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In a previous study, we isolated a Vibrio sp. strain MA3 and its virulence factor, a hemolysin encoded by vhe1. This strain is associated with mass mortalities of the pearl oyster Pinctada fucata. In the present study, the vhe1 gene from strain MA3 was cloned and its encoded product was purified and characterized. Our results show that the vhe1 gene encodes a protein of 417 amino acids with an estimated molecular mass of 47.2 kDa and a pI of 5.14. The deduced protein, Vhe1, was found to contain the conserved amino acid sequence (GDSL motif) of the hydrolase/esterase superfamily and five conserved blocks characteristic of SGNH hydrolases. A BLAST homology search indicated that Vhe1 belongs the lecithin-dependent hemolysin/thermolabile hemolysin (LDH/TLH) family. In activity analyses, the optimal temperature for both the hemolytic and phospholipase activities of Vhe1 was 50 °C. Vhe1 hemolytic activity and phospholipase activity were highest at pH 8.5 and pH 8.0, respectively. However, both enzymatic activities sharply decreased at high temperature (> 50 °C) and pH < 7.0. Compared with previously reported hemolysins, Vhe1 appeared to be more thermal- and pH-labile. Both its hemolytic activity and phospholipase activity were significantly inhibited by CuCl2, CdCl2, ZnCl2, and NiCl2, and slightly inhibited by MnCl2 and CoCl2. Vhe1 showed higher phospholipase activity toward medium-chain fatty acids (C8-C12) than toward shorter- and longer-chain fatty acids. These results accumulate knowledge about the LDH/TLH of V. alginolyticus, which detailed characterization has not been reported, and contribute to solving of the mass mortality of pearl oyster.
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Pinctada , Vibrio , Animais , Pinctada/genética , Pinctada/metabolismo , Proteínas Hemolisinas/genética , Proteínas Hemolisinas/metabolismo , Lecitinas , Vibrio/genética , Vibrio/metabolismo , Fosfolipases/genética , Clonagem MolecularRESUMO
Solid-state Li batteries using 5 V-class positive electrode materials display a higher energy density. However, the high resistance at the interface of the electrolyte and positive electrode (interface resistance, Ri) hinders their practical applications. Here, we report the relaxation of Ri between a solid electrolyte (Li3PO4) and a 5 V-class electrode (LiCo0.5Mn1.5O4). Although Ri is small at the Mn3+/4+ redox voltage of 4.0 V vs Li/Li+ (11 Ω cm2), it rapidly increases by more than 2 orders of magnitude as the voltage increases above the Co3+/4+ redox voltage of 5.2 V vs Li/Li+. After the applied voltage is reduced to 4.0 V vs Li/Li+, Ri decays to the original value after 3 h. The relaxation of Ri after exposure to high voltages suggests that the increase in Ri above 5 V vs Li/Li+ is attributable to the formation of an interfacial layer at the LPO/LCMO interface.
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In electrochemical devices, it is important to control the ionic transport between the electrodes and solid electrolytes. However, it is difficult to tune the transport without applying an electric field. This paper presents a method to modulate the transport via tuning of the electrochemical potential difference by controlling the electronic states at the interfaces. We fabricated thin-film solid-state Li batteries using LiTi2O4 thin films as positive electrodes. The spontaneous Li-ion transport between the solid electrolyte and LiTi2O4 is controlled by tuning the electrochemical potential difference via use of an electrically conducting Nb-doped SrTiO3 substrate. This study establishes the foundation for rectifying the ionic transport via electronic energy band alignment.
