High-pressure studies on Tc and crystal structure of iron chalcogenide superconductors

The superconducting transition temperature, T_c, in iron-based solids can be enhanced by applied pressure: T_c increases from 8 to 37 K for the 11-type FeSe when the pressure is raised from 0 to 4 GPa. High-pressure studies can elucidate the mechanism of superconductivity in such novel materials. In this paper, we present a high-pressure study of Fe(Se_1−xTe_x) and Fe(Se_1−xS_x). In the case of Fe(Se_1−xTe_x), the maximum T_c under high pressure did not exceed the T_c of FeSe, which can be attributed to the structural transition to the monoclinic phase. For Fe(Se_1−xS_x) (0 < x < 0.3), T_c exhibited a significant increase with pressure; however, the maximum T_c under high pressure did not exceed the T_c of FeSe. This may be due to the disorder induced by substituting S for Se, which is similar to the pressure effect on T_c for the 1111-type superconductor Ca(Fe_1−xCo_x)AsF. The T_c of Fe(Se_1−xS_x) showed a complex behavior below 1 GPa, first decreasing and then increasing with increasing pressure. From high-pressure x-ray diffraction measurements, the T_c (P) curve was correlated with the local structural parameter.     

Gas analysis of the CVD process for high yield growth of carbon nanotubes over metal-supported catalysts

Changes in the gas composition during the methane chemical vapor deposition growth of single- and double-walled carbon nanotubes over metal-supported MgO catalysts were investigated in an attempt to increase the nanotube yield. Monitoring the gas composition by gas chromatography as a function of the reaction time provides information on the activity and lifetime of the catalyst. The degree of methane decomposition, i.e., the C-H bond dissociation, was closely related to the nanotube yield, and the Fe-Mo binary catalyst exhibited a high activity. The effects of water vapor on the catalytic nanotube growth were also studied by introducing water vapor in the inlet gas. An appropriate amount of water prolonged the lifetime of the catalyst and increased the nanotube yield by 35%.     

The characteristics of the external‐electrode mercury fluorescent lamp for backlighting liquid‐crystal‐television displays

Abstract— A reliable external‐electrode mercury fluorescent lamp (EEFL) has been developed for backlighting a liquid‐crystal‐television (LC‐TV) display. This involved the investigation of the EEFL characteristics and the improvement in the construction of the EEFL and drive waveforms, in the frequency range of 50–200 kHz, that affects the EEFL characteristics. The results showed that a sinusoidal waveform is suitable for driving the EEFL, and EEFL's voltage decreases when the frequency of the drive waveform is increased.     

Structural Distortion and Compositional Gradients Adjacent to Epitaxial LiMn2O4 Thin Film Interfaces

Thin film electrode materials are key components in the development of high rate, high capacity solid‐state Li‐ion batteries. Detailed knowledge of the epitaxial film/substrate(current‐collector) interface structures, which provides insights into epitaxial growth mechanisms and the effects of microstructure on electrochemical properties, is essential for efficient materials and device design. Here we report the epitaxial growth mechanism of a typical cathodic LiMn₂O₄ thin film by exploring the detailed structural and compositional variations in the vicinity of a film/substrate interface using state‐of‐the‐art scanning transmission electron microscopy. Direct observation of atom columns shows the epitaxial film forms an atomically flat and coherent heterointerface with the substrate, but that the crystal lattice is tetragonally distorted with a measurable compositional gradient from the interface to the crystal bulk. The growth mechanism is interpreted in terms of a combination of chemical and physicomechanical effects, namely a complex interplay between the internal Jahn‐Teller distortions induced by oxygen non‐stoichiometry and the lattice misfit strain.     

Characterization of doped single-wall carbon nanotubes by Raman spectroscopy

Single-wall carbon nanotubes were grown by thermal chemical vapor deposition using either boron- or nitrogen-containing feedstocks or both. Carrier doping was evidenced by hardenings of the G band in Raman spectra, and the estimated carrier concentration reached ∼0.4%. In the G′ and D band spectra, a doping-induced component was observed at the high- or low-energy side of the original one. However, the appearance of the new component did not always coincide with the carrier doping. The doped SWCNTs often show radial breathing mode peaks in the off-resonance region, indicating a defect-induced modification of absorption spectrum.     

Single-step synthesis and characterization of single-walled carbon nanohorns hybridized with Pd nanoparticles using N2 gas-injected arc-in-water method

Single-walled carbon nanohorns (SWCNHs) hybridized with palladium (Pd) nanoparticles were synthesized by a single-step gas-injected arc-in-water method (GI-AIW) with a Pd wire inserted inside the anode hole. In the arc zone, carbon and Pd were vaporized simultaneously, leading to the formation of hybrid material of SWCNHs and Pd nanoparticles due to effective quenching. Based on TEM and CO chemisorption analyses, Pd nanoparticles were found to be embedded inside SWCNH aggregates. The size of Pd nanoparticles, determined by X-ray diffraction, was in the range of 3–6 nm when Pd wires with diameters of 0.1 and 0.3 mm were used. Using a Pd wire with a diameter larger than 0.5 mm results in larger Pd nanoparticles which tend to be exposed to the outer surface of the hybrid material. According to thermogravimetric analyses, the weight fraction of Pd nanoparticles is increased by increasing the Pd wire diameter although the yield of Pd nanoparticles decreased. SWCNHs hybridized with dispersed Pd nanoparticles, synthesized with 0.1 mm Pd wire, exhibited strong anti-oxidation resistance with a highly graphitic structure.     

