2F2.8, positive electrode was investigated using synchrotron-radiation X-ray diffraction, X-ray absorption spectroscopy, and transmission electron microscopy. The Bi0.8Ba0.2F2.8 electrode showed a higher reversible capacity in the first cycle and improved capacity retention compared to the BiF3 electrode. The pristine Bi0.8Ba0.2F2.8 showed a tysonite-type structure, and metallic Bi and BaF2 nanoparticles were observed in the fully defluorinated state. Moreover, we found that the (re-)fluorinated material consisted of BiF3 and BaF2 nanoparticles, indicating that bismuth is the only redox-active element, and that the tysonite structure is not recovered after the initial discharging. This suggests that the cycle performance of the Bi0.8Ba0.2F2.8 electrode may be improved due to the suppression of the coarsening of BiF3 nanoparticles by the adhesion of BaF2 nanoparticles formed after initial defluorination.

Simple Summary Previous investigations described bioinformatic analyses based on the mRNA expression and somatic mutation as useful strategies for identifying cancer-associated molecules that were potential candidates of therapeutic targets. However, these data included secondary changes and non-functional alterations that do not influence tumor progression. Investigations, including our own studies, have shown that some RBPs shuttle cytoplasm and nuclei, and their affinity to RNAs is regulated by posttranslational modifications, such as phosphorylation. Therefore, the functional assessment of individual molecules is the most suitable strategy for identifying cancer-associated genes with or without expressional changes and mutations. This report showed for the first time that a functional assessment using an siRNA library was useful for identifying therapeutic targets from molecular groups, including RBPs, that had not been identified by expressional and mutational analyses. Abstract Previous investigations have indicated that RNA-binding proteins (RBPs) are key molecules for the development of organs, differentiation, cell growth and apoptosis in cancer cells as well as normal cells. A bioinformatics analysis based on the mRNA expression and a somatic mutational database revealed the association between aberrant expression/mutations of RBPs and cancer progression. However, this method failed to detect functional alterations in RBPs without changes in the expression, thus leading to false negatives. To identify major tumor-associated RBPs, we constructed an siRNA library based on the database of RBPs and assessed the influence on the growth of colorectal, pancreatic and esophageal cancer cells. A comprehensive analysis of siRNA functional screening findings using 1198 siRNAs targeting 416 RBPs identified 41 RBPs in which 50% inhibition of cell growth was observed in cancer cells. Among these RBPs, 12 showed no change in the mRNA expression and no growth suppression in non-cancerous cells when downregulated by specific siRNAs. We herein report for the first time cancer-promotive RBPs identified by a novel functional assessment using an siRNA library of RBPs combined with expressional and mutational analyses.

The electrochemical reaction mechanism for Bi1-xBaxF3-x (x=0, 0.1, 0.2, and 0.4) electrode materials, which have several crystal structures, was investigated. As the barium content x increased, the crystal structure changed from orthorhombic (x=0) to hexagonal (x=0.1 and 0.2) and cubic (x=0.4). For x=0.1 and 0.2, the discharge voltage and capacity decreased during cycling. In contrast, for x=0 and 0.4, the discharge voltage increased from the 1st to the 2nd cycle. The results obtained by X-ray diffraction measurements showed that the crystal structures of Bi1-xBaxF3-x (x=0 and 0.4) changed from orthorhombic and cubic to hexagonal after one cycle. This indicates that the transformation of the structure to hexagonal contributes to the improvement of electrochemical properties. Furthermore, when Bi1-xBaxF3-x (x=0) in which the orthorhombic and hexagonal phases coexisted was partly discharged, the hexagonal phase contributed preferentially to the discharge reaction. These results indicate that, for Bi1-xBaxF3-x, regardless of the crystal structure in the pristine state, the crystal structure changes into the hexagonal phase after one discharge-charge cycle, and this structural change improves the electrochemical performance of the electrode materials.