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Hard X-ray phase-contrast imaging is sensitive to density variation in objects and shows a dose advantage for in vivo observation over absorption-contrast imaging. We examined the capability of propagation-based phase-contrast tomography (PB-PCT) with single-distance phase retrieval for tracking of bone structure and mineral changes using monochromatic synchrotron light. Female mice underwent ovariectomy and drill-hole surgery in the right tibial diaphysis and were divided into two groups: OVX and OVX-E (n = 6 each); the latter group was treated with intraperitoneal administration of 14,15-epoxyeicosatrienoic acid (14,15-EET) for promoting bone repair. Age-matched mice subjected to sham ovariectomy and drill-hole surgery (Sham) were also prepared (n = 6). In vivo CT scans of the drilled defect were acquired 3, 7, and 11 days after surgery, and tomographic images were matched by three-dimensional registration between successive time points for monitoring the process of defect filling. In addition, using absorption-contrast CT as the reference method, the validity of PB-PCT was evaluated in one mouse by comparing images of tibial metaphyseal bone between the two methods in terms of bone geometry as well as the measure of mineralization. Although phase retrieval is strictly valid only for single-material objects, PB-PCT, with its lower radiation dose, could provide a depiction of bone structure similar to that from absorption-contrast CT. There was a significant correlation of linear absorption coefficients between the two methods, indicating the possibility of a rough estimate of the measure of mineralization by PB-PCT. Indeed, delayed bone regeneration (OVX vs. Sham) and the efficacy of 14,15-EET for improving osteoporotic bone repair (OVX-E vs. OVX) could be detected in both bone volume and mineralization by PB-PCT. Thus, in combination with single-distance phase retrieval, PB-PCT would have great potential for providing a valuable tool to track changes in bone structure and mineralization, and for evaluating the effects of therapeutic interventions as well.
Assuntos
Osso e Ossos/diagnóstico por imagem , Microscopia de Contraste de Fase/métodos , Microtomografia por Raio-X/métodos , Animais , Feminino , Camundongos Endogâmicos C57BLRESUMO
We investigated the superconducting transport properties of the one-unit-cell FeSe ultrathin films epitaxially grown on undoped SrTiO_{3}(001) (STO) with a well-defined surface structure by in situ independently-driven four-point-probe measurements. Our results unambiguously revealed the detection of the two-dimensional electrical conduction of the films without parallel conduction through the underlying substrate, both in the normal and superconducting states. The monolayer film exhibited a superconducting transition at an onset temperature of 40 K. Surprisingly, the onset of superconductivity was constantly observed at 40 K even for three- and five-unit-cell-thick FeSe films, even though the normal resistivity decreased with increasing thickness. These results agree with the picture of the interfacial superconductivity, where only the FeSe/STO interface and/or the adjacent first layer of FeSe becomes superconducting while the upper layers stay in the normal metallic state. The observed T_{c} is much lower than that reported by a previous in situ transport measurement for FeSe/Nb:STO but consistent with the results obtained by ex situ measurements for FeSe-undoped STO with a capping layer. This suggests that the capping layer is not an essential factor to limit T_{c}. We rather propose that the charge transfer from the doped substrate has a key role to achieve the higher temperature superconductivity in the one-unit-cell FeSe.
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We describe the epitaxial growth process of single-phase magnesium dihydride (MgH2) thin films on MgO(100) substrates, achieved by reactive magnetron sputtering. We find that direct growth at substrate temperatures higher than 100 °C leads to partial MgH2 decomposition to Mg, hindering single-phase epitaxy of MgH2. To improve the crystallinity and suppress the decomposition of Mg, we optimize MgH2 growth using a two-step process, consisting of (1) precursor growth at room temperature and (2) postdeposition annealing at 380 °C, under a pressure of 1.0 × 105 Pa with H2 (4%)/Ar (96%) premixed gases. Using this two-step process, we obtain single-phase MgH2 epitaxial films with high crystallinity, transparency, and resistivity. Further, the application of this method to grow MgH2 thin films on different MgF2 and Al2O3 substrates enables us to use the epitaxial effects to control the growth orientation of MgH2 thin films; we show that MgH2(100) and MgH2(001) epitaxial thin films can be grown on Al2O3(001) and MgF2(001) substrates, respectively.