Preparation of π-conjugated polymers consisting of 1-aminopyrrole and 4-amino-1,2,4-triazole units

π-Conjugated polymers based on 1-aminopyrrole and 4-amino-1,2,4-triazole were prepared. Pd-catalyzed organometallic polycondensation gave poly(arylene-ethynylene) (PAE)-type π-conjugated polymers consisting of BOC-protected 4-amino-1,2,4-triazole (Taz(BOC)) units (BOC = t-butoxycarbonyl). The number average molecular weights (M_n) were determined to be 5200–19,200 using GPC. An alternating copolymer of Taz(BOC) and bithiophene (Th–Th) units, P(Taz(BOC)-Th-Th)_n-Pd, with an M_n of 10,800 was also prepared by Pd-catalyzed organometallic polycondensation. (Taz(BOC)-Th-Th)_n-Pd showed a UV–Vis absorption peak at λ_max = 425 nm, which is reasonable for a π-conjugated five-membered ring polymer with a coplanar structure. The deprotection of the BOC group of the polymers proceeded at 200 °C; this BOC-deprotection was investigated using a model compound. The optical and electrochemical properties of the π-conjugated polymers are reported.     

Development of Laser Ionization Techniques for Evaluation of the Effect of Cancer Drugs Using Imaging Mass Spectrometry

Recently, combined therapy using chemotherapy and photodynamic therapy (PDT) has been proposed as a means of improving treatment outcomes. In order to evaluate the efficacy of combined therapy, it is necessary to determine the distribution of the anticancer drug and the photosensitizer. We investigated the use of imaging mass spectrometry (IMS) to simultaneously observe the distributions of an anticancer drug and photosensitizer administered to cancer cells. In particular, we sought to increase the sensitivity of detection of the anticancer drug docetaxel and the photosensitizer protoporphyrin IX (PpIX) by optimizing the ionization-assisting reagents. When we used a matrix consisting of equal weights of a zeolite (NaY5.6) and a conventional organic matrix (6-aza-2-thiothymine) in matrix-assisted laser desorption/ionization, the signal intensity of the sodium-adducted ion of docetaxel (administered at 100 μM) increased about 13-fold. Moreover, we detected docetaxel with the zeolite matrix using the droplet method, and detected PpIX by fluorescence and IMS with α-cyano-4-hydroxycinnamic acid (CHCA) using the spray method.     

Monolithiation of 5,5′‐Dibromo‐2,2′‐bithiophene Using Flow Microreactors: Mechanistic Implications and Synthetic Applications

The lithiation of 5,5′‐dibromo‐2,2′‐bithiophene with one equivalent of an alkyllithium such as n‐BuLi or s‐BuLi was studied by varying the residence time in flow microreactors. With a short residence time, the product 2,2′‐bithiophene (3) derived from dilithiation was obtained preferentially and a significant amount of the starting material 5,5′‐dibromo‐2,2′‐bithiophene remained unchanged. An increase in the residence time caused a higher yield of the product 5‐bromo‐2,2′‐bithiophene derived from monolithiation with expense in the yields of 2,2′‐bithiophene and 5,5′‐dibromo‐2,2′‐bithiophene. The lithiation using MeLi gave the product 5‐bromo‐2,2′‐bithiophene preferentially even with a very short residence time.     

Controlling the drug release rate from biocompatible polymers with micro-patterned diamond-like carbon (DLC) coating

During the past year, we have witnessed the evolution of an intense public controversy regarding late thrombosis following implantation of drug eluting stent (DES) in patients with obstructive coronary artery disease. To overcome the problem, DES should possess sufficient biocompatibility and non-thrombogenicity with a controlled drug release system. A new DES composed of biocompatible polymers coated with antithrombogenic diamond-like carbon (DLC) coating was proposed. In this study, the drug release profile of the newly proposed drug eluting system was thoroughly investigated. Three polymers were selected as base drug-reservoir materials: hydrophilic 2-methacryloyloxyethyl phosphorylcholine (MPC), hydrophobic poly (ethylene-co-vinyl acetate) (EVA) and less hydrophobic polyurethane (PU). The three polymers are currently used or studied for biomedical materials, while MPC and DLC were already confirmed as excellent biocompatible materials with antithrombogenicity. After coating the lattice-like patterned DLC on both polymers containing drug, samples were soaked in 2 ml of medium of phosphate-buffered saline with 10% ethanol. The drug release rate was measured by a spectrophotometer. The percentile cover area of patterned DLC on polymers was varied from 0% (without DLC) to 100% (fully covered). The sample without DLC coating presented an initial burst of the drug release from the polymer matrix, whereas the DLC-coated samples inhibited the initial burst release from polymers within the first five days of the experiments. It was found that the drug eluting profiles could be effectively controlled by changing the cover area of micro-patterned DLC coatings on polymers, which may be applicable to the next-generation DES system that eventually prevents late thrombosis.