Double-Layered Perovskite Oxyfluoride Cathodes with High Capacity Involving O-O Bond Formation for Fluoride-Ion Batteries.

Developing electrochemical high-energy storage systems is of crucial importance toward a green and sustainable energy supply. A promising candidate is fluoride-ion batteries (FIBs), which can deliver a much higher volumetric energy density than lithium-ion batteries. However, typical metal fluoride cathodes with conversion-type reactions cause a low-rate capability. Recently, layered perovskite oxides and oxyfluorides, such as LaSrMnO4 and Sr3Fe2O5F2, have been reported to exhibit relatively high rate performance and cycle stability compared to typical metal fluoride cathodes with conversion-type reactions, but their discharge capacities (∼118 mA h/g) are lower than those of typical cathodes used in lithium-ion batteries. Here, we show that double-layered perovskite oxyfluoride La1.2Sr1.8Mn2O7-δF2 exhibits (de) intercalation of two fluoride ions to rock-salt slabs and further (de) intercalation of excess fluoride ions to the perovskite layer, leading to a reversible capacity of 200 mA h/g. The additional fluoride-ion intercalation leads to the formation of O-O bond in the structure for charge compensation (i.e., anion redox). These results highlight the layered perovskite oxyfluorides as a new class of active materials for the construction of high-performance FIBs.

[Endovascular Repair of Traumatic Injury to the Descending Aorta and the Right Subclavian Artery;Report of a Case].

A 32-year-old man leaping down from the 3rd floor of his house got injured and was transferred to our center. Pseudoaneurysm at the aortic isthmus as well as pelvic and lower limb fractures were observed by computed tomography (CT) scan. Thoracic endovascular aortic repair(TEVAR)of the thoracic aorta was performed from zone 2, followed by external skeletal fixation. Postoperative chest X-ray revealed right hemothorax, and CT scan showed active bleeding from the right subclavian artery in addition to splenic artery pseudoaneurysm. A 10×60 mm covered stent was deployed at the right subclavian artery and coiling of the splenic artery was performed. He was discharged without complication. The timing and procedures of surgery are difficult to decide in treatment of aortic injury with multiple trauma, TEVAR makes quick control of bleeding possible by less invasive approach. Moreover, endovascular approach to the subclavian artery avoides median sternotomy.

Amorphous Metal Polysulfides: Electrode Materials with Unique Insertion/Extraction Reactions.

A unique charge/discharge mechanism of amorphous TiS4 is reported. Amorphous transition metal polysulfide electrodes exhibit anomalous charge/discharge performance and should have a unique charge/discharge mechanism: neither the typical intercalation/deintercalation mechanism nor the conversion-type one, but a mixture of the two. Analyzing the mechanism of such electrodes has been a challenge because fewer tools are available to examine the "amorphous" structure. It is revealed that the electrode undergoes two distinct structural changes: (i) the deformation and formation of S-S disulfide bonds and (ii) changes in the coordination number of titanium. These structural changes proceed continuously and concertedly for Li insertion/extraction. The results of this study provide a novel and unique model of amorphous electrode materials with significantly larger capacities.

Blood-brain barrier permeability of ginkgolide: Comparison of the behavior of PET probes 7α-[18F]fluoro- and 10-O-p-[11C]methylbenzyl ginkgolide B in monkey and rat brains.

The blood-brain barrier permeability of ginkgolide B was examined using positron emission tomography (PET) probes of a 18F-incorporated ginkgolide B ([18F]-2) and a 11C-incorporated methylbenzyl-substituted ginkgolide B ([11C]-3). PET studies in monkeys showed low uptake of [18F]-2 into the brain, but small amounts of [11C]-3 were accumulated in the parenchyma. Furthermore, when cyclosporine A was preadministered to rats, the accumulation of [18F]-2 in the rat brain did not significantly change, however, the accumulation of [11C]-3 was five times higher than that in the control rat. These results provide effective approaches for investigating the drug potential of ginkgolides.

Fulminant adenovirus hepatitis after hematopoietic stem cell transplant: Retrospective real-time PCR analysis for adenovirus DNA in two cases.