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The interfaces of complex oxide heterostructures exhibit intriguing phenomena not observed in their constituent materials. The oxide thin-film growth of such heterostructures has been successfully controlled with unit-cell precision; however, atomic-scale understandings of oxide thin-film surfaces and interfaces have remained insufficient. We examined, with atomic precision, the surface and electronic structures of oxide thin films and their growth processes using low-temperature scanning tunneling microscopy. Our results reveal that oxide thin-film surface structures are complicated in contrast to the general perception and that atomically ordered surfaces can be achieved with careful attention to the surface preparation. Such atomically ordered oxide thin-film surfaces offer great opportunities not only for investigating the microscopic origins of interfacial phenomena but also for exploring new surface phenomena and for studying the electronic states of complex oxides that are inaccessible using bulk samples.
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We report the observation of coherent surface states on cubic perovskite oxide SrVO_{3}(001) thin films through spectroscopic-imaging scanning tunneling microscopy. A direct link between the observed quasiparticle interference patterns and the formation of a d_{xy}-derived surface state is supported by first-principles calculations. We show that the apical oxygens on the topmost VO_{2} plane play a critical role in controlling the coherent surface state via modulating orbital state.
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In this paper, we report the surprisingly low electrolyte/electrode interface resistance of 8.6 Ω cm(2) observed in thin-film batteries. This value is an order of magnitude smaller than that presented in previous reports on all-solid-state lithium batteries. The value is also smaller than that found in a liquid electrolyte-based batteries. The low interface resistance indicates that the negative space-charge layer effects at the Li3PO(4-x)N(x)/LiCoO2 interface are negligible and demonstrates that it is possible to fabricate all-solid state batteries with faster charging/discharging properties.
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We report the emergence of a charge-density wave (CDW) in Ca-intercalated bilayer graphene (C_{6}CaC_{6}), the thinnest limit of superconducting C_{6}Ca, observed by low-temperature, high-magnetic-field scanning tunneling microscopy or spectroscopy, and angle-resolved photoemission spectroscopy. While the possible superconductivity was not observed in epitaxially grown C_{6}CaC_{6} on a SiC substrate, a CDW order different from that observed on the surface of bulk C_{6}Ca was observed. It is inferred that the CDW state is induced by the potential modulation due to the commensurate lattice matching between the C_{6}CaC_{6} film and the SiC substrate.
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Success in isolating a 2D graphene sheet from bulky graphite has triggered intensive studies of its physical properties as well as its application in devices. Graphite intercalation compounds (GICs) have provided a platform of exotic quantum phenomena such as superconductivity, but it is unclear whether such intercalation is feasible in the thinnest 2D limit (i.e., bilayer graphene). Here we report a unique experimental realization of 2D GIC, by fabricating calcium-intercalated bilayer graphene C(6)CaC(6) on silicon carbide. We have investigated the structure and electronic states by scanning tunneling microscopy and angle-resolved photoemission spectroscopy. We observed a free-electron-like interlayer band at the Brillouin-zone center, which is thought to be responsible for the superconductivity in 3D GICs, in addition to a large π* Fermi surface at the zone boundary. The present success in fabricating Ca-intercalated bilayer graphene would open a promising route to search for other 2D superconductors as well as to explore its application in devices.
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Oxide electronics is a promising alternative to the conventional silicon-based semiconductor technology, owing to the rich functionalities of oxide thin films and heterostructures. In contrast to the silicon surface, however, the electronic structure of the SrTiO3 surface, the most important substrate for oxide thin films growth, is not yet completely understood. Here we report on the electronic states of a reconstructed (001) surface of SrTiO3 determined in real space, with scanning tunneling microscopy/spectroscopy and density functional theory calculations. We found a remarkable energy dependence of the spectroscopic image: Theoretical analysis reveals that symmetry breaking at the surface lifts the degeneracy in the t2g state (dxy, dyz, and dzx) of Ti 3d orbitals, whose anisotropic spatial distribution leads to a sharp transition in the spectroscopic image as a function of energy. The knowledge obtained here could be used to gain further insights into emergent phenomena at the surfaces and interfaces with SrTiO3.
