Effect of adhesive thickness on the stringiness of crosslinked polyacrylic pressure‐sensitive adhesives

The effect of adhesive thickness on stringiness behavior during 90° peel testing was investigated for crosslinked poly(n‐butyl acrylate‐acrylic acid) (A) and poly(2‐ethylhexyl acrylate‐acrylic acid) (B) with a constant crosslinker content. The adhesive thickness was varied over the range from 15 to 60 μm. All adhesive thicknesses exhibited sawtooth‐type peeling with a front frame for B, but only the 30‐μm thickness generated a front frame‐type for A. The peel rate decreased from 15 to 45 μm and plateaued above 45 μm under a constant load test. These results indicate that the adhesion strength increases with adhesive thickness, but reaches a constant value at high thicknesses. The stringiness was also analysed for B and the sawtooth interval observed to increase with increasing thickness. This means the sawtooth number decreased. As a result, the concentrated stress per sawtooth induces easier peeling and so this factor tend to increase the peel rate. Conversely, the stringiness width increased with increasing thickness. The stress load over the stringiness region decreased with an increase in thickness, meaning that a decrease in the concentrated stress decreases the peel rate. The actual peel rate is influenced by the contributions of these two factors. The strain rates during constant peel rate tests decreased slightly with increasing thickness, due to a reduction in the apparent modulus. The molecular mobilities near the adherend and the backing surfaces were evidently restrained by these surfaces, and the relative rates of motion of such restrained molecules decrease with increased thickness. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42210.     

Deciphering Structural Alterations Associated with Activity Reductions of Genetic Polymorphisms in Cytochrome P450 2A6 Using Molecular Dynamics Simulations

Cytochrome P450 (CYP) 2A6 is a monooxygenase involved in the metabolism of various endogenous and exogenous chemicals, such as nicotine and therapeutic drugs. The genetic polymorphisms in CYP2A6 are a cause of individual variation in smoking behavior and drug toxicities. The enzymatic activities of the allelic variants of CYP2A6 were analyzed in previous studies. However, the three-dimensional structures of the mutants were not investigated, and the mechanisms underlying activity reduction remain unknown. In this study, to investigate the structural changes involved in the reduction in enzymatic activities, we performed molecular dynamics simulations for ten allelic mutants of CYP2A6. For the calculated wild type structure, no significant structural changes were observed in comparison with the experimental structure. On the other hand, the mutations affected the interaction with heme, substrates, and the redox partner. In CYP2A6.44, a structural change in the substrate access channel was also observed. Those structural effects could explain the alteration of enzymatic activity caused by the mutations. The results of simulations provide useful information regarding the relationship between genotype and phenotype.     

Synthesis of dioctyl sulfosuccinate-doped polypyrrole grains by aqueous chemical oxidative polymerization and their use as light-responsive liquid marble stabilizer

Polypyrrole grains are synthesized by aqueous chemical oxidative polymerization using ferric chloride as an oxidant in the presence of bis(2-ethylhexyl) sulfosuccinate sodium salt as both a dopant and a hydrophobizing agent. The resulting grain products are characterized in terms of their size, morphology, surface and bulk chemical compositions, hydrophilicity-hydrophobicity balance, (photo) thermal property, and electrical conductivity. Scanning electron microscopy studies indicate that the grains are aggregates of atypical primary grains with submicrometer size. Elemental microanalysis and thermogravimetric analysis confirm that the polypyrrole is preferably doped with dioctyl sulfosuccinate compared with chloride ion, and dioctyl sulfosuccinate/chloride ion dopant ratio increases with an increase of bis(2-ethylhexyl) sulfosuccinate sodium salt concentration in the polymerization systems. The grains show near-infrared light-to-heat photothermal property, which is confirmed by thermography. The data obtained through X-ray photoelectron spectroscopy indicate the presence of dioctyl sulfosuccinate dopants on the surface of the grains, and therefore the dried polypyrrole grains show hydrophobic character. The dried grains can work as a light-responsive liquid marble (LM) stabilizer. Motions of the LM can be driven by near-infrared laser irradiation-induced Marangoni flow on planar air-water surface. The release of internal liquid can be achieved by controlled disruption of the LM via external stimulus application.     

Cooling action of grinding fluid in shallow grinding

A new method is proposed for measuring the heat transfer coefficient in the vicinity of the wheel-workpiece contact zone. The accuracy of measurement is estimated by using a finite element method and the factor for correcting the measured results is derived. The experiments are performed in a number of conditions where grinding fluid is supplied and the following measures are consequently recommended for increasing the cooling efficiency: (1) set the velocity of coolant to more than the critical value to penetrate the air flow layer formed around the wheel periphery; (2) use a nozzle with a thin throat, about 1 mm in height, and attach a scraper plate above the nozzle outlet; (3) choose a wheel of large grain size and dress roughly, or form shallow grooves on the wheel periphery; and (4) set a higher wheel speed.     

