Synthesis of a Stable Selenoaldehyde by Self‐Catalyzed Thermal Dehydration of a Primary‐Alkyl‐Substituted Selenenic Acid

The unprecedented dehydration of a selenenic acid (RCH₂SeOH) to a selenoaldehyde (RCH?Se) has been demonstrated. A primary‐alkyl‐substituted selenenic acid was synthesized for the first time by taking advantage of a bulky cavity‐shaped substituent. Upon heating in solution, the selenenic acid underwent thermal dehydration to produce a stable selenoaldehyde, which was isolated as stable crystals and crystallographically characterized. Investigation of the reaction mechanism revealed that this β dehydration reaction involves two processes, both of which reflect the characteristics of a selenenic acid: 1) dehydrative condensation of two molecules of selenenic acid to generate a selenoseleninate intermediate [RCH₂SeSe(O)CH₂R], an isomer of a selenenic anhydride, and 2) subsequent β elimination of the selenenic acid from this intermediate to form a C?Se double bond, which establishes the self‐catalyzed β dehydration of the selenenic acid.     

Electrochemically Mediated Atom Transfer Radical Polymerization from a Substrate Surface Manipulated by Bipolar Electrolysis: Fabrication of Gradient and Patterned Polymer Brushes

We report the first ever use of electrochemically mediated atom transfer radical polymerization (eATRP) employing a bipolar electrochemical method for the fabrication of both gradient and patterned polymer brushes. A potential gradient generated on a bipolar electrode allowed the formation of a concentration gradient of a Cu^I polymerization catalyst through the one‐electron reduction of Cu^II, resulting in the gradient growth of poly(NIPAM) brushes from an initiator‐modified substrate surface set close to a bipolar electrode. These polymer brushes could be fabricated in three‐dimensional gradient shapes with control over thickness, steepness, and modified area by varying the electrolytic conditions. Moreover, by site‐selective application of potential during bipolar electrolysis, a polymer brush with a circular pattern was successfully formed. Polymerization was achieved using both a polar monomer (NIPAM) and a nonpolar monomer (MMA) with the eATRP system.     

Temporal diet changes recorded by stable isotopes in Asiatic black bear (Ursus thibetanus) hair

Carbon and nitrogen stable isotope ratios were measured in hair samples of the Asiatic black bear (Ursus thibetanus) inhabiting the Northern Japanese Alps (NJA) (n?=?20) and the periphery of Nagano City (NC) (n?=?6), in Nagano Prefecture, Japan. The hair of NJA bears, which did not have access to anthropogenic foods, showed lower values of δ¹³C and δ¹⁵N than that of NC bears which had access to garbage and corn fields, especially during the summer. These results reflect somewhat differing diets between the NJA and NC bears. We attempted to assess the feeding history during the hair growth cycle using the growth section analysis method. Each hair sample had been cut into 3?mm lengths from root to tip, labeled, and analyzed along the hair growth. We measured the carbon and nitrogen stable isotope ratios of each 3?mm length of hair sample from one NC bear which had been killed while raiding a corn field. The sections showed wide ranges of isotope ratios, from ?23.2‰ to ?14.6‰ for δ¹³C, and from 0.3‰ to 4.6‰ for δ¹⁵N. It was shown that the diet of this bear shifted dramatically from principally C₃ plants to more C₄ plants and to foods of animal origin. An analysis of the whole hair reflects just the average feeding habit during hair growth, but the present method can trace its diet history. This method can contribute to obtain precise ecological information of wildlife.     

Surface pressure and flow field behind an oscillating fence submerged in turbulent boundary layer

Phase-locked PSP and PIV measurements were used to study the evolution of three-dimensional disturbances produced by an oscillating fence actuator immersed in a zero pressure gradient turbulent boundary layer. For the single fence frequency studied, strong three-dimensionality is observed in the vortical structure that varies along the span of the fence soon after the fence enters the flow. At the midspan, the structure grows, weakens, and convects faster than at other locations. As the fence height increases, the data indicate that the vortical structure terminates near the edge of the fence. In contrast, the vortex structure terminates on the plate surface adjacent to the fence edge as the fence descends, similar to a wake vortex of a stationary obstacle. This study demonstrates that the combined use of surface and flow-field diagnostics provide a link between flow field and surface features, yielding an understanding of the flow that would have not been possible with any one technique.     