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Complex oxide surfaces and interfaces, consisting of two or more cations and oxygen anions, have attracted a great deal of attention because their properties are crucial factors in the performance of catalysts, fuel cells, and Li-ion batteries. However, atomic-scale investigations of these oxide surfaces have been hindered because of the difficulties in surface preparation. Here, we demonstrate atomic-scale surface studies of complex perovskite oxides and the initial growth processes in oxide epitaxial films deposited on (â13 × â13)-R33.7° reconstructed SrTiO3 (001) substrates using a scanning tunneling microscope integrated with a pulsed laser deposition system. The atomically ordered, reconstructed SrTiO3 (001) surface is stable under the typical conditions necessary for the growth of oxide thin films, and hence is considered suitable for the study of the initial growth processes in oxide films. The atomic-scale microscopic/spectroscopic characterizations performed here shed light on the microscopic origin of electronic properties observed in complex oxides and their heterostructures.
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Metal-organic frameworks (MOFs) are attractive materials with periodic pore structures constructed by coordinating metal ions and organic ligands. Recently, Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), a two-dimensional conductive MOF, has attracted attention as a promising device material. Owing to the anisotropy of Cu3(HHTP)2 properties, oriented thin films of this MOF are desired for evaluating its physical properties and device integration. To date, wet processes have been used to fabricate Cu3(HHTP)2 films, whereas dry processes are essential for high-quality devices. However, oriented Cu3(HHTP)2 thin films have not yet been fabricated by using dry processes. In this study, we succeed in fabricating an orientation-controlled Cu3(HHTP)2 film on Al2O3 (001) by using a two-step dry process involving (1) the multilayer deposition of copper acetate and HHTP using a vapor deposition system and (2) pyridine vapor-assisted annealing. In-plane and out-of-plane X-ray diffraction patterns confirm the successful fabrication of the (001)-oriented Cu3(HHTP)2 films. The conductivity evaluated by four-probe measurements is 2.6 × 10-2 S cm-1, comparable to that of films fabricated by wet processes. This study provides a novel guideline for the orientation control of two-dimensional conductive MOF thin films via a dry process.
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X-linked adrenoleukodystrophy (X-ALD) is a genetic disorder associated with peroxisomal dysfunction. Patients with this rare disease accumulate very long-chain fatty acids (VLCFAs) in their bodies because of impairment of peroxisomal VLCFA ?-oxidation. Several clinical types of X-ALD, ranging from mild (axonopathy in the spinal cord) to severe (cerebral demyelination), are known. However, the molecular basis for this phenotypic variability remains largely unknown. In this study, we determined plasma ceramide (CER) profile using liquid chromatography-tandem mass spectrometry. We characterized the molecular species profile of CER in the plasma of patients with mild (adrenomyeloneuropathy;AMN) and severe (cerebral) X-ALD. Eleven X-ALD patients (five cerebral, five AMN, and one carrier) and 10 healthy volunteers participated in this study. Elevation of C26:0 CER was found to be a common feature regardless of the clinical types. The level of C26:1 CER was significantly higher in AMN but not in cerebral type, than that in healthy controls. The C26:1 CER level in the cerebral type was significantly lower than that in the AMN type. These results suggest that a high level of C26:0 CER, along with a control level of C26:1 CER, is a characteristic feature of the cerebral type X-ALD. J. Med. Invest. 70 : 403-410, August, 2023.
Assuntos
Adrenoleucodistrofia , Ceramidas , Humanos , Adrenoleucodistrofia/genética , Ceramidas/sangueRESUMO
Despite the attempt by the Japanese government to reduce alcohol consumption, reduction of alcohol consumption requires improvement. We explore this issue from the impulsivity perspective and investigate whether a causal relationship exists between impulsivity and drinking behavior. We used data from the Preference Parameter Study of Osaka University to capture respondents' drinking status. Our probit regression showed that procrastination, a proxy measure of impulsivity, was significantly associated with drinking behavior, while hyperbolic discounting, a direct measure of impulsivity, was insignificant. Our findings suggest that impulsive people will discount their health in the future; thus, the government should consider impulsivity in policymaking. For example, awareness programs should focus more on future healthcare costs from alcohol-related problems so that impulsive drinkers can understand how much they may need to spend in the future compared to current satisfaction with alcohol drinking.