BACKGROUND: Viral infection is one of the major causes of mortality in patients undergoing hematopoietic stem cell transplant (HSCT). Systemic infection of adenovirus (AdV) has emerged as a not uncommon viral infection with significant morbidity and mortality as with cytomegalovirus and Epstein-Barr virus infection. Routine surveillance for these viruses has become a clinical practice and subsequent preemptive therapy improves patients' outcomes; however, the effectiveness of preemptive therapy for AdV has not been fully investigated in patients with a lethal form of AdV infection. METHODS: Sequential AdV loads were retrospectively analyzed in children with fulminant AdV hepatitis after HSCT. RESULTS: The AdV DNA became detectable (1 × 10(4) copies/mL) as early as 2 weeks after HSCT. These levels reached >1 × 10(8) copies/mL at the onset of fulminant hepatitis. However, we determined that γ-glutamyltransferase levels were elevated to >100 IU/L at least 2 weeks before the diagnosis of hepatitis. CONCLUSIONS: Our observation raises the possibility that elevated γ-glutamyltransferase could be a sentinel marker for AdV hepatitis, which prompts elaborated monitoring of AdV load and targeted treatment.

Synthesis of antioxidants for prevention of age-related macular degeneration.

Photooxidation of A2E may be involved in diseases of the macula, and antioxidants could serve as therapeutic agents for these diseases. Inhibitors of A2E photooxidation were prepared by Mannich reaction of the antioxidant quercetin. These compounds contain water-solubilizing amine groups, and several were more potent inhibitors of A2E photooxidation than quercetin.

Changes in Standing Postural Control Ability in a Case of Spinocerebellar Ataxia Type 31 With Physical Therapy Focusing on the Center of Gravity Sway Variables and Lower Leg Muscle Activity.

Spinocerebellar degeneration (SCD) is a progressive disease characterized by cerebellar ataxia or the posterior spinal cord. Among these, spinocerebellar ataxia type 31 (SCA31) is genetically more common in the Japanese population and is characterized by pure ataxia, resulting in severe disturbances in postural balance, with common falls. Therefore, rehabilitation is important to improve postural balance. Light touch is a known method of reducing postural sway, which acts with the light touching of an object with the body. We herein present a case of a patient with SCA31 who was trained in a standing position by lightly touching the back of the body to a wall surface. Dynamic interarticular coordination exercises were also performed as part of the rehabilitation program. As a result, even in the progressive SCA31, improvements in standing postural balance and activities of daily living contributed to improvements in the patient's postural balance. We followed the progress of postural control ability using the center of gravity sway measurement and electromyography and described some interesting characteristics of the patient's postural control ability in this report.

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

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

Preparation of alkyl-modified silicon nanosheets by hydrosilylation of layered polysilane (Si6H6).

Alkyl-modified crystalline silicon nanosheets 2 were synthesized and maintained the crystal structure of a Si(111) plane, in which the dangling silicon bond is stabilized by capping with the alkyl group. 2 was characterized using UV-vis, Fourier transform-infrared, and X-ray photoelectron spectroscopies; X-ray diffraction; and X-ray absorption near edge structure analysis. A model structure is proposed that has a periodicity through the nanosheet surface.

SYBR green-based real-time reverse transcription-PCR for typing and subtyping of all hemagglutinin and neuraminidase genes of avian influenza viruses and comparison to standard serological subtyping tests.

Continuing outbreaks of H5N1 highly pathogenic (HP) avian influenza virus (AIV) infections of wild birds and poultry worldwide emphasize the need for global surveillance of wild birds. To support the future surveillance activities, we developed a SYBR green-based, real-time reverse transcriptase PCR (rRT-PCR) for detecting nucleoprotein (NP) genes and subtyping 16 hemagglutinin (HA) and 9 neuraminidase (NA) genes simultaneously. Primers were improved by focusing on Eurasian or North American lineage genes; the number of mixed-base positions per primer was set to five or fewer, and the concentration of each primer set was optimized empirically. Also, 30 cycles of amplification of 1:10 dilutions of cDNAs from cultured viruses effectively reduced minor cross- or nonspecific reactions. Under these conditions, 346 HA and 345 NA genes of 349 AIVs were detected, with average sensitivities of NP, HA, and NA genes of 10(1.5), 10(2.3), and 10(3.1) 50% egg infective doses, respectively. Utility of rRT-PCR for subtyping AIVs was compared with that of current standard serological tests by using 104 recent migratory duck virus isolates. As a result, all HA genes and 99% of the NA genes were genetically subtyped, while only 45% of HA genes and 74% of NA genes were serologically subtyped. Additionally, direct subtyping of AIVs in fecal samples was possible by 40 cycles of amplification: approximately 70% of HA and NA genes of NP gene-positive samples were successfully subtyped. This validation study indicates that rRT-PCR with optimized primers and reaction conditions is a powerful tool for subtyping varied AIVs in clinical and cultured samples.