Biochemical changes in phosphorus compounds and in the activity of phytase and α-amylase in the rice (Oryza sativa) grain during germination

Changes in the phytic acid, inorganic phosphorus and ATP contents, and in the activity of phytase and α-amylase in rice (Oryza sativa L) grains were determined during 18 days of germination in a dark room. The effect of phytic acid on α-amylase activity was studied in vitro. Rice grains immersed in sterilised deionised water at 14^°C germinated on the fifth day. Phytase activity, detected in the ripening rice grains, increased linearly until the eighth day and reached a maximum on the tenth day. There was a marked decrease in phytate and an increase in inorganic phosphorus accompanying germination. There was a good inverse correlation between the levels of both phytase activity and inorganic phosphorus, and phytate breakdown. α-Amylase activity was detected on the fourth day and increased markedly from the 12th to the 16th day of germination. ATP level increased from the second to the fourth day and slightly decreased from the fourth to the eighth day; it increased rapidly again from the eighth to the 18th day of germination. α-Amylase activity was influenced by both pH and phytic acid concentration in the assay system. At 75 mM phytic acid, α-amylase activity was lowered by 23%, 93% and 52% at pH 4–0, 5–0 and 6–0 respectively. When the enzyme, phytate and Ca²⁺ were incubated together at pH 5–0, the inhibition of α-amylase by phytic acid was markedly decreased by addition of Ca²⁺. The chemical affinity of Ca²⁺ for phytic acid was higher in the reaction at pH 5–0 than in those at pH 4–0 and pH 6–0, and over 98% of Ca²⁺ in the reaction system was precipitated as Ca-phytate.     

Function of second glucan binding site including tyrosines 54 and 101 in Thermus aquaticus amylomaltase

Amylomaltase from Thermus aquaticus catalyzes three types of transglycosylation reaction, as well as a weak hydrolytic reaction of alpha-1,4 glucan. From our previous study [Fujii et al., Appl. Environ. Microbiol., 71, 5823-5827 (2005)], tyrosine 54 (Y54) was identified as an amino acid controlling the reaction specificity of this enzyme. Since Y54 is not located around the active site but in the proposed second glucan binding site that is 14 A away from catalytic residues, the functions of Y54 and the second glucan binding site are of great interest. In this study, we introduced mutations into another tyrosine (Y101) in the second glucan binding site. The obtained mutated enzymes were subjected to all four types of enzyme assay and the effects of mutations on the reaction specificities of these enzymes were comprehensively investigated. These studies indicated that the amino acid substitution at Y54 or Y101 for removing their aromatic side chain increases cyclization activity (intra-molecular transglycosylation reaction) but decreases disproportionation, coupling and hydrolytic activities (inter-molecular reactions). The superimposition of the reported structures of the enzyme with and without substrate analog revealed the occurrence of a conformational change in which a donor binding site becomes open. From lines of evidence, we conclude that the binding of glucan substrate to the second glucan binding site through an interaction with the aromatic side chains of Y54 and Y101 is a trigger for the enzyme to take a completely active conformation for all four types of activity, but prevents the cyclization reaction to occur since the flexibility of the glucan is restricted by such binding.     

Photoluminescence of Cerium-Doped α-SiAlON Materials

Cerium-doped α-SiAlON (M _x Si_{12−( m + n )}Al _{m + n} O _n N_{16– n} ) materials have been prepared by gas-pressure sintering and post-hot-isostatic-press (HIP) annealing, using four powder mixtures of α-Si₃N₄, AlN, and either (i) CeO₂, (ii) CeO₂+ Y-α-SiAlON seed, (iii) CeO₂+ Y₂O₃, or (iv) CeO₂+ CaO. Cerium-containing CeAl(Si_{6– z} Al _z )(N_{10– z} O _z ) (JEM) phase, rather than Ce-α-SiAlON phase, forms in the sample with only CeO₂, whereas a single-phase α-SiAlON generates in samples with dual doping (CeO₂+ Y₂O₃ and CeO₂+ CaO). On ultraviolet-light excitation, JEM gives one broad emission band with maximum at 465 nm and a shoulder at 498 nm; α-SiAlON shows an intense and broad emission band that peaks at 500 nm. The unusual long-wavelength emissions in JEM and α-SiAlON are due to increases in the nephelauxetic effect and the ligand-field splitting of the 5 d band, because the coordination of Ce³⁺ in JEM and α-SiAlON is nitrogen enriched.     

Effect of Sintering Additives on Superplastic Deformation of Nano-Sized β-Silicon Nitride Ceramics

The effect of sintering additives on superplastic deformation of nano-sized β-Si₃N₄ ceramics has been studied by compression tests at 1500°C. The sintering additives were (i) Y₂O₃+Al₂O₃; (ii) Y₂O₃+MgO; and (iii) Y₂O₃. Nano-sized Si₃N₄ ceramics with different sintering additives had similar microstructures. For the first two sintering additives, the stress exponents were determined to be ∼2 at a lower stress region and ∼1 at a higher stress region, where the strain rate was dependent on sintering additives only at the higher stress region, and was independent at the lower stress region. Nano-ceramics with Y₂O₃ additives had only one region, which had a stress exponent of ∼1 within the stress range that we studied. The results could be explained by the different deformation mechanisms at the higher and lower stress regions and the influence of viscosity of liquid phase on the transition stress.     

A translucent display algorithm for G-octree represented grey-scale images

A new translucent display algorithm is proposed for grey-scale images represented by G-octrees. The algorithm generates a special triangle quadtree as the display image for the isometric projection of a G-octree, while traversing the G-octree from front to back, with respect to the viewpoint. A method of using the translucent effect to analyse the interiors of three-dimensional objects is also described, together with its implementation results.