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Low interfacial resistance between the solid sulfide electrolyte and the electrode is critical for developing all-solid-state Li batteries; however, the origin of interfacial resistance has not been quantitatively reported in the literature. This study reports the resistance values across the interface between an amorphous Li3PS4 solid electrolyte and a LiCoO2(001) epitaxial thin film electrode in a thin-film Li battery model. High interfacial resistance is observed, which is attributed to the spontaneous formation of an interfacial layer between the solid electrolyte and the positive electrode upon contact. That is, the interfacial resistance originates from an interphase mixed layer instead of a space charge layer. The introduction of a 10 nm thick Li3PO4 buffer layer between the solid electrolyte and positive electrode layers suppresses the formation of the interphase mixed layer, thereby leading to a 2800-fold decrease in the interfacial resistance. These results provide insight into reducing the interfacial resistance of all-solid-state Li batteries with sulfide electrolytes by utilizing buffer layers.
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The origin of electrical resistance at the interface between the positive electrode and solid electrolyte of an all-solid-state Li battery has not been fully determined. It is well known that the interface resistance increases when the electrode surface is exposed to air. However, an effective method of reducing this resistance has not been developed. This report demonstrates that drastic reduction of the resistance is achievable by annealing the entire battery cell. Exposing the LiCoO2 positive electrode surface to H2O vapor increases the resistance by more than 10 times (to greater than 136 Ω cm2). The magnitude can be reduced to the initial value (10.3 Ω cm2) by annealing the sample in a battery form. First-principles calculations reveal that the protons incorporated into the LiCoO2 structure are spontaneously deintercalated during annealing to restore the low-resistance interface. These results provide fundamental insights into the fabrication of high-performance all-solid-state Li batteries.
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Calcium compounds with N and H are promising catalysts for NH3 conversion, and their epitaxial thin films provide a platform to quantitatively understand the catalytic activities. Here we report the selective epitaxial growth of Ca2NH and CaNH thin films by controlling the hydrogen partial pressure (PH2) during reactive magnetron sputtering. We find that the hydrogen charge states can be tuned by PH2: Ca2NH containing H- is formed at PH2 < 0.04 Pa, while CaNH containing H+ is formed at PH2 > 0.04 Pa. In situ plasma emission spectroscopy reveals that the intensity of the Ca atomic emission (â¼422 nm) decreases as PH2 increases, suggesting that Ca reacts with H2 and N2 to form Ca2NH at lower PH2, whereas at higher PH2, CaHx is first formed on the target surface and then sputtered to produce CaNH. This study provides a novel route to control the hydrogen charge states in Ca-N-H epitaxial thin films.
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Solid-state lithium (Li) batteries using spinel-oxide electrode materials such as LiNi0.5Mn1.5O4 are promising power supplies for mobile devices and electric vehicles. Here, we demonstrate stable battery cycling between the Li0Ni0.5Mn1.5O4 and Li2Ni0.5Mn1.5O4 phases with working voltages of approximately 2.9 and 4.7 V versus Li/Li+ in solid-state Li batteries with contamination-free clean Li3PO4/LiNi0.5Mn1.5O4 interfaces. This clean interface has the effect of doubling the capacity of conventional battery cycling between the Li0Ni0.5Mn1.5O4 and Li1Ni0.5Mn1.5O4 phases. We also investigated the structural changes between the Li0Ni0.5Mn1.5O4 and Li2Ni0.5Mn1.5O4 phases during battery cycling. Furthermore, we found an inhomogeneous distribution of the Li2Ni0.5Mn1.5O4 phase in the LiNi0.5Mn1.5O4 electrode, induced by spontaneous Li migration after the formation of the Li3PO4/LiNi0.5Mn1.5O4 interface. These results indicate that the formation of a contamination-free clean Li3PO4/LiNi0.5Mn1.5O4 interface is key to increase the battery capacity.