Analysis of the HLA and non-HLA susceptibility loci in Japanese type 1 diabetes.

BACKGROUND: We previously reported the associations of human leukocyte antigen (HLA) (DRB1 and DQB1), INS, CTLA4, IL2RA, ERBB3 and CLEC16A with Japanese type 1 diabetes (T1D). In this study, we jointly analysed these loci in addition to IFIH1 and IL7R. METHODS: A maximum of 790 T1D patients and 953 control subjects were analysed. HLA was determined by sequencing-based typing. Seven non-HLA single nucleotide polymorphisms were genotyped using TaqMan assay. RESULTS: HLA DRB1*0405, DRB1*0901 and DRB1*0802-DQB1*0302 haplotypes were positively associated with T1D, while the DRB1*15 haplotypes were negatively associated. Non-HLA single nucleotide polymorphisms, INS, IL2RA, ERBB3, CLEC16A and IL7R were associated with T1D. By a prediction model using the HLA loci alone (HLA model) or the non-HLA loci alone (non-HLA model), it was revealed that the cumulative effect of the non-HLA model was much weaker than that of the HLA model (average increase in odds ratio: 1.17 versus 3.14). Furthermore, the area under the receiver operating characteristic curve of the non-HLA model was also much smaller than that of the HLA model (0.65 versus 0.81, p<10(-11)). Finally, a patient-only analysis revealed the susceptible HLA haplotypes and the risk allele of INS to be negatively associated with slower onset of the disease. In addition, the DRB1*0901 haplotype and the risk alleles of ERBB3, CLEC16A and CTLA4 were positively associated with the co-occurrence of thyroid autoimmunity. CONCLUSIONS: Although several non-HLA susceptibility genes in Japanese were confirmed trans-racially and appear to contribute to the heterogeneity of the clinical phenotypes, the cumulative effect on the ability to predict the development of T1D was weak.

Interaction of FANCD2 and NBS1 in the DNA damage response.

Fanconi anaemia (FA) and Nijmegen breakage syndrome (NBS) are autosomal recessive chromosome instability syndromes with distinct clinical phenotypes. Cells from individuals affected with FA are hypersensitive to mitomycin C (MMC), and cells from those with NBS are hypersensitive to ionizing radiation. Here we report that both NBS cell lines and individuals with NBS are hypersensitive to MMC, indicating that there may be functional linkage between FA and NBS. In wild-type cells, MMC activates the colocalization of the FA subtype D2 protein (FANCD2) and NBS1 protein in subnuclear foci. Ionizing radiation activates the ataxia telangiectasia kinase (ATM)-dependent and NBS1-dependent phosphorylation of FANCD2, resulting in an S-phase checkpoint. NBS1 and FANCD2 therefore cooperate in two distinct cellular functions, one involved in the DNA crosslink response and one involved in the S-phase checkpoint response.

Bulky melamine-based Zn-porphyrin tweezer as a CD probe of molecular chirality.