To evaluate the effect of transition metal composition on the electrochemical properties of Li-rich layer-structured cathode materials, Li 1.2 Ni x Mn 0.8− x O 2 ( x =0.2, 0.25, 0.3, and 0.4) were synthesized, and their electrochemical properties were investigated. As nickel content x increased in Li 1.2 Ni x Mn 0.8− x O 2 ( x =0.2, 0.25, 0.3, and 0.4), charge-discharge capacities at a low C-rate (0.05 C) decreased. The results obtained by dQ/dV curves indicate that, as the nickel content increased, the discharge capacity below 3.6 V greatly decreased, but that above 3.6 V increased. As the C-rate of the discharge process increased, the discharge reaction of Li 1.2 Ni x Mn 0.8− x O 2 ( x =0.2) below 3.6 V greatly decreased. In contrast, that above 3.6 V slightly decreased. This indicates that the discharge reaction above 3.6 V exhibits higher rate performance than that below 3.6 V. For the high-nickel-content cathodes, the ratio of the discharge capacity above 3.6 V to the total discharge capacity was high. Therefore, they exhibited high rate performance.

The mechanism responsible for the large potential hysteresis between charge and discharge reactions in Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 was investigated. The relationship between open circuit potential and the oxidation state of each transition metal during charge-discharge processes was evaluated. The results indicated that the electrochemical reaction in Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 , which can be expressed as 0.5Li 2 MnO 3 −0.5LiNi 0.33 Mn 0.33 Co 0.33 O 2 , was composed of two kinds of reactions such as LiNi 0.33 Mn 0.33 Co 0.33 O 2 -like and Li 2 MnO 3 -like reactions. For the LiNi 0.33 Mn 0.33 Co 0.33 O 2 -like reaction, nickel and cobalt contributed to the redox reaction. The electrochemical reaction progressed within a potential range of 3.6–4.6 V, both during charge and discharge processes; thereby, there was little potential hysteresis between charge and discharge processes. For Li 2 MnO 3 -like reaction, manganese and oxygen contributed to the redox reaction. The reaction that occurred within a potential range of 3.6–4.6 V in a charge process mainly progressed within a potential range of 3.6–2.5 V during the discharge process, which indicated that there was large potential hysteresis between charge and discharge processes in the Li 2 MnO 3 -like reaction. Therefore, the large hysteresis of reaction potential between charge and discharge processes in the Li 2 MnO 3 -like reaction was mainly related to that in the 0.5Li 2 MnO 3 −0.5LiNi 0.33 Mn 0.33 Co 0.33 O 2 .

Derivatives of the highly antitumor-active compound [{cis-Pt(NH3)2}2(μ-OH)(μ-tetrazolato-N2,N3)]2+ (5-H-Y), which is a tetrazolato-bridged dinuclear platinum(II) complex, were prepared by substituting a linear alkyl chain moiety at C5 of the tetrazolate ring. The general formula for the derivatives is [{cis-Pt(NH3)2}2(μ-OH)(μ-5-R-tetrazolato-N2,N3)]2+, where R is (CH2)nCH3 and n = 0 to 8 (complexes 1–9). The cytotoxicity of complexes 1–4 in NCI-H460 human non-small-cell lung cancer cells decreased with increasing alkyl chain length, and those of complexes 5–9 increased with increasing alkyl chain length. That is, the in vitro cytotoxicity of complexes 1–9 was found to have a U-shaped association with alkyl chain length. This U-shaped association is attributable to the degree of intracellular accumulation. Although circular dichroism spectroscopic measurement indicated that complexes 1–9 induced comparable conformational changes in the secondary structure of DNA, the tetrazolato-bridged complexes induced d...

To expand the applications of secondary batteries, we have developed a new reserve-type fluoride shuttle battery (FSB) as a promising next-generation secondary battery candidate. For a FSB, a metal fluoride and an organic solvent are applied as the active material and electrolyte, respectively, and the dissolution and deposition of the active material facilitate the electrochemical reaction. In the present study, a new electrolyte for FSBs was developed and used to investigate the electrochemical properties of a BiF3 electrode. Dissolution of the active material and a supporting fluoride salt in the electrolyte is critical for FSBs; however, the solubility of metal fluorides and fluoride salts in organic solvents is very low. To increase the solubility, an anion acceptor was added to the organic solvent, which greatly increased the solubility of these components. Using this electrolyte, we succeeded in progressive discharge-charge cycling of the BiF3 electrode. The associated discharge-charge reactions were confirmed using XRD and SEM-EDX analyses.

