Nido-Hydroborate-Based Electrolytes for All-Solid-State Lithium Batteries

Hydroborate-based solid electrolytes have recently been successfully employed in high voltage, room temperature all-solid-state sodium batteries. The transfer to analogous lithium systems has failed up to now due to the lower conductivity of the corresponding lithium compounds and their high cost. Here LiB₁₁H₁₄ nido-hydroborate as a cost-effective building block and its high-purity synthesis is introduced. The crystal structures of anhydrous LiB₁₁H₁₄ as well as of LiB₁₁H₁₄-based mixed-anion solid electrolytes are solved and high ionic conductivities of 1.1 × 10⁻⁴ S cm⁻¹ for Li₂(B₁₁H₁₄)(CB₁₁H₁₂) and 1.1 × 10⁻³ S cm⁻¹ for Li₃(B₁₁H₁₄)(CB₉H₁₀)₂ are obtained, respectively. LiB₁₁H₁₄ exhibits an oxidative stability limit of 2.6 V versus Li⁺/Li and the proposed decomposition products are discussed based on density functional theory calculations. Strategies are discussed to improve the stability of these compounds by modifying the chemical structure of the nido-hydroborate cage. Galvanostatic cycling in symmetric cells with two lithium metal electrodes shows a small overpotential increase from 22.5 to 30 mV after 620 h (up to 0.5 mAh cm⁻²), demonstrating that the electrolyte is compatible with metallic anodes. Finally, the Li₂(B₁₁H₁₄)(CB₁₁H₁₂)  electrolyte is employed in a proof-of-concept half cell with a TiS₂ cathode with a capacity retention of 82% after 150 cycles at C/5.     

以辉锑矿为原料放电等离子烧结快速制备黝铜矿Cu_(12)Sb_4S_(13)及反应机理

采用辉锑矿为原料成功制备出Cu_(12)Sb_4S_(13)块体。研究以Sb_2S_3矿物为原料时烧结工艺对Cu_(12)Sb_4S_(13)合成的影响。在400 ～ 440℃温度区间内均可快速合成Cu_(12)Sb_4S_(13)块体且二次烧结能够进一步减小中间相CuSbS_2和Cu_3SbS_3。第二相Cu_3SbS_4和残留相CuS随着烧结时间的延长而降低。二次烧结前进行机械化球磨处理,干磨比湿磨更容易减小残留相。初次烧结块体的断面SEM和EDS能谱分析表明内部存在Cu或Cu_2S颗粒团聚现象。适当降低Cu或CuS摩尔量(化学计量比0.1 mol)能促进烧结块表面反应进行。烧结过程中,硫磺蒸汽压的导致烧结块表面成分和内部粉末的成分不同。     

Abscopal Effect of Frozen Autograft Reconstruction Combined with an Immune Checkpoint Inhibitor Analyzed Using a Metastatic Bone Tumor Model

We evaluated the abscopal effect of re-implantation of liquid nitrogen-treated tumor-bearing bone grafts and the synergistic effect of anti-PD-1 (programmed death-1) therapy using a bone metastasis model, created by injecting MMT-060562 cells into the bilateral tibiae of 6–8-week-old female C3H mice. After 2 weeks, the lateral tumors were treated by excision, cryotreatment using liquid nitrogen, excision with anti-PD-1 treatment, and cryotreatment with anti-PD-1 treatment. Anti-mouse PD-1 4H2 was injected on days 1, 6, 12, and 18 post-treatment. The mice were euthanized after 3 weeks; the abscopal effect was evaluated by focusing on growth inhibition of the abscopal tumor. The re-implantation of frozen autografts significantly inhibited the growth of the remaining abscopal tumors. However, a more potent abscopal effect was observed in the anti-PD-1 antibody group. The number of CD8+ T cells infiltrating the abscopal tumor and tumor-specific interferon-γ (IFN-γ)-producing spleen cells increased in the liquid nitrogen-treated group compared with those in the excision group, with no significant difference. The number was significantly higher in the anti-PD-1 antibody-treated group than in the non-treated group. Overall, re-implantation of tumor-bearing frozen autograft has an abscopal effect on abscopal tumor growth, although re-implantation of liquid nitrogen-treated bone grafts did not induce a strong T-cell response or tumor-suppressive effect.     

A Strategy for Discovering Heterochiral Bioactive Peptides by Using the OB2nP Library and SPOTs Method

d -Amino acid containing peptides are promising as drug lead compounds because of their expected higher stability in vivo. A heterochiral random peptide library called the one-bead–2ⁿ-peptide (OB2ⁿP) library, which can display 2ⁿ peptide diastereomers per bead, has been developed. Through screening of the OB2ⁿP library and subsequent binding assay among the peptide diastereomers synthesized in parallel by means of the SPOTs method, new heterochiral mimotopes for the anti-β-endorphin monoclonal antibody have been obtained. One mimotope was a new ligand for the μ-opioid receptor. The screening strategy enabled d -amino acid containing drug leads to be obtained efficiently by expanding searchable chemical space without increasing the experimental scale.     

Real-Time Duplex Applications of Loop-Mediated AMPlification (LAMP) by Assimilating Probes

Isothermal nucleic-acid amplification methods such as Loop-Mediated isothermal AMPlification (LAMP) are increasingly appealing alternatives to PCR for use in portable diagnostic system due to the low cost, weight, and power requirements of the instrumentation. As such, interest in developing new probes and other functionality based on the LAMP reaction has been intense. Here, we report on the development of duplexed LAMP assays for pathogen detection using spectrally unique Assimilating Probes. As proof of principle, we used a reaction for Salmonella enterica as a model coupled with a reaction for λ-phage DNA as an internal control, as well as a duplexed assay to sub-type specific quarantine strains of the bacterial wilt pathogen Ralstonia solanacearum. Detection limits for bacterial DNA analyzed in individual reactions was less than 100 genomic equivalents in all cases, and increased by one to two orders of magnitude when reactions were coupled in duplexed formats. Even so, due to the more robust activity of newly available strand-displacing polymerases, the duplexed assays reported here were more powerful than analogous individual reactions reported only a few years ago, and represent a significant advance for incorporation of internal controls to validate assay results in the field.     

