Monolayer assemblies of a sandwich-type double-decker porphyrin complex of cerium with an additional pendant porphyrin unit

We have prepared a novel sandwich-type double-decker porphyrin complex with cerium, in which one of the porphyrins has long alkyl chains and the other has a pendant free-base porphyrin unit. The preparation of the complex was achieved with a Sonogashira coupling reaction between a preformed double-decker complex bearing an ethynyl moiety and an iodophenyl porphyrin. This complex forms moderately ordered self-assembled monolayers at the interface of 1-phenyloctane and highly oriented pyrolytic graphite. STM images with submolecular resolution revealed that the double-decker complexes form monolayers through adsorption of the alkyl-substituted porphyrin unit, presenting the other porphyrin having the additional porphyrin unit to the solution. All molecules are oriented in the same direction within single ordered domains. The double-decker complex and the corresponding free-base porphyrin form mixed monolayers due to their common adsorbing group and the matching unit cell parameters. The high spots for the double-decker cores are accompanied by lower spots, which can be assigned as the pendant free-base porphyrin units, revealing that the double-decker complexes predominantly take perpendicular orientation, in which the additional porphyrin unit orients perpendicular to the molecular row. Both the double-decker complex and the free-base porphyrin adsorb on the surface initially after the mixture was deposited, but the double-decker complex is gradually replaced by free-base porphyrin toward the thermodynamically stable assembly, in which the free-base porphyrin predominates. This behavior is unique to this particular complex among some analogous complexes with the same adsorbing group, which implies that groups not directly involved in adsorption may have profound effects on the adsorption and assembling properties of the molecule.     

Solution‐processable colorless polyimides with ultralow coefficients of thermal expansion for optoelectronic applications

This work reports colorless polyimides (PIs) that are applicable as plastic substrates in image display devices, which produce an ultralow coefficient of thermal expansion (CTE) by solution casting without thermal imidization and mechanical stretching. An effective monomer molecular design is proposed for this purpose. Chemical imidization (CI) process compatibility is the key factor in attaining the target properties. We focused on a PI system derived from 1,2,3,4‐cyclobutanetetracarboxylic dianhydride (CBDA) and a novel para‐amide‐linked diamine (AB‐TFMB) with CF₃ groups as it has great potential as an ultralow CTE material, although it offers no CI process compatibility because of its poor solubility. The CBDA/AB‐TFMB system was modified by copolymerizing with 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride. This approach drastically improved CI process compatibility. The CTE of the PI films linearly decreased with increasing CBDA content. At a CBDA content of 70 mol%, the PI achieved an ultralow CTE of 7.3 ppm K^?1, non‐coloration/non‐turbidity, a very high glass transition temperature of 329 °C and sufficient ductility. The ultralow CTE results from the highly oriented main chains along the X–Y direction during the casting process as supported by the very high birefringence exceeding 0.1. Thus, our materials almost achieved the target properties required for novel coating‐type high‐temperature plastic substrate materials. © 2016 Society of Chemical Industry     

The aging of the anodic oxide of titanium during potentiostatic condition by ellipsometry

The aging effect of the anodic oxide film on titanium under constant potential oxidation was investigated by 3-parameter (3-P) ellipsometry in 0.1 mol dm⁻³ sulfuric acid solution. The oxide film was initially formed by a potential sweep oxidation, where the film with a low refractive index grew at relatively high rate. From the low value of the refractive index, the oxide film is assumed to be a hydrated structure. After the sweep oxidation to 4.26 V vs. reversible hydrogen electrode, the constant potential oxidation was performed at a potential of 4.26 V to examine the aging effect of the hydrated oxide film by 3-P ellipsometry. It was found that the refractive index of the oxide film increased from 2.39 to 2.59 during the aging of the constant potential oxidation, and the thickness decreased. The increase of the refractive index and the decrease of thickness may be explained by conversion from the hydrated oxide to a dehydrated oxide during the aging.     

A study of three‐dimensional observation of prebreakdown phenomena in dielectric liquids

This paper presents a new method which visualizes the high‐speed three‐dimensional images of prebreakdown streamers in dielectric liquids. A new optical system, having two crossed light axes to observe the needle tip from different directions, was designed. The shadowgraphic images from these two directions were combined through a beam splitter and focused on the photo‐cathode of an image converter camera. The photograph taken by this high‐speed shadowgraph system was reconstructed to three‐dimensional images using an image scanner and a computer. Using this system, the growth and decay processes of the streamer in cyclohexane were investigated. © 1999 Scripta Technica, Electr Eng Jpn, 128(4): 9–15, 1999     

Overexpression of the fanconi anemia group C gene (FAC) protects hematopoietic progenitors from death induced by Fas-mediated apoptosis

Fanconi anemia is a rare, inherited disorder characterized by bone marrow failure, congenital malformations, and cancer susceptibility. The group C Fanconi anemia gene, FAC, identified by expression cloning methods, encodes a protein of unknown function that may be involved in the response to apoptotic stimuli. Hematopoietic progenitor cells from Fac knock-out mice are hypersensitive to IFN-gamma, a molecule that can induce apoptosis through up-regulation of the Fas death receptor. In this study, we used FAC-overexpressing transgenic mice to examine the relationship between FAC and Fas-triggered cell death. Hematopoietic progenitors from FAC-transgenic mice were up to 10-fold less sensitive to the cytolytic effect of Fas-ligation. Our experiments implicate FAC in the regulation of apoptosis mediated by the Fas death receptor.     

