Showing papers by "Tokyo University of Science published in 2011"

Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard-Carbon Electrodes and Application to Na-Ion Batteries

Abstract: Recently, lithium-ion batteries have been attracting more interest for use in automotive applications. Lithium resources are confirmed to be unevenly distributed in South America, and the cost of the lithium raw materials has roughly doubled from the first practical application in 1991 to the present and is increasing due to global demand for lithium-ion accumulators. Since the electrochemical equivalent and standard potential of sodium are the most advantageous after lithium, sodium based energy storage is of great interest to realize lithium-free high energy and high voltage batteries. However, to the best of our knowledge, there have been no successful reports on electrochemical sodium insertion materials for battery applications; the major challenge is the negative electrode and its passivation. In this study, we achieve high capacity and excellent reversibility sodium-insertion performance of hard-carbon and layered NaNi0.5Mn0.5O2 electrodes in propylene carbonate electrolyte solutions. The structural change and passivation for hard-carbon are investigated to study the reversible sodium insertion. The 3-volt secondary Na-ion battery possessing environmental and cost friendliness, Na+-shuttlecock hard-carbon/NaNi0.5Mn0.5O2 cell, demonstrates steady cycling performance as next generation secondary batteries and an alternative to Li-ion batteries.

Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li2MnO3−LiCo1/3Ni1/3Mn1/3O2

Abstract: Lithium-excess manganese layered oxides, which are commonly described by the chemical formula zLi2MnO3−(1 − z)LiMeO2 (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, LixCo0.13Ni0.13Mn0.54O2−δ samples are prepared from Li1.2Ni0.13Co0.13Mn0.54O2 (or 0.5Li2MnO3−0.5LiCo1/3Ni1/3Mn1/3O2) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li+. Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported ...

Reduced Graphene Oxide as a Solid-state Electron Mediator in Z-scheme Photocatalytic Water Splitting under Visible Light

Abstract: The effectiveness of reduced graphene oxide as a solid electron mediator for water splitting in the Z-scheme photocatalysis system is demonstrated. We show that a tailor-made, photoreduced graphene oxide can shuttle photogenerated electrons from an O2-evolving photocatalyst (BiVO4) to a H2-evolving photocatalyst (Ru/SrTiO3:Rh), tripling the consumption of electron–hole pairs in the water splitting reaction under visible-light irradiation.

Fluorinated Ethylene Carbonate as Electrolyte Additive for Rechargeable Na Batteries

Abstract: Fluoroethylene carbonate is an efficient electrolyte additive to improve the reversibility of electrochemical sodium insertion for hard-carbon and NaNi1/2Mn1/2O2 electrodes in aprotic Na cells. The additive is also capable of the electrochemical deposition/dissolution of metallic Na with higher reversibility because of improved passivation and suppression of side reactions between Na metal and propylene carbonate solution containing Na salts.

Photocatalytic reduction of carbon dioxide over Ag cocatalyst-loaded ALa4Ti4O15 (A = Ca, Sr, and Ba) using water as a reducing reagent.

Abstract: Ag cocatalyst-loaded ALa4Ti4O15 (A = Ca, Sr, and Ba) photocatalysts with 3.79–3.85 eV of band gaps and layered perovskite structures showed activities for CO2 reduction to form CO and HCOOH by bubbling CO2 gas into the aqueous suspension of the photocatalyst powder without any sacrificial reagents. Ag cocatalyst-loaded BaLa4Ti4O15 was the most active photocatalyst. A liquid-phase chemical reduction method was better than impregnation and in situ photodeposition methods for the loading of the Ag cocatalyst. The Ag cocatalyst prepared by the liquid-phase chemical reduction method was loaded as fine particles with the size smaller than 10 nm on the edge of the BaLa4Ti4O15 photocatalyst powder with a plate shape during the CO2 reduction. CO was the main reduction product rather than H2 even in an aqueous medium on the optimized Ag/BaLa4Ti4O15 photocatalyst. Evolution of O2 in a stoichiometric ratio (H2+CO:O2 = 2:1 in a molar ratio) indicated that water was consumed as a reducing reagent (an electron donor) fo...

