Generation of New Artificial Metalloproteins by Cofactor Modification of Native Hemoproteins

Heme can be removed from a number of native hemoproteins, thus forming corresponding apoproteins, each of which provides a site for binding of a metal complex. In one example, myoglobin, an O₂ storage protein, can be reconstituted with iron porphycene to dramatically enhance the O₂ affinity. Although it is known that myoglobin has poor enzymatic activity, the insertion of iron corrole or iron porphycene into apomyoglobin increases its H₂O₂-dependent peroxidase/peroxygenase activities. Furthermore, reconstitution with manganese porphycene promotes hydroxylation of an inert C H bond. It is also of interest to insert a non-porphyrinoid complex into an apoprotein. A cavity of apocytochrome c has been found to bind a diiron carbonyl complex, serving as a functional model of diiron hydrogenase. Aponitrobindin has a rigid β-barrel structure that provides an excellent cavity for covalently anchoring a metal complex. A rhodium complex embedded in the cavity of genetically modified nitrobindin has been found to promote stereoselective polymerization of phenylacetylene.     

Perpendicular oriented cylinders via directional coalescence of spheres embedded in block copolymer films induced by solvent annealing

Polystyrene-b-poly(methyl acrylate) (PS-b-PMA) block copolymer with PS volume fraction of 25.2 vol% was synthesized by atom transfer radical polymerization. Non-pretreated silicon wafers were used as the substrates to prepare perpendicular oriented PS cylinders in PMA matrix via solvent annealing which could induce the transformation of spheres to vertically oriented and hexagonally packed cylinders. The spherical microdomains were formed after the evaporation of solvents from the solutions of the block copolymer in selective solvents mixed from methanol, acetone and dichloromethane. The thickness of films could be as thick as 1000 nm, which were much thicker than usual cases and the cylinders came from the directional coalescence of the spheres, thus any pre-treatments of the substrates were not required for perpendicular orientation. The structures were characterized by small angle X-ray scattering (SAXS), transmission electron microscope (TEM), atom force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS).     

Human behavior in a staircase during a total evacuation drill in a high‐rise building

Many studies have been conducted on the evacuation behavior on the staircases of buildings, but very little data are available for a situation with many occupants in a crowded high‐rise building. Therefore, this study investigated the evacuation behavior of a large number of evacuees on the staircase of a 25‐story high‐rise building. A total evacuation drill was conducted with 2088 evacuees, and the behavior of 1136 evacuees on the landings of the south staircase was recorded by a video recorder on the ceiling. The relationship between the density and speed of the evacuees on the landings was analyzed from the evacuation data for two situations: without and with merging in the stair flow. The evacuation stair flow in this drill had merging occupants entering from the floors, but no one entered from the lower floors during the latter period of the drill. Therefore, the flow during the latter period was treated as non‐merging flow, for which it was observed that, when the staircase was fully crowded, the density on the landings in the moving situation was different from that in the stopped situation. Moreover, the density on the landings was different from that on the treads. Furthermore, in the merging flow, a merging ratio of approximately 50:50 occurred during the congested evacuation. Copyright © 2016 John Wiley & Sons, Ltd.     

Rubber‐toughened polyamide‐6 with a low thermal expansion coefficient: effect of preferential distribution of rubber and inorganic filler

The effects of morphological changes on the thermal expansion, toughness and heat resistance of polyamide‐6 (PA)/styrene–ethylene–butylene–styrene (SEBS)/polyphenylene ether (PPE) blends were investigated. Compared with the typical ‘sea (PA matrix)–island (PPE domain)–lake (SEBS in PPE domain)’ morphology, an injection‐molded ternary blend with a preferential distribution of SEBS component at the interface between PA and PPE exhibited a low coefficient of linear thermal expansion (CLTE) in the flow direction. This low CLTE was ascribed to the deformation of SEBS and PA into a co‐continuous microlayer network structure during injection molding. Consequently, the expansion preferentially occurred towards the thickness direction. Further CLTE reduction either by a change in PA viscosity or by the selective location of an inorganic filler was examined, and its influences on impact strength and heat resistance are discussed based on transmission electron microscopy observations. © 2015 Society of Chemical Industry     

Superconductivity in Boron-Doped Carbon Nanotubes

Carbon nanotubes (CNTs), which are one-dimensional (1D) molecular conductors, have attracted considerable attention. However, none of the research has reported on superconductivity (SC) in carrier-doped CNTs. Here, we report on SC with the world??s highest transition temperature (T _c) of 12 K in highly uniform thin films of boron-doped single-walled CNTs (B-SWNTs). We clarify correlation of SC with Fermi level tuning with van Hove singularities (VHS) in electronic density of states (DOS) in the SWNT. Moreover, we show fabrication of paper-like thin films consisting of a pseudo two-dimensional network of weakly coupled B-SWNTs (called the Buckypaper) and show an enhancement of the onset T _c up to 19 K by applying only a small pressure. The present observations will shed light on the high feasibility of using CNTs as a 1D superconductor and also on the research of 1D electron correlation.     