Radiophotoluminescence phenomenon in copper-doped aluminoborosilicate glass

Radiophotoluminescence phenomena have been widely investigated on various types of materials for dosimetry applications. We report that an aluminoborosilicate glass containing 0.005 mol% copper exhibits intense photoluminescence in the visible region induced by X-ray and γ-ray irradiation. The luminescence is assigned to the 3d⁹4s¹ → 3d¹⁰ transition of Cu⁺. The proportionality of the intensity of the induced photoluminescence to the irradiation dose was confirmed up to 0.5 kGy using ⁶⁰Co γ-ray irradiation. Based on the spectroscopic results, a potential mechanism was proposed for the enhancement of the photoluminescence. The exposure to the ionizing radiation generates electron-hole pairs in the glass, and the electrons are subsequently captured by the Cu²⁺ ions, which are converted to Cu⁺ and emit the luminescence. For the glass containing 0.01 mol% copper, the pronounced enhancement of the photoluminescence was not observed because the reverse reaction, ie, the capture of the holes by the Cu⁺ ions, becomes prominent. The photoluminescence induced by the irradiation was stably observed for the glasses kept at room temperature and even for the glasses heat-treated at 150°C. However, the induced photoluminescence could be eliminated by the heat treatment at a temperature at 500°C, and the glass returned to the initial pre-irradiation state. The Cu-doped aluminoborosilicate glass is a potential candidate for use in dosimetry applications.     

Oxidation behavior of ytterbium silicide

Si-rich ytterbium silicide was fabricated by through an arc-melting technique for applying use as a bond coat material in an environmental barrier coating system. Evaluation of its potential was accomplished through oxidation tests in dry air and an inert atmosphere. The experimental results showed that the changes in weight and morphologies of ytterbium silicide observed after the tests depended on the oxygen partial pressure. Extensive oxidation and weight gain occurred after oxidation in air. In order to apply this material for hot structures, improvement of the oxidation resistance is needed.     

Chemical Synthesis of a Synthetic Analogue of the Sialic Acid‐Binding Lectin Siglec‐7

As a basis for the development of an artificial carbohydrate‐binding lectin, we chemically synthesized a domain of siglec‐7, a well‐characterized sialic‐acid‐binding lectin. The full polypeptide (127 amino acids) was constructed by sequential native chemical ligation (NCL) of five peptide segments. Because of poor cysteine availability for NCL, cysteine residues were introduced at suitable ligation sites; these cysteine residues were alkylated in order to mimic native glutamine or asparagine residues, or converted to an alanine residue by desulfurization after NCL. After folding the full‐length polypeptide, the sialic‐acid‐binding activity of the synthetic siglec‐7 was clearly demonstrated by STD NMR and ELISA experiments. We succeeded in the synthesis of siglec‐7 by installing three extra cysteine residues with side‐chain modifications and found that these modifications did not affect the binding activity.     

Precipitation recovery of boron from wastewater by hydrothermal mineralization

It is well known that boric acid exhibits various toxic effects on plant, animal and human beings even at very low concentrations. Thus, the development of boron-removal technique from wastewater has been intensively investigated. In this study, a new hydrothermal treatment technique was developed to recover boron as recyclable precipitate Ca(2)B(2)O(5).H(2)O from aqueous solutions. As a result, it was found that the hydrothermal treatment using calcium hydroxide as a mineralizer converted boron in the aqueous media effectively into calcium borate, Ca(2)B(2)O(5).H(2)O. In the optimal hydrothermal condition, more than 99% of boron was collected from the synthetic wastewater of 500 ppm. Thus, the present hydrothermal treatment in the presence of calcium hydroxide is recommended as one of the effective techniques to recover boron from aqueous media.     

Natural denitrification in the Kakamigahara groundwater basin,Gifu prefecture,central Japan

Although nitrate is recognized as the most common groundwater contaminant due to growing anthropogenic sources, such as agriculture in particular, its adverse effects on human and animal health are debatable. The current issue, however, is to control and reduce nitrate contamination with regards to the long residence time of groundwater within aquifers. Denitrification has recently been recognized for its ability to reduce high nitrate concentrations in groundwater. The Kakamigahara groundwater basin, Gifu prefecture, Japan, witnessed rising levels of nitrate (>12 mg/l NO(3)-N) originating from agricultural sources. Chemical analyses for the determination of major constituents of groundwater and delta(15)N of residual nitrate were performed on representative groundwater samples in order to fulfill two main objectives. One is to investigate the current situation of nitrate groundwater pollution. The second objective is to determine whether the denitrification is a potential natural mechanism, which eliminates nitrate pollution in the Kakamigahara aquifer. Agricultural nitrate contamination of groundwater was obvious from characteristically high concentrations of Ca(2+), Mg(2+), NO(3)(-) and SO(4)(2-). High nitrate concentrations were found on the eastern side of the basin in association with vegetable cultivation fields, and decreased gradually towards the west of the basin along the direction of groundwater flow. The decrease of nitrate concentration was conveniently coupled with increase of HCO(3)(-) (the heterotrophic denitrification product), pH and delta(15)N of residual nitrate (due to isotopic fractionation) from east to west. Therefore, denitrification in situ is continuously removing nitrate from the Kakamigahara groundwater system.