The transfer of chirality from a guest molecule to an achiral host is the subject of significant interest especially when, upon chiral induction, the chiroptical response of the host/guest complex can effectively report the absolute configuration (AC) of the guest. For more than a decade, dimeric metalloporphyrin hosts (tweezers) have been successfully applied as chirality probes for determination of the AC for a wide variety of chiral synthetic compounds and natural products. The objective of this study is to investigate the utility of a new class of melamine-bridged Zn-porphyrin tweezers as sensitive AC reporters. A combined approach based on an experimental CD analysis and a theoretical prediction of the prevailing interporphyrin helicity demonstrates that these tweezers display favorable properties for chiral recognition. Herein, we discuss the application of the melamine-bridged tweezer to the chiral recognition of a diverse set of chiral guests, such as 1,2-diamines, α-amino-esters and amides, secondary alcohols, and 1,2-amino-alcohols. The bulky periphery and the presence of a rigid porphyrin linkage lead, in some cases, to a more enhanced CD sensitivity than that reported earlier with other tweezers.

Synthesis and optical properties of monolayer organosilicon nanosheets.

The synthesis of silicon nanosheets for fabricating electronic devices, without using conventional vacuum processes and vapor deposition, is challenging and is anticipated to receive significant attention for a wide range of applications. Here, we report the synthesis of oxygen-free, phenyl-modified organosilicon nanosheets with atomic thickness. In organic solvents, a consequence of this new silicon structure is its uniform dispersion and the possibility of exfoliation into unilamellar nanosheets. Light-induced photocurrent in [Si(6)H(4)Ph(2)] was observed, leading to the possibility of various organosilicon nonamaterials with useful properties.

Silicon nanosheets and their self-assembled regular stacking structure.

Silicon nanomaterials are encouraging candidates for application to photonic, electronic, or biosensing devices, due to their size-quantization effects. Two-dimensional silicon nanosheets could help to realize a widespread quantum field, because of their nanoscale thickness and microscale area. However, there has been no example of a successful synthesis of two-dimensional silicon nanomaterials with large lateral size and oxygen-free surfaces. Here we report that oxygen-free silicon nanosheets covered with organic groups can be obtained by exfoliation of layered polysilane as a result of reaction with n-decylamine and dissolution in an organic solvent. The amine residues are covalently bound to the Si(111) planes. It is estimated that there is ca. 0.7 mol of residue per mole of Si atoms in the reaction product. The amine-modified layered polysilane can dissolve in chloroform and exfoliate into nanosheets that are 1-2 microm wide in the lateral direction and with thicknesses on the order of nanometers. The nanosheets have very flat and smooth surfaces due to dense coverage of n-decylamine, and they are easily self-assembled in a concentrated state to form a regularly stacked structure. The nanosheets could be useful as building blocks to create various composite materials.

Bilateral iliopsoas hematomas under sedation: a complication of postoperative therapy after coronary artery bypass grafting.

We report a case of bilateral iliopsoas hematomas that occurred during postoperative therapy after coronary artery bypass grafting (CABG). An 81-year-old woman receiving anticoagulant and antiplatelet therapies under sedation after CABG developed sudden anemia and went into shock. Abdominal ultrasonography showed a right retroperitoneal hematoma. She improved gradually with conservative treatment. Many patients with an iliopsoas hematoma complain of low-abdominal pain or femoral neuropathy, but such local signs may be absent under sedation. In anticoagulant and antiplatelet therapies under sedation, when the cause of anemia and shock is not clear, we should suspect peritoneal hematoma and examine the peritoneal space.

Operando soft X-ray absorption spectroscopic study on microporous carbon-supported sulfur cathodes.

Sulfur is a promising material for next-generation cathodes, owing to its high energy and low cost. However, sulfur cathodes have the disadvantage of serious cyclability issues due to the dissolution of polysulfides that form as intermediate products during discharge/charge cycling. Filling sulfur into the micropores of porous carbon is an effective method to suppress its dissolution. Although microporous carbon-supported sulfur cathodes show an electrochemical behavior different from that of the conventional sulfur ones, the corresponding reaction mechanism is not clearly understood. In this study, we focused on clarifying the reaction mechanism of microporous carbon-supported sulfur cathodes by operando soft X-ray absorption spectroscopy. In the microporous carbon support, sulfur was present as smaller fragments compared to conventional sulfur. During the first discharge process, the sulfur species in the microporous carbon were initially reduced to S6 2- and S2 2- and then to Li2S. The S6 2- and S2 2- species were observed first, with S2 2- being the main polysulfide species during the discharge process, while Li2S was produced in the final discharge process. The narrow pores of microporous carbon prevent the dissolution of polysulfides and influence the reaction mechanism of sulfur cathodes.

