Spherulitic formation and characterization of partially fluorinated copolymers and their nanohybrids with functional fillers

Poly[vinylidenefluoride‐co‐(tetrafluoroethylene)] (P(VDF‐TeFE)) exhibited clear spherulitic texture with negative birefringence. The number and growth rates of the spherulites decreased at high crystallization temperature than at low crystallization temperature. Nonetheless, overall larger spherulites were found at high crystallization temperature and the brightness of the spherulites increased very fast at low crystallization temperature, thereafter it seemed as diminution of birefringence. AFM was used to investigate the impact of organo modified nanodiamond(ND) on spherulitic textures, lamellar thickness, and thickness distribution of P(VDF‐TeFE) copolymer. Poly[ethylene‐co‐(tetrafluoroethylene)] (ETFE) also confirmed spherulites structure and the boundaries could be clearly observed. By incorporation of the organo modified nanodiamond (ND) and organo‐modified montmorillonite (MMT) in fluropolymer matrix, it was found that spherulitic texture was seriously disordered and their nanohybrids was found only to have poorly developed spherulite structure. Both of the nanohybrids samples show better crystallization temperature as compared to their neat copolymer samples. Furthermore, the incorporation of nanoparticles decreased the size of the spherulites. POLYM. ENG. SCI., 57:161–171, 2017. © 2016 Society of Plastics Engineers     

The study on change of mechanical properties of NBR due to deterioration

Rubber is an important industrial material. However, mechanical properties and deformation of the high polymer including rubber are not clear. A method of estimating the mechanical properties which can be used for the deteriorated rubber is demanded to improve the reliability of it. Improved VBO (Viscoplasticity theory based on overstress) model is a constitutive equation. We applied it for the compression stress-strain behavior of deteriorated NBR (acryloNitrile-Butadiene rubber). Furthermore, we proposed a method of estimating the mechanical properties of deteriorated NBR. In this paper, deterioration tests in water and in air were conducted. To confirm the validity of the proposed improved VBO model and estimated mechanical properties, simulations of the stress-strain curves obtained in the tests were conducted.     

In situ X-ray diffraction of surface oxide on type 430 stainless steel in breakaway condition using synchrotron radiation

Changes in the crystal structure of type 430 stainless steel and the oxides on its surface were studied in situ at 1373 K using a high-intensity synchrotron X-ray source provided by SPring-8 in Japan. The surface of the steel was initially covered with Cr₂O₃, which was then converted to FeCr₂O₄, and finally Fe₃O₄ and Fe₂O₃ formed on it. These results indicated that the reason for the breakaway oxidation in type 430 stainless steel is Cr depletion beneath Cr₂O₃ layer and the subsequent ionisation of Fe, not the simple mechanical failure of Cr₂O₃.     

Identification of Sex Pheromones of Anadevidia peponis and Macdunnoughia confusa and Field Tests of Their Role in Reproductive Isolation of Closely Related Plusiinae Moths

Anadevidia peponis and Macdunnoughia confusa are defoliators of plants in the family Cucurbitaceae and Compositae, respectively, in Japan. GC-MS analyses of crude pheromone gland extracts treated with or without dimethyl disulfide indicated that females of A. peponis produced six monoene acetates and two monoene alcohols and that M. confusa females produced five monoene acetates. These components include (Z)-7-dodecenyl acetate as a major common constituent and three other acetates as minor common constituents. The minor constituents are quite different in blend composition. In addition, with (Z)-7-dodecenyl acetate, an indispensable component for male attraction is (Z)-5-decenyl acetate for A. peponis and (Z)-9-tetradecenyl acetate is essential for M. confusa. Field tests with synthetic lures showed synergistic effects of some other minor components and male attraction of three additional Plusiinae species, Macdunnoughia purissima, Ctenoplusia albostriata, and Chrysodeixis eriosoma, suggesting their reproductive isolation is based in part on pheromonal communication.     

Active Polymer Gel Actuators

Many kinds of stimuli-responsive polymer and gels have been developed and applied to biomimetic actuators or artificial muscles. Electroactive polymers that change shape when stimulated electrically seem to be particularly promising. In all cases, however, the mechanical motion is driven by external stimuli, for example, reversing the direction of electric field. On the other hand, many living organisms can generate an autonomous motion without external driving stimuli like self-beating of heart muscles. Here we show a novel biomimetic gel actuator that can walk spontaneously with a worm-like motion without switching of external stimuli. The self-oscillating motion is produced by dissipating chemical energy of oscillating reaction. Although the gel is completely composed of synthetic polymer, it shows autonomous motion as if it were alive.     