Cardiolipin and phosphatidic acid-binding protein (CLPABP) is a pleckstrin homology domain-containing protein and is localized on the surface of mitochondria of cultured cells as a large protein–RNA complex. To analyze the physiological functions of CLPABP, we established and characterized a CLPABP knockout (KO) mouse. Although expression levels of CLPABP transcripts in the developmental organs were high, CLPABP KO mice were normal at birth and grew normally when young. However, old male mice presented a fatty phenotype, similar to that seen in metabolic syndrome, in parallel with elevated male- and age-dependent CLPABP gene expression. One of the reasons for this obesity in CLPABP KO mice is dependence on increases in leptin concentration in plasma. The leptin transcripts were also upregulated in the adipose tissue of KO mice compared with wild-type (WT) mice. To understand the difference in levels of the transcriptional product, we focused on the effect of CLPABP on the stability of mRNA involving an AU-rich element (ARE) in its 3′UTR dependence on the RNA stabilizer, human antigen R (HuR), which is one of the CLPABP-binding proteins. Increase in stability of ARE-containing mRNAs of leptin by HuR was antagonized by the expression of CLPABP in cultured cells. Depletion of CLPABP disturbed the normal subcellular localization of HuR to stress granules, and overexpression of CLPABP induced instability of leptin mRNA by inhibiting HuR function. Consequently, leptin levels in old male mice might be regulated by CLPABP expression, which might lead to body weight control.

We applied a thermally stabilized LiNi0.6Co0.2Mn0.2O2-based cathode active material for lithium-ion batteries, which we had developed by partial substitution of molybdenum for the transition metal, to 0.6 Ah-class single cells. Cycling test of the cell unexpectedly showed capacity retention of 87% after 3000 cycles, which is better than a cell using cathode active material without molybdenum-substitution. Disassembled analyses of the cells cycled for 3000 times definitely demonstrated that no degradation in both the cathodes and anodes of the molybdenum-substituted and non-substituted. However, there was definite potential slippage in both the cells; that of the non-substituted cell was larger than the molybdenum-substituted cell. Analysis showed that very small amount of molybdenum, in the molybdenum-substituted cell, eluted from the cathode and deposited on the surface of the anode. It is speculated that the deposition might suppress the SEI growth on the anode, and restrain the slippage of the operating potentials for the cathode and anode.

The goal of ulcerative colitis (UC) treatment has recently been shown to be "mucosal healing," as no drug directly induces mucosal healing. Probiotics possess sufficient safety, but their efficacy in the treatment of UC remains controversial because of the influence of intestinal conditions. It is believed that the identification of bioactive molecules produced by probiotics and their application will help to solve this issue. We therefore identified a probiotic-derived long-chain polyphosphate as a molecule enhancing the intestinal barrier function. This study demonstrated that long-chain polyphosphate exhibited antiinflammatory effects in a human macrophage and interleukin-10 knockout transfusion mouse model. The first-in-human trial showed that 7 of the 10 enrolled patients acquired clinical remission, 4 of whom achieved endoscopic remission despite a history of treatment with anti-tumor necrosis factor (TNF)-α agents. No adverse reactions were observed. Long-chain polyphosphate might be useful for the treatment of refractory UC, even in patients with failure or intolerance to anti-TNF-α therapy.

Previous reports have suggested that some probiotics inhibit tumorigenesis and cancer progression. However, the molecules involved have not yet been identified. Here, we show that the culture supernatant of Lactobacillus casei ATCC334 has a strong tumour-suppressive effect on colon cancer cells. Using mass spectrometry, we identify ferrichrome as a tumour-suppressive molecule produced by L. casei ATCC334. The tumour-suppressive effect of ferrichrome is greater than that of cisplatin and 5-fluorouracil, and ferrichrome has less of an effect on non-cancerous intestinal cells than either of those agents. A transcriptome analysis reveals that ferrichrome treatment induces apoptosis, which is mediated by the activation of c-jun N-terminal kinase (JNK). Western blotting indicates that the induction of apoptosis by ferrichrome is reduced by the inhibition of the JNK signalling pathway. This we demonstrate that probiotic-derived ferrichrome exerts a tumour-suppressive effect via the JNK signalling pathway., Probiotics have tumour-suppressive effects in cancer cell lines and in animal models. In this study, the authors demonstrate that ferrichrome produced by Lactobacillus casei ATCC334 can suppress colon cancer growth inducing apoptosis via the JNK pathway.