TSLP promotes interleukin-3-independent basophil haematopoiesis and type 2 inflammation

Abstract: CD4(+) T-helper type 2 (T(H)2) cells, characterized by their expression of interleukin (IL)-4, IL-5, IL-9 and IL-13, are required for immunity to helminth parasites and promote the pathological inflammation associated with asthma and allergic diseases. Polymorphisms in the gene encoding the cytokine thymic stromal lymphopoietin (TSLP) are associated with the development of multiple allergic disorders in humans, indicating that TSLP is a critical regulator of T(H)2 cytokine-associated inflammatory diseases. In support of genetic analyses, exaggerated TSLP production is associated with asthma, atopic dermatitis and food allergies in patients, and studies in murine systems demonstrated that TSLP promotes T(H)2 cytokine-mediated immunity and inflammation. However, the mechanisms through which TSLP induces T(H)2 cytokine responses remain poorly defined. Here we demonstrate that TSLP promotes systemic basophilia, that disruption of TSLP-TSLPR interactions results in defective basophil responses, and that TSLPR-sufficient basophils can restore T(H)2-cell-dependent immunity in vivo. TSLP acted directly on bone-marrow-resident progenitors to promote basophil responses selectively. Critically, TSLP could elicit basophil responses in both IL-3-IL-3R-sufficient and -deficient environments, and genome-wide transcriptional profiling and functional analyses identified heterogeneity between TSLP-elicited versus IL-3-elicited basophils. Furthermore, activated human basophils expressed TSLPR, and basophils isolated from eosinophilic oesophagitis patients were distinct from classical basophils. Collectively, these studies identify previously unrecognized heterogeneity within the basophil cell lineage and indicate that expression of TSLP may influence susceptibility to multiple allergic diseases by regulating basophil haematopoiesis and eliciting a population of functionally distinct basophils that promote T(H)2 cytokine-mediated inflammation.

Rh-Doped SrTiO3 Photocatalyst Electrode Showing Cathodic Photocurrent for Water Splitting under Visible-Light Irradiation

Abstract: A Rh-doped SrTiO3 (SrTiO3:Rh) photocatalyst electrode that was readily prepared by pasting SrTiO3:Rh powder onto a transparent indium tin oxide electrode gave a cathodic photocurrent under visible-light irradiation (λ > 420 nm), indicating that the SrTiO3:Rh photocatalyst electrode possessed p-type semiconductor character. The cathodic photocurrent increased with an increase in the amount of doped Rh up to 7 atom %. The incident-photon-to-current efficiency at 420 nm was 0.18% under an applied potential of −0.7 V vs Ag/AgCl for the SrTiO3:Rh(7 atom %) photocatalyst electrode. The photocurrent was confirmed to be due to water splitting by analyzing the evolved H2 and O2. The water splitting proceeded with the application of an external bias smaller than 1.23 V versus a Pt counter electrode under visible-light irradiation and also using a solar simulator, suggesting that solar energy conversion should be possible with the present photoelectrochemical water splitting.

Effect of alkali treatment on interfacial and mechanical properties of coir fiber reinforced poly(butylene succinate) biodegradable composites

Abstract: The poly(butylene succinate) (PBS) biodegradable composites reinforced with coir fibers were developed. The effect of alkali treatment on the surface morphology and mechanical properties of coir fibers, interfacial shear strength (IFSS) and mechanical properties of coir fiber/PBS composites was studied. The effect of fiber mass content varying from 10% to 30% on the mechanical properties of coir fiber/PBS composites was also investigated. The coir fibers which are soaked in 5% sodium hydroxide solution at room temperature (RT) for 72 h showed the highest IFSS with 55.6% higher than untreated coir fibers. The mechanical properties of alkali-treated coir fiber/PBS composites are significantly higher than those of untreated fibers. The best mechanical properties of alkali-treated coir fiber/PBS composite were achieved at fiber mass content of 25% in this study, which showed an increase of tensile strength by 54.5%, tensile modulus by 141.9%, flexural strength by 45.7% and flexural modulus by 97.4% compared to those of pure PBS resin. The fiber surface morphologies and fractured surface of the composites exhibited an improvement of interfacial fiber–matrix adhesion in the composites reinforced with alkali-treated coir fibers.

Study on polymer binders for high-capacity SiO negative electrode of Li-Ion batteries

Abstract: High-capacity SiO powder composite electrodes for rechargeable lithium-ion batteries are prepared with different polymer binders of poly(acrylic acid) (PAA), poly(vinyl alcohol) (PVA), sodium carboxymethyl cellulose (CMCNa), and conventional poly(vinylidene fluoride) (PVdF). Electrode performance of the SiO composites highly depends on selection of binders, and their electrochemical reversibility is drastically improved by using PAA as the binder in comparison to the PVdF, CMCNa, and PVA binders. Coulombic efficiency at the initial cycle is improved for the SiO–PAA composite electrode, and the reversible capacity reaches 700–750 mAh g–1 for continuous fifty cycling test at a rate of 100 mA g–1. The improvement mechanism of SiO–PAA composite electrode is characterized by X-ray diffraction, electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, self-discharge test, and adhesive strength test. Amorphous PAA polymer not only tightly binds but also covers the individual SiO particles. Mo...

