Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

Syntheses and structural properties of four Rb-aluminosilicate zeolites

Four types of Rb-aluminosilicate zeolites were hydrothermally synthesized in pure phase for the first time from Rb-aluminosilicate gels without using any organic structure-directing agent (SDA) under stirring conditions. The crystal structure of each zeolite was refined by Rietveld analysis of the X-ray diffraction (XRD) data. These crystal structures were confirmed to be Rb-mordenite, Rb-merlinoite, a new aluminosilicate zeolite with an ATT framework topology, and Rb-offretite denoted by RMA-1, RMA-2, RMA-3, and RMA-4, respectively. The Si/Al ratio of RMA-1 with an MOR topology varied from 5.3 to 8.0; however, the variation of the Si/Al ratios of the other zeolites was rather small. The crystal system of RMA-2 was tetragonal with space group I4/mmm, where two Rb sites were distributed at the center of an 8-membered ring (MR). On the other hand, two Rb sites in RMA-3 were located at the center of the 8-MR in small two cages. The structure of RMA-4 was identified as the OFF type with a local disorder or defect, which included a small amount of an intergrown ERI phase.     

Age-related accumulation of phosphatidylcholine hydroperoxide in cultured human diploid cells and its prevention by α-tocopherol

The levels of phosphatidylcholine hydroperoxide in serially cultured human fetal diploid fibroblasts at various population doubling levels were determined by high-performance liquid chromatography combined with chemiluminescence detections. This methodology utilizes a mixture of cytochromec and luminol as post-column hydroperoxide group specific luminescent reagents. The cellular hydroperoxide content increased with age from 0.34 to 27.72 pmol/10⁶ cells. At the end of the cells'in vitro lifespan (51st population doubling level), the hydroperoxide content per 10⁶ cells reached about 80 times the level found in cells of the 20th population doubling level. Supplementation of exogenous α-tocopherol to the culture medium prevented hydroperoxide accumulation, but did not extent the lifespanin vitro. The results indicate that substantial intracellular phospholipid hydroperoxide accumulation occurred in the course of aging of human fetal liploid fibroblasts.     

Arrangements of uniformly sized particles in a powder bed

The volume of the unit cell of a powder bed in a general case is calculated, and an equation is proposed for calculating the porosity of the bed consisting of uniformly sized ellipsoidal particles in contact and regularly arranged. In the case of uniformly sized spherical particles in contact, the equation can be simplified.Three dimensions and face angles of the unit cell are given for each regular arrangement both in cases of ellipsoidal and spherical particles. The values of the porosity are calculated by using the author's equation: the results for both ellipsoids and spheres are equal when tire particle arrangements are the same.The face angles of the unit cells proposed by Graton and Fraser are modified in two cases by the author's method of calculation and a system omitted from their classification is described. Other equations for calculation of the porosity are discussed.     

Electrochemical characteristics of iron carbide as an active material in alkaline batteries

Electrochemical properties of iron carbide (Fe₃C) for use as an alkaline battery anode were investigated during charge–discharge cycles. Results of electrochemical measurements and Mössbauer spectroscopy suggested that Fe₃C is oxidized irreversibly to Fe₃O₄ during discharge processes and that the produced Fe₃O₄ is subsequently changed to Fe(OH)₂ and Fe during the charging process, raising the discharge/charge capacity in further galvanostatic cycles. In addition, the electrode particles were observed to be less than 100 nm in diameter and to be highly dispersed on the surface of carbon black. These phenomena seems to be caused by dissolution and deposition of Fe(OH)₂ and Fe via intermediate iron species, leading to exposure of a fresh Fe₃C surface to the electrolyte after the second discharge.     

Magnetostatic wave resonators using microstrip disk

The authors propose a magnetostatic wave resonator using yttrium-iron-garnet (YIG) film with a microstrip disk. Assuming a magnetic wall at the edge of the disk, a dispersion relation is derived and solved numerically to obtain the resonant frequency. Resonant mode charts are given for various parameters of resonator. The quality factor is also given as a function of the resonator dimensions. Resonant characteristics are confirmed experimentally using 40-μm- and 13.5-μm-thick YIG films with 5-mm-diameter strip disk at S band     

Metal Single-Atom Cocatalyst on Carbon Nitride for the Photocatalytic Hydrogen Evolution Reaction: Effects of Metal Species