Synthesis and catalytic properties of sulfonic acid-functionalized monodispersed mesoporous silica spheres

A new type of sulfonic acid-functionalized monodispersed mesoporous silica spheres (MMSS) were synthesized directly by co-condensation and subsequent oxidation. By changing the methanol ratio, sulfonic acid-functionalized MMSS with different particle diameters (390–830 nm) and the same mesopore sizes were successfully synthesized. TEM observations revealed that the mesopores were aligned radially from the center towards the outside of the spheres, even in the sulfonic acid-functionalized MMSS. The catalytic activities of the sulfonic acid-functionalized MMSS were studied in condensation reactions between 2-methylfuran and acetone, and it was found that their catalytic activities are highly dependent on the particle diameters. In addition, the catalytic activity of MMSS was much higher than that of other forms of mesoporous silica due to its radially-aligned mesopores.     

Acrolein formation in the oxidation of ethane over silica catalysts supporting iron and cesium

A significant yield of aldehydes was obtained by the partial oxidation of ethane over alkali‐modified Fe/SiO₂ catalysts at 475°C (<2% in the case of Cs–Fe/SiO₂). Not only acetaldehyde and formaldehyde but also acrolein were produced in the present system. There are no reports regarding the catalysts for the direct acrolein formation from partial oxidation of ethane. Such significant promoting effect of alkali‐modified Fe/SiO₂ catalysts in the partial oxidation of hydrocarbons has never been observed. Aldol‐type condensation for formation of acrolein could occur in the partial oxidation of ethane over alkali‐modified Fe/SiO₂ catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of friction stir processing on microstructure of laser clad cobalt-based alloy

(The microstructural refinement of cobalt-based alloy (Stellite No. 6) by laser cladding and friction stir processing (FSP) was studied. A nanometer-sized microstructure consisting of fine carbide (particle size: 100–200 nm) and a grain (grain size: 150–250 nm) was successfully fabricated by the FSP on the laser clad cobalt-based alloy. The nanostructured cobalt-based alloy (Stellite No. 6) had an extremely high hardness of about 750 HV.     

Two Triterpene Synthases from Imperata cylindrica Catalyzing the Formation of a Pair of Diastereoisomers through Boat or Chair Cyclization

Imperata cylindrica is known to produce a pair of triterpenes, isoarborinol and fernenol, that exhibit identical planar structures but possess opposite stereochemistry at six of the nine chiral centers. These differences arise from a boat or a chair cyclization of the B-ring of the substrate. Herein, we report the characterization of three OSC genes from I. cylindrica. IcOSC1 and IcOSC5 were identified as isoarborinol and fernenol synthases, respectively, while IcOSC3 was characterized as a multifunctional enzyme that produces glutinol and friedelin as its major products. Mutational studies of isoarborinol and fernenol synthases revealed that the residues surrounding the DCTAE motif partially affected the conformation of the B-ring during cyclization. Additionally, the IcOSC1-W255H mutant produced the rare triterpene boehmerol. The introduced histidine residue presumably abstracted a proton from the intermediary carbocation at C18 during the 1,2-rearrangement. Expression analysis indicated that all OSC genes were highly expressed in stems.     

Chemical Modification of Phage-Displayed Helix-Loop-Helix Peptides to Construct Kinase-Focused Libraries

Conformationally constrained peptides hold promise as molecular tools in chemical biology and as a new modality in drug discovery. The construction and screening of a target-focused library could be a promising approach for the generation of de novo ligands or inhibitors against target proteins. Here, we have prepared a protein kinase-focused library by chemically modifying helix-loop-helix (HLH) peptides displayed on phage and subsequently tethered to adenosine. The library was screened against aurora kinase A (AurA). The selected HLH peptide Bip - 3 retained the α-helical structure and bound to AurA with a K_D value of 13.7 μM. Bip - 3 and the adenosine-tethered peptide Bip - 3 - Adc provided IC₅₀ values of 103 μM and 7.7 μM, respectively, suggesting that Bip - 3 - Adc bivalently inhibited AurA. In addition, the selectivity of Bip - 3 - Adc to several protein kinases was tested, and was highest against AurA. These results demonstrate that chemical modification can enable the construction of a kinase-focused library of phage-displayed HLH peptides.