Crystal Structure of Fast Lithium-ion-conducting Cubic Li7La3Zr2O12

Abstract: The detailed crystal structure of cubic Li7La3Zr2O12 has been successfully determined by single-crystal X-ray structure analysis. The three-dimensional network of the Li-ion migration pathway with ...

Binding of metal ions by pyrimidine base pairs in DNA duplexes

Abstract: Pyrimidine base pairs in DNA duplexes selectively capture metal ions to form metal ion-mediated base pairs, which can be evaluated by thermal denaturation, isothermal titration calorimetry, and nuclear magnetic resonance spectroscopy. In this critical review, we discuss the metal ion binding of pyrimidine bases (thymine, cytosine, 4-thiothymine, 2-thiothymine, 5-fluorouracil) in DNA duplexes. Thymine-thymine (T-T) and cytosine-cytosine (C-C) base pairs selectively capture Hg(II) and Ag(I) ions, respectively, and the metallo-base pairs, T-Hg(II)-T and C-Ag(I)-C, are formed in DNA duplexes. The metal ion binding properties of the pyrimidine-pyrimidine pairs can be changed by small chemical modifications. The binding selectivity of a metal ion to a 5-fluorouracil-5-fluorouracil pair in a DNA duplex can be switched by changing the pH of the solution. Two silver ions bind to each thiopyrimidine-thiopyrimidine pair in the duplexes, and the duplexes are largely stabilized. Oligonucleotides containing these bases are commercially available and can readily be applied in many scientific fields (86 references).

Torque Density and Efficiency Improvements of a Switched Reluctance Motor Without Rare-Earth Material for Hybrid Vehicles

Abstract: A machine design of a switched reluctance motor having competitive torque and efficiency as well as compactness with respect to an interior permanent-magnet (IPM) synchronous motor (IPMSM) in a hybrid electric vehicle (Toyota Prius 2003) has been investigated. A torque of 400 N·m is set as a target with an outer diameter of 269 mm with an axial length of 156 mm, including coil end lengths. In addition, a 50-kW field weakening capability must be competitive to the IPMSM. The highest efficiency of 95% is also aimed. Stator and rotor structures and iron material are investigated. Test machines are built. Static and light load tests are carried out.

In-vitro derived germinal centre B cells differentially generate memory B or plasma cells in vivo

Abstract: In response to T cell-dependent antigens, B cells proliferate extensively to form germinal centres (GC), and then differentiate into memory B (B(mem)) cells or long-lived plasma cells (LLPCs) by largely unknown mechanisms. Here we show a new culture system in which mouse naive B cells undergo massive expansion and isotype switching, and generate GC-phenotype B (iGB) cells. The iGB cells expressing IgG1 or IgM/D, but not IgE, differentiate into B(mem) cells in vivo after adoptive transfer and can elicit rapid immune responses with the help of cognate T cells. Secondary culture with IL-21 maintains the proliferation of the iGB cells, while shifting their in vivo developmental fate from B(mem) cells to LLPCs, an outcome that can be reversed by withdrawal of IL-21 in tertiary cultures. Thus, this system enables in vitro manipulation of B-cell fate, into either B(mem) cells or LLPCs, and will facilitate dissection of GC-B cell differentiation programs.

Surfactant Effects on Bubble Motion and Bubbly Flows

Abstract: Small amounts of surfactant can drastically change bubble behavior. For example, a bubble in aqueous surfactant solution rises much slower than one in purified water. This phenomenon is explained by the so-called Marangoni effect caused by a nonuniform concentration distribution of surfactant along the bubble surface. In other words, a tangential shear stress appears on the bubble surface due to the surface tension variation caused by the surface concentration distribution, which results in the reduction of the rising velocity of the bubble. More interestingly, this Marangoni effect influences not only the rising velocity, but also the lateral migration in the presence of mean shear. Furthermore, these phenomena influence the multiscale nature of bubbly flows and cause a drastic change in the bubbly flow structure. In this article, we review the recent studies related to these interesting behaviors of bubbles caused by the surfactant adsorption/desorption on the bubble surface.