Conserved quantity of elastic waves in multi-layered media: 2D SH case — Normalized Energy Density

We introduce a new conserved quantity, Normalized Energy Density (NED), alternative to the conventional definition of energy for a layered structure in a 2D SH problem. NED is defined by the average of power of a half transfer function multiplied by the impedance, and the conservation across the material interface is analytically proved for a two-layered case. For three, four, and ten-layered cases, the conservation is examined by applying the Monte Carlo simulation method, and then NED is supposed to be conserved through the layers.     

A combined use of DEA (Data Envelopment Analysis) with Strong Complementary Slackness Condition and DEA–DA (Discriminant Analysis)

This study discusses a combined use of DEA (Data Environment Analysis) with SCSC (Strong Complementary Slackness Condition) and DEA–DA (Discriminant Analysis). Many studies use DEA to evaluate the performance of various organizations in private and public sectors. A conventional use of DEA is not perfect because it still contains zero in many multipliers. This implies that DEA does not fully utilize information on all inputs and outputs. As a result, DEA produces many efficient organizations. To overcome the methodological difficulty, this study proposes a new use of DEA/SCSC and DEA–DA to reduce the number of efficient organizations.     

Single-nanometer focusing of hard x-rays by Kirkpatrick-Baez mirrors

We have constructed an extremely precise optical system for hard-x-ray nanofocusing in a synchrotron radiation beamline. Precision multilayer mirrors were fabricated, tested, and employed as Kirkpatrick-Baez mirrors with a novel phase error compensator. In the phase compensator, an at-wavelength wavefront error sensing method based on x-ray interferometry and an in situ phase compensator mirror, which adaptively deforms with nanometer precision, were developed to satisfy the Rayleigh criterion to achieve diffraction-limited focusing in a single-nanometer range. The performance of the optics was tested at BL29XUL of SPring-8 and was confirmed to realize a spot size of approximately 7 nm.     

Creation of coating surfaces possessing superhydrophobic and superoleophobic characteristics with fluoroalkyl end-capped vinyltrimethoxysilane oligomeric nanocomposites having biphenylene segments

Fluoroalkyl end-capped vinyltrimethoxysilane oligomeric nanocomposites having biphenylene units [R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2)] were prepared by the sol-gel reaction of the corresponding oligomer [R(F)-(VM)(n)-R(F)] with 4,4'-bis(triethoxysilyl)-1,1'-biphenyl [Ar-Si(OEt)(3)] under alkaline conditions. R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites were applied to the surface modification of PMMA to exhibit not only a good oleophobicity imparted by fluorine but also a fluorescent emission ability on the surface. Methanol sol solutions of R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites were effective for the surface modification of glass through the dipping technique to exhibit good oleophobicity with superhydrophobicity on the modified glass surface. On the other hand, 1,2-dichloroethane sol solutions enabled R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites to exhibit both superhydrophobic and superoleophobic characteristics on the modified surface through dipping the glass in these sol solutions.     

Preparation of perfluoro-1,3-propanedisulfonic acid/silica nanocomposites-encapsulated low molecular weight aromatic compounds possessing a nonflammable characteristic

Perfluoro-1,3-propanedisulfonic acid/silica [PFPS/SiO(2)] nanocomposites were prepared by the sol-gel reactions of the corresponding disulfonic acid [PFPS] with tetraethoxysilane and silica nanoparticles under alkaline conditions. These fluorinated nanocomposites thus obtained can exhibit no weight loss behavior corresponding to the contents of PFPS in the composites after calcination at 800°C, although the parent PFPS can decompose completely around 270°C. In addition, we succeeded in encapsulation of a variety of low molecular weight aromatic compounds such as bisphenol-A, bisphenol-AF, bisphenol-F, 4,4'-biphenol and 1,1'-bi-2-naphthol into PFPS/SiO(2) nanocomposite cores. (1)H MAS NMR spectra, UV-vis spectra, fluorescence spectra and HPLC measurements of PFPS/SiO(2) nanocomposites-encapsulated bisphenol-A showed the presence of encapsulated bisphenol-A in the composites before and even after calcination at 800°C. Interestingly, it was verified that fluorescence spectra of PFPS/SiO(2) nanocomposites-encapsulated bisphenol-A after calcination at 800°C can exhibit an extremely red-shifted and enhanced fluorescence peak, compared to that before calcination or parent bisphenol-A.