Improved Non-Grignard Electrolyte Based on Magnesium Borate Trichloride for Rechargeable Magnesium Batteries.

The high anodic stability of electrolytes for rechargeable magnesium batteries enables the use of new positive electrodes, which can contribute to an increase in energy density. In this study, novel Ph3COMgCl-, Ph3SiOMgCl-, and B(OMgCl)3-based electrolytes were prepared with AlCl3 in triglyme. The Ph3COMgCl-based electrolyte showed anodic stability over 3.0 V vs. Mg but was chemically unstable, whereas the Ph3SiOMgCl-based electrolyte was chemically stable but featured lower anodic stability than the Ph3COMgCl-based electrolyte. Advantageously, the B(OMgCl)3-based electrolyte showed both anodic stability over 3.0 V vs. Mg (possibly due to the Lewis acidic nature of B in B(OMgCl)3) and chemical stability (possibly due to the hard acid character of B(OMgCl)3). B(OMgCl)3, which was prepared by reacting boric acid with a Grignard reagent, was characterized by nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared spectroscopy (FTIR), and X-ray absorption spectroscopy (XAS). The above analyses showed that B(OMgCl)3 has a complex structure featuring coordinated tetrahydrofuran molecules. 27Al NMR spectroscopy and Al K-edge XAS showed that when B(OMgCl)3 was present in the electrolyte, AlCl3 and AlCl2+ species were converted to AlCl4-. Mg K-edge XAS showed that the Mg species in B(OMgCl)3-based electrolytes are electrochemically positive. As a rechargeable magnesium battery, the full cell using the B(OMgCl)3-based electrolyte and a Mo6S8 Chevrel phase cathode showed stable charge-discharge cycles. Thus, B(OMgCl)3-based electrolytes, the anodic stability of which can be increased to ~3 V by the use of appropriate battery materials, are well suited for the development of practical Mg battery cathodes.

Determining Factor on the Polarization Behavior of Magnesium Deposition for Magnesium Battery Anode.

To clarify the origin of the polarization of magnesium deposition/dissolution reactions, we combined electrochemical measurement, operando soft X-ray absorption spectroscopy (operando SXAS), Raman, and density functional theory (DFT) techniques to three different electrolytes: magnesium bis(trifluoromethanesulfonyl)amide (Mg(TFSA)2)/triglyme, magnesium borohydride (Mg(BH4)2)/tetrahydrofuran (THF), and Mg(TFSA)2/2-methyltetrahydrofuran (2-MeTHF). Cyclic voltammetry revealed that magnesium deposition/dissolution reactions occur in Mg(TFSA)2/triglyme and Mg(BH4)2/THF, while the reactions do not occur in Mg(TFSA)2/2-MeTHF. Raman spectroscopy shows that the [TFSA]- in the Mg(TFSA)2/triglyme electrolyte largely does not coordinate to the magnesium ions, while all of the [TFSA]- in Mg(TFSA)2/2-MeTHF and [BH4]- in Mg(BH4)2/THF coordinate to the magnesium ions. In operando SXAS measurements, the intermediate, such as the Mg+ ion, was not observed at potentials above the magnesium deposition potential, and the local structure distortion around the magnesium ions increases in all of the electrolytes at the magnesium electrode|electrolyte interface during the cathodic polarization. Our DFT calculation and X-ray photoelectron spectroscopy results indicate that the [TFSA]-, strongly bound to the magnesium ion in the Mg(TFSA)2/2-MeTHF electrolyte, undergoes reduction decomposition easily, instead of deposition of magnesium metal, which makes the electrolyte inactive electrochemically. In the Mg(BH4)2/THF electrolyte, because the [BH4]- coordinated to the magnesium ions is stable even under the potential of the magnesium deposition, the magnesium deposition is not inhibited by the decomposition of [BH4]-. Conversely, because [TFSA]- is weakly bound to the magnesium ion in Mg(TFSA)2/triglyme, the reduction decomposition occurs relatively slowly, which allows the magnesium deposition in the electrolyte.