Generalized Galileon cosmology

Abstract: We study the cosmology of a generalized Galileon field $\ensuremath{\phi}$ with five covariant Lagrangians in which $\ensuremath{\phi}$ is replaced by general scalar functions ${f}_{i}(\ensuremath{\phi})$ ($i=1,\dots{},5$). For these theories, the equations of motion remain at second order in time derivatives. We constrain the forms of the functions ${f}_{i}(\ensuremath{\phi})$ from the requirement to possess de Sitter solutions responsible for dark energy. There are two possible choices for power-law functions ${f}_{i}(\ensuremath{\phi})$, depending on whether the coupling $F(\ensuremath{\phi})$ with the Ricci scalar $R$ is independent of $\ensuremath{\phi}$ or depends on $\ensuremath{\phi}$. The former corresponds to the covariant Galileon theory that respects the Galilean symmetry in the Minkowski space-time. For generalized Galileon theories we derive the conditions for the avoidance of ghosts and Laplacian instabilities associated with scalar and tensor perturbations as well as the condition for the stability of de Sitter solutions. We also carry out a detailed analytic and numerical study for the cosmological dynamics in those theories.

Inflationary non-Gaussianities in the most general second-order scalar-tensor theories

Abstract: For very general scalar-field theories in which the equations of motion are at second order, we evaluate the three-point correlation function of primordial scalar perturbations generated during inflation. We show that the shape of non-Gaussianities is well approximated by the equilateral type. The equilateral nonlinear parameter ${f}_{\mathrm{NL}}^{\mathrm{equil}}$ is derived on the quasi-de Sitter background, where the slow-variation parameters are much smaller than unity. We apply our formula for ${f}_{\mathrm{NL}}^{\mathrm{equil}}$ to a number of single-field models of inflation---such as k-inflation, k-inflation with Galileon terms, potential-driven Galileon inflation, nonminimal coupling models (including field-derivative coupling models), and Gauss-Bonnet gravity.

Gapless spin liquid of an organic triangular compound evidenced by thermodynamic measurements

Abstract: In frustrated magnetic systems, long-range ordering is forbidden and degeneracy of energy states persists, even at extremely low temperatures. Under certain conditions, these systems form an exotic quantum spin-liquid ground state, in which strongly correlated spins fluctuate in the spin lattices. Here we investigate the thermodynamic properties of an anion radical spin liquid of EtMe(3)Sb[Pd(dmit)(2)](2), where dmit represents 1,3-dithiole-2-thione-4,5-dithiolate. This compound is an organic dimer-based Mott insulator with a two-dimensional triangular lattice structure. We present distinct evidence for the formation of a gapless spin liquid by examining the T-linear heat capacity coefficient, γ , in the low-temperature heat capacity. Using comparative analyses with κ-(BEDT-TTF)(2)Cu(2)(CN)(3), a generalized picture of the new spin liquid in dimer-based organic systems is discussed. We also report anomalous enhancement of γ, produced by a kind of criticality inherent to the Pd(dmit)(2) phase diagram.

Functional Tooth Regeneration Using a Bioengineered Tooth Unit as a Mature Organ Replacement Regenerative Therapy

Abstract: Donor organ transplantation is currently an essential therapeutic approach to the replacement of a dysfunctional organ as a result of disease, injury or aging in vivo Recent progress in the area of regenerative therapy has the potential to lead to bioengineered mature organ replacement in the future In this proof of concept study, we here report a further development in this regard in which a bioengineered tooth unit comprising mature tooth, periodontal ligament and alveolar bone, was successfully transplanted into a properly-sized bony hole in the alveolar bone through bone integration by recipient bone remodeling in a murine transplantation model system The bioengineered tooth unit restored enough the alveolar bone in a vertical direction into an extensive bone defect of murine lower jaw Engrafted bioengineered tooth displayed physiological tooth functions such as mastication, periodontal ligament function for bone remodeling and responsiveness to noxious stimulations This study thus represents a substantial advance and demonstrates the real potential for bioengineered mature organ replacement as a next generation regenerative therapy

Crystal Structure Analysis of Poly(l-lactic Acid) α Form On the basis of the 2-Dimensional Wide-Angle Synchrotron X-ray and Neutron Diffraction Measurements