Single-atom (SA) catalysts exhibit high activity in various reactions because there are no inactive internal atoms. Accordingly, SA cocatalysts are also an active research fields regarding photocatalytic hydrogen (H₂) evolution which can be generated by abundant water and sunlight. Herein, it is investigated whether 10 transition metal elements can work as an SA on graphitic carbon nitride (g-C₃N₄; i.e., gCN), a promising visible-light-driven photocatalyst. A method is established to prepare SA-loaded gCN at high loadings (weight of ≈3 wt.% for Cu, Ni, Pd, Pt, Rh, and Ru) by modulating the photoreduction power. Regarding Au and Ag, SAs are formed with difficulty without aggregation because of the low binding energy between gCN and the SA. An evaluation of the photocatalytic H₂-evolution activity of the prepared metal SA-loaded gCN reveals that Pd, Pt, and Rh SA-loaded gCN exhibits relatively high H₂-evolution efficiency per SA. Transient absorption spectroscopy and electrochemical measurements reveal the following: i) Pd SA-loaded gCN exhibits a particularly suitable electronic structure for proton adsorption and ii) therefore they exhibit the highest H₂-evolution efficiency per SA than other metal SA-loaded gCN. Finally, the 8.6 times higher H₂-evolution rate per active site of Pd SA is achieved than that of Pd-nanoparticles cocatalyst.     

Photorefractive device using self-assembled monolayer coated indium-tin-oxide electrodes

Photorefractive (PR) performances of methyl-substituted poly(triarylamine) (PTAA)-based PR device were demonstrated using chemically modified electrodes (CMEs) of self-assembled monolayer (SAM) coated indium-tin-oxide (ITO) electrodes. The SAM-ITO electrodes successfully suppressed dark current which blocks the formation of space-charge field and also causes the dielectric breakdown. The PR device consisted of composite of PTAA, 4-azacycloheptylbenzylidenemalononitrile (7-DCST), N-ethylcarbazole (ECz), and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) sandwiched between the SAM-ITO electrodes. The PR devices showed the PR performances: optical gain Γ, refractive index Δn, diffraction efficiency η, response time τ, sensitivity S, phase shift Φ, trap-limited field E_q, number density of traps N_T, and space-charge field E_SC. The remarkable response time of 11.3 ms was achieved at the low electric field of 20 V μm⁻¹, which was comparable to the response time of high-definition television (HDTV) quality of 16 ms. Our approach will widen the usage of higher mobility materials to photorefractive field and give us more favorable materials to achieve the best performance of photorefractivity in the future.     

Network copolyesters from benzenepolycarboxylic acids and 1,6-hexanediol

Network copolyesters were prepared from trimesic (Y), pyromellitic (X) or mellitic (Y_H) acids and 1,6-hexanediol (6G). Prepolymers prepared by meltpolycondensation were cast from dimethylformamide solution and postpolymerized at 260°C for 6h to form a network. The resultant films were transparent, flexible and insoluble in any organic solvents. Degree of reaction estimated from the infrared absorbance of ester and methylene groups was almost the same for all films, 94–96%. X-ray diffraction intensity curves and densities showed that the ordering of networks was decreased by the copolymerization, which was remarkable for 6G–X/Y_H copolymer films and was consistent with the higher decreases of heat-distortion temperature for these copolymer films. The copolymerization also caused decrease of thermal stability, tensile properties and alkali resistance and increase of dye absorption.     

A case of ventricular septal perforation treated surgically with an infarction exclusion technique

We report an 85-year-old woman with postinfarction interventricular septal perforation. She underwent successful emergent surgical treatment by a slightly modified method based on David-Komeda's procedure. Perforation in this case occurred four days after acute myocardial infarction. Preoperative Qp/Qs was 2.58, and pulmonary artery pressure was 34/25 mmHg. The area of infarction was large, and the perforation was the linear type 2.5 cm long near the apex. A probe was not able to pass through the perforation due to its complicated configuration. A double Xenomedica patch was sutured on the left side of the interventricular septum without excising the infarcted area. The suture line was placed on healthy myocardium apart from the infarcted area. The Xenomedica patch was sandwiched between the closure line of the ventriculotomy. Four days after surgery, residual shunt was observed by echocardiogram, but this subsequently disappeared on the 17th postoperative day. The patient was discharged from our hospital on the 57th postoperative day, and is now doing quite well.