Hyperspectral mapping-combining cathodoluminescence and X-ray collection in an electron microprobe

An optical spectrometer has been integrated into a JEOL 8900R electron microprobe, which allows simultaneous collection of light, X-ray, and electron signals. The cathodoluminescence signal is collected from a monocular eyepiece, which is integrated into the electron optics of the electron microprobe. The optical acquisition is synchronized with the stage motion. X-ray lines of major elements are collected using an energy dispersive spectrometer, X-ray lines of minor elements are collected using wavelength dispersive spectrometers, and the secondary and backscattered electron signals are collected using standard detectors. In mapping mode of operation the different signals are collected at each pixel with map sizes typically ranging from 1 million to 10 million pixels. This represents a significant amount of data from which the major correlations and associations in the map can be determined. Summing over a small number of channels and examining only a subset of the complete wavelength range are the strategies that have been developed to reduce the size of the data handled. The application of this mapping technique is demonstrated with two examples, zircons and refractory bricks. Zircons with various degrees of metamictization have been characterized, and inclusions differentiated using a combination of cathodoluminescence and X-ray maps. Examination of refractory bricks reveals subtle chemical changes in the spinel grains.     

Crystal structure of troponin and the molecular mechanism of muscle regulation

Troponin plays a central role in the regulation of skeletal and cardiac muscle contraction. The protein consists of three polypeptide chains (TnT, TnI and TnC) and is located on polymerized actin together with tropomyosin, forming muscle thin filament. We have determined the molecular structures of the core domains (relative molecular mass of 46,000 and 52,000) of human cardiac troponin in the Ca2+-saturated form by X-ray crystallography. Analysis of the four structures derived from the two crystal forms reveals that the core domain is further divided into sub-domains, connected by linkers, making the entire molecule highly flexible. The structures of the troponin ternary complex suggests that the Ca2+-binding to the regulatory TnC site displaces the carboxyl-terminal portion of TnI from actin/tropomyosin, thereby altering mobility and/or flexibility of the troponin/tropomyosin strand on the actin filament. These Ca2+-dependent changes in the properties of the tropomyosin strand on the actin filament may in turn alter accessibility of myosin heads (motor protein) to the actin filament.     

Resistance to gentamicin and vancomycin in enterococcal strains isolated from retail broiler chickens in Japan

A total of 137 Enterococcus strains isolated from chicken meat were subjected to antimicrobial susceptibility tests. Strains with the vanCl gene were isolated from seven of nine samples of chicken meat processed in Japan and from all chickens from China and Brazil between July 2001 and April 2002. The pulsed-field gel electrophoresis (PFGE) patterns of the isolates were distinguishable from each other, suggesting that VanCl-type vancomycin-resistant Enterococcus is preferentially colonized in broiler chickens in these countries. The incidence of high-level gentamicin resistant (HLGR) enterococci that harbored the aac(6')-le-aph(2")-la or aph(2')-Id gene varied among the countries from which the chickens originated (Japan, 2 of 65; China, 11 of 43; Brazil, 6 of 29). Moreover, the PFGE patterns of the HLGR strains were distinguishable from each other, except for two strains obtained from chickens from Brazil. The results suggest that HLGR Enterococcus is highly prevalent in broiler chickens.     

N-terminal amino acid sequences of troponin T fragments, including 30 kDa one, produced during postmortem aging of bovine longissimus muscle

We have determined the amino (N)-terminal amino acid (AA) sequences of five troponin T (TnT) fragments produced during postmortem aging of bovine longissimus muscle. Western blot analysis showed that 32.1, 28.8, 27, and 25.8 kDa anti-fast-type TnT (fTnT)-positive fragments and a 31 kDa anti-slow-type TnT (sTnT)-positive fragment were present at 14 d postmortem. The N-terminal AA sequences of the 32.1, 28.8 (conventional 30 kDa), 27, and 25.8 kDa fragments were APPPPAEV, EVHEPEEK, EKPRPRLT, and APKIPEGE, respectively, and they were mapped to the N-terminal region of bovine fTnT isoforms. The N-terminal sequences of the 31 kDa fragment, EAPEEPEP, were mapped to the sTnT isoforms. These findings indicate that the two isoform types of fTnT predominantly expressed in the longissimus muscle are cleaved specifically at Glu(21)-Ala(22) and Glu(15)-Ala(16), His(37)-Glu(38) and His(31)-Glu(32), Glu(43)-Glu(44) and Glu(37)-Glu(38), and/or Thr(51)-Ala(52) and Thr(45)-Ala(46), respectively, and that a sTnT isoform is cleaved specifically at Glu(23)-Glu(24).     

Solar coal gasification

A preliminary evaluation of the technical and economic feasibility of solar coal gasification has been performed. The analysis indicates that the medium-Btu product gas from a solar coal-gasification plant would not only be less expensive than that from a Lurgi coal-gasification plant but also would need considerably less coal to produce the same amount of gas. A number of possible designs for solar coal-gasification reactors are presented. These designs allow solar energy to be chemically stored while at the same time coal is converted to a clean-burning medium-Btu gas.