Abstract: The crystal structure of poly(l-lactic acid) (PLLA) α form has been analyzed in detail by utilizing the 2-dimensional wide-angle X-ray (WAXD) and neutron diffraction (WAND) data measured for the ultradrawn sample. The WAXD data were collected using a synchrotron-sourced high-energy X-ray beam of wavelength 0.328 A at SPring-8, Japan and the WAND data were measured using a neutron beam of wavelength 1.510 A with a cylindrical imaging-plate camera of BIX-3 system at Japan Atomic Energy Agency. The initial crystal structure model was extracted successfully by a direct method under the assumption of the space group P212121 using about 700 X-ray reflections observed at −150 °C, the number of which was overwhelmingly large compared with the data reported by the previous other researchers and allowed us to perform more precise structural analysis. The crystal structure model obtained by the direct method was refined so that the best agreement between the observed and calculated integrated intensities was obtaine...

The Transcription Factor E4BP4 Regulates the Production of IL-10 and IL-13 in CD4+ T Cells

Abstract: Chronic stimulation of lymphocytes results in upregulation of immunomodulatory IL-10, but the molecular mechanisms of this process have remained unknown. Kubo and colleagues demonstrate that the transcription factor E4BP4 is responsible for this plasticity.

Z-scheme photocatalyst systems for water splitting under visible light irradiation.

Abstract: Water splitting to produce H2 using sunlight is a form of artificial photosynthesis in that light energy is converted to chemical energy. As such, water splitting using powdered photocatalysts has attracted attention in the framework of energy and environmental issues. This article reviews z-scheme photocatalyst systems for water splitting under visible light irradiation, especially focused on the systems consisting of SrTiO3:Rh of a H2-evolving photocatalyst, and O2-evolving photocatalysts with and without electron mediators. These photocatalyst systems showed activities for water splitting into H2 and O2 in a stoichiometric amount under visible light irradiation and even under sunlight irradiation. The photocatalytic activity was sensitive to pH. The optimum pH was 2.4 when iron ions were used as electron mediators. Co-catalysts also affected the activity. The photodeposited Ru co-catalyst gave an excellent performance. The best performance achieved by the pH adjustment and the selection of a co-catalyst was obtained mainly by suppression of back reactions to form H2O from evolved H2 and O2.

Organocatalyzed Michael Addition of Aldehydes to Nitro Alkenes – Generally Accepted Mechanism Revisited and Revised

Abstract: The amine-catalyzed enantioselective Michael addition of aldehydes to nitro alkenes (Scheme 1) is known to be acid-catalyzed (Fig. 1). A mechanistic investigation of this reaction, catalyzed by diphenylprolinol trimethylsilyl ether is described. Of the 13 acids tested, 4-NO2C6H4OH turned out to be the most effective additive, with which the amount of catalyst could be reduced to 1 mol-% (Tables 2–5). Fast formation of an amino-nitro-cyclobutane 12 was discovered by in situ NMR analysis of a reaction mixture. Enamines, preformed from the prolinol ether and aldehydes (benzene/molecular sieves), and nitroolefins underwent a stoichiometric reaction to give single all-trans-isomers of cyclobutanes (Fig. 3) in a [2+2] cycloaddition. This reaction was shown, in one case, to be acid-catalyzed (Fig. 4) and, in another case, to be thermally reversible (Fig. 5). Treatment of benzene solutions of the isolated amino-nitro-cyclobutanes with H2O led to mixtures of 4-nitro aldehydes (the products 7 of overall Michael addition) and enamines 13 derived thereof (Figs. 6–9). From the results obtained with specific examples, the following tentative, general conclusions are drawn for the mechanism of the reaction (Schemes 2 and 3): enamine and cyclobutane formation are fast, as compared to product formation; the zwitterionic primary product 5 of C,C-bond formation is in equilibrium with the product of its collapse (the cyclobutane) and with its precursors (enamine and nitro alkene); when protonated at its nitronate anion moiety the zwitterion gives rise to an iminium ion 6, which is hydrolyzed to the desired nitro aldehyde 7 or deprotonated to an enamine 13. While the enantioselectivity of the reaction is generally very high (>97% ee), the diastereoselectivity depends upon the conditions, under which the reaction is carried out (Fig. 10 and Tables 1–5). Various acid-catalyzed steps have been identified. The cyclobutanes 12 may be considered an off-cycle ‘reservoir’ of catalyst, and the zwitterions 5 the ‘key players’ of the process (bottom part of Scheme 2 and Scheme 3).