The K-line, which is a virtual line that connects the midpoints of the anteroposterior diameter of the spinal canal at C2 and C7 in a plain lateral radiogram, is a useful preoperative predictive indicator for sufficient decompression by laminoplasty (LMP) for ossification of the posterior longitudinal ligament (OPLL). K-line is defined as (+) when the peak of OPLL does not exceed the K-line, and is defined as (–) when the peak of OPLL exceeds the K-line. For patients with K-line (–) OPLL, LMP often results in poor outcome. The aim of the present study was to compare the clinical outcome of LMP, posterior decompression with instrumented fusion (PDF) and anterior decompression and fusion (ADF) for patients with K-line (–) OPLL. The present study included patients who underwent surgical treatment including LMP, PDF and ADF for K-line (–) cervical OPLL. We retrospectively compared the clinical outcome of those patients in terms of Japanese Orthopedic Association score (JOA score) recovery rate. JOA score recovery rate was significantly higher in the ADF group compared with that in the LMP group and the PDF group. The JOA score recovery rate in the PDF group was significantly higher than that in the LMP group. LMP should not be used for K-line (–) cervical OPLL. ADF is one of the suitable surgical treatments for K-line (–) OPLL. Both ADF and PDF are applicable for K-line (–) OPLL according to indications set by each institute and surgical decisions.

Li1.2Ni0.2-xMn0.6-xCo2xO2 (x=0, 0.033, and 0.067) cathodes were synthesized and their electrochemical properties and stabilities at high temperature were investigated. As cobalt content x decreased, discharge capacity slightly decreased. However, even non-cobalt-content cathode exhibited high capacity (> 240 Ah kg−1). Oxygen release from charged Li1.2Ni0.2-xMn0.6-xCo2xO2 (x=0, 0.033, and 0.067) at high temperatures was evaluated with thermal desorption spectroscopy-mass spectroscopy (TDS-MS) and it was compared with that from a charged conventional Ni-based layer-structured cathode, LiNi0.8Co0.2O2. The oxygen release from charged Li1.2Ni0.2-xMn0.6-xCo2xO2 (x=0, 0.033, and 0.067), especially that from a non-cobalt-content cathode, was much less than that from charged LiNi0.8Co0.2O2. This indicated that the stability of charged Li1.2Ni0.2-xMn0.6-xCo2xO2 (x=0, 0.033, and 0.067) was high, and it was further improved by substituting cobalt with nickel and manganese. The results obtained from X-ray absorption fine structure (XAFS) measurements suggested that the stability of the high-oxidation state of manganese was higher than those of nickel and cobalt. Furthermore, cobalt ions easily migrated from octahedral to tetrahedral sites, and formed spinel-like structure upon heating. In contrast, manganese ions occupied octahedral sites at high temperature. Therefore, as the manganese content increased and the total amount of nickel and cobalt decreased, the structure in a fully charged state was stabilized.

There is large hysteresis between charge and discharge curves in lithium-rich layer-structured cathode material, Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 . The mechanism for hysteresis was examined by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) measurement as a first step in solving this issue. XRD measurements clarified that there was hysteresis in the lattice parameter between charge and discharge processes. XAFS spectra indicated that transition metals were oxidized and reduced in the same potential region during charge and discharge processes. Oxygen was oxidized at higher potential than transition metals during charge process; however, the former was reduced at lower potential than the latter during discharge process. Therefore, large hysteresis of potential between charge and discharge processes in Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 was mainly related to the reaction which is compensated with redox of oxygen.

While the progress of chemotherapy and molecular targeted therapy has improved the outcome of colorectal cancer patients, the mortality of colon cancer remains high, indicating the need to develop novel therapeutic targets for improving the outcome of colon cancer. Heterogeneous ribonucleoprotein A1 (hnRNP A1) is highly expressed in colorectal cancer and its expression correlates with malignant transformation. In this study, we performed a microarray analysis with the RNA immunoprecipitation (RNA-IP) method and identified hnRNP A1-interacting miRs, including miR-26a and -584, in a colorectal cancer cell line, SW620. A SRB assay revealed the tumor suppressive effect of miR-26a and -584, and the tumor suppressive effect of these miRs was diminished by the downregulation of hnRNP A1. The combined method of a transcriptome analysis and RNA-IP revealed hnRNP A1-interacting mRNAs, including cyclin dependent kinase 6 (CDK6). A Western blot analysis revealed the downregulation of CDK6 in miR-26a and -584 overexpression cells, as well as hnRNP A1 knockdown cells. The binding assay indicated that the binding of hnRNP A1-CDK6 mRNA was reduced by transfection of miR-26a and -584. The expression of cleaved caspase-3 was induced in miR-26a and -584 overexpression cells. These data indicate that miR-26a and -584 inhibit the binding of hnRNP A1-CDK6 mRNA and induce colorectal cancer cell apoptosis.