Freeze-dried solid foams prepared from carbon nanotube aqueous suspension: Application to gas diffusion layers of a proton exchange membrane fuel cell

Freeze-dried macroporous solid foams were prepared from the multi-walled carbon nanotube (MWCNT) aqueous suspensions dispersed by chitosan. Thin film shaped CNT solid foams were prepared, and applied to the gas diffusion layers (GDLs) of a laboratory scale proton exchange membrane fuel cell (PEMFC). It was demonstrated that the prepared carbon foams in this study were useful to a fuel cell GDL material. The prepared cell performances were fairly comparable to the cell prepared with conventional carbon paper for GDL material. The microstructures of the prepared carbon foams were found to affect on the PEMFC performances. It was suggested that the interconnected carbon networks formed during the freezing step closely link to the cell performances. Hence, the defection of the interconnected microstructure lead degradation of the GDL quality. The impedance measurement made clear that the prepared foam materials were also advantageous for reducing the ohmic resistance in PEMFC assembly. The kinetic resistance values and the thermal conductive characteristics suggested that the freezing process would also control the degree of overlaps among single CNTs in a freeze-dried bulk that influenced on the electrochemical properties.     

Estimation of Small Reservoir Storage Capacities with Remote Sensing in the Brazilian Savannah Region

Small reservoirs play an important role in supporting the local economy in the savannah areas of Brazil and are primarily used for the provision of water for irrigation and watering livestock. Hundreds of small reservoirs have been built in the last few decades in the Preto River Basin, but efficient water management and sound planning are hindered by inadequate knowledge of the number, storage capacity and spatial distribution of reservoirs in the basin. The main reason for the lack of this information is that current methodologies for quantifying the physical parameters of reservoirs are laborious, time consuming and costly. To address this lack of data, a simple method to estimate reservoir storage volumes based on remotely sensed reservoir surface area measured with LANDSAT was developed. The method was validated with a subset of reservoirs in the Preto River Basin for which surface areas, shapes and depths were determined with ground-based survey measurements. The agreement between measured and the remotely sensed reservoir volumes was satisfactory, indicating that remotely-sensed images can be used for improved management of water in the Brazilian Savannah region. With the newly developed methods we found that the Preto River Basin’s 147 small reservoirs can store 19 × 10⁶ m³ of water at full capacity.     

Hybrid Counterfactual Logics

The purpose of this paper is to argue that the hybrid formalism fits naturally in the context of David Lewis’s counterfactual logic and that its introduction into this framework is desirable. This hybridization enables us to regard the inference “The pig is Mary; Mary is pregnant; therefore the pig is pregnant” as a process of updating local information (which depends on the given situation) by using global information (independent of the situation). Our hybridization also has the following technical advantages: (i) it preserves the completeness and decidability of Lewis’s logic; (ii) it allows us to characterize the Limit Assumption as a proof-rule with some side-conditions; and (iii) it enables us to establish a general Kripke completeness result by using the proof-rule corresponding to the Limit Assumption.     

Generation of disk-like domains with nanometer scale thickness in merocyanine dye LB film induced by hydrothermal treatment

We have characterized the binary LB films of merocyanine dye (MS) and arachidic acid (C₂₀) before and after hydrothermal treatment (HTT), which is defined as a heat treatment under relative humidity of 100%, focusing on the morphology studied by bright field (BF) microscopy and fluorescence (FL) microscopy. BF microscopy observation has revealed that the as-deposited MS-C₂₀ binary LB film is found to emit intense red fluorescence over the whole film area by 540-nm excitation. Since the surface image is almost featureless, it is considered that the crystallite sizes of J-aggregate are less than 10 μm. Interestingly, after HTT, round-shaped domains are observed in the LB systems, and the sizes are reaching 100 μm in diameter. Crystallites of J-aggregate, which are bluish in color and emit intense red fluorescence, tend to be in the round domains. We have observed two different types of domains, i.e., blue-rimmed domains and white-rimmed domains, which are postulated to be confined in the inner layers and located at the outermost layer, respectively. The thickness of the domains is equal to or less than that of the double layer of the MS-C₂₀ mixed LB film, which is ca. 5.52 nm. The molecular order of MS in the J-aggregate is improved by the HTT process leading to the significant sharpening of the band shape together with the further red shift of the band (from 590 to 594 nm up to 597 to 599 nm). The reorganized J-band is considered to be ‘apparently’ isotropic owing to the random growth of the J-aggregate in the film plane. We consider that the lubrication effect by the presence of water molecules predominates in the HTT process.