To distinguish the charge/discharge reaction of two components such as Li2MnO3-like and LiNi0.5Mn0.5O2-like in 0.5Li2MnO3–0.5LiNi0.5Mn0.5O2, the electrochemical characteristics, structural change, and oxidation state change of each element for 0.5Li2MnO3–0.5LiNi0.5Mn0.5O2 during charging and discharging were compared with those of LiNi0.5Mn0.5O2 and Li2MnO3. The electrochemical measurement results indicate that the charge/discharge reaction potentials of two components can be clearly distinguished in the first charging; however, the reaction potentials of two components partially overlapped after the first charging. Although the two components cannot be distinguished in XRD patterns obtained before charging/discharging, the existence of two components can be confirmed in XRD patterns obtained during charging/discharging. The XAFS results indicate that Li2MnO3-like and LiNi0.5Mn0.5O2-like components mainly contributed to the discharge reaction of 0.5Li2MnO3–0.5LiNi0.5Mn0.5O2 in the low and high potential ranges, respectively. To evaluate the effect of x (ratio of Li2MnO3-like and LiNi0.5Mn0.5O2-like components) in xLi2MnO3–(1-x)LiNi0.5Mn0.5O2 on the material's electrochemical performance, xLi2MnO3–(1-x)LiNi0.5Mn0.5O2 (x = 0.4, 0.5, and 0.6) were prepared, and their electrochemical performance was investigated. The results indicate that the increase in the ratio of LiNi0.5Mn0.5O2-like component in xLi2MnO3–(1–x)LiNi0.5Mn0.5O2 (x = 0.4, 0.5, and 0.6) affects suppression of initial irreversible capacity and improvement of rate and cycling performance.

An electrolyte for fluoride shuttle battery was composed of bis[2-(2-methoxyethoxy)ethyl]ether, a cesium fluoride, and an anion acceptor (AA; triphenylborane, fluorobis(2,4,6-trimethylphenyl)borane, or triphenylboroxine). The battery performance of bismuth(III) fluoride in the electrolytes with fluorobis(2,4,6-trimethylphenyl)borane and triphenylboroxine was much higher than that in the electrolyte with triphenylborane. To evaluate the AA type on battery performance, the chemical state of each ion in the electrolyte was evaluated by nuclear magnetic resonance. The chemical shift of fluoride ion interacted with fluorobis(2,4,6-trimethylphenyl)borane and triphenylboroxine was different from that interacted with triphenylborane, indicating that the chemical state of fluoride ion in the electrolyte affects battery performance.

The electrochemical reaction in a fluoride shuttle battery (FSB) requires an organic solvent containing a supporting electrolyte salt. To dissolve an insoluble inorganic fluoride compound (e.g., cesium fluoride (CsF)) in an organic solvent (e.g., bis[2-(2-methoxyethoxy)ethyl]ether [tetraglyme, G4]), an anion acceptor (AA) (e.g., triphenylborane (TPhB) or triphenylboroxine (TPhBX)) is typically added. This study investigates the effect of AA type and CsF/AA molar ratio on the electrochemical performance of a lead (II) fluoride (PbF2) FSB electrode. The PbF2 electrodes were cycled in an FSB with G4 containing CsF (0.45 mol dm−3) and TPhB (0.5 mol dm−3) as the electrolyte. The capacity was high during the first cycle, but drastically decreased during subsequent cycling. X-ray diffraction (XRD) and atomic absorption spectrometry (AAS) revealed Pb formation during the discharging process, but PbF2 formation and Pb dissolution during the charging process. The loss of active material through Pb dissolution caused the capacity degradation. Changing the AA type from TPhB to TPhBX promoted Pb dissolution, thereby aggravating the capacity retention problem. In contrast, increasing the CsF concentration from 0.45 mol dm−3 to its saturation concentration effectively preserved the capacity during cycling by suppressing the Pb dissolution, as confirmed in the AAS results. However, increasing the CsF concentration deteriorated the discharge and charge capacities of the PbF2 electrode. Changing the AA type from TPhB to TPhBX in the electrolyte containing saturated CsF increased the discharge and charge capacities during the first cycle, and maintained a high capacity in the subsequent discharging and charging processes, as supported in the XRD results. Overall, the AA type and CsF concentration in the electrolyte strongly affected the electrochemical performance of the PbF2 electrodes. Thus, an FSB with high electrochemical performance requires judicious selection of both AA type and CsF/AA ratio.