Synthesis of end‐functionalized poly(N‐isopropyl acrylamide) with zinc porphyrin and its photocatalytic activity under visible light

A series of well‐defined linear poly(N‐isopropyl acrylamide) with an asymmetrical zinc(II) porphyrin (ZnPor–PAM) end group was synthesized by atom transfer radical polymerization, wherein 5,10,15,20‐tetra(p‐bromopropanoyloxyethylphenyl) zinc porphyrin tripropionate was used as the initiator and CuBr/tris(2‐dimeoethyl)amine was used as the catalyst system. The structure of the ZnPor–PAM was characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. In addition, the polydispersity index (PDI) obtained by gel permeation chromatography indicated that the molecular weight distribution was narrow; thus, the polymerization was well controlled (1.05 < PDI < 1.21). Because of the incorporation of hydrophobic porphyrin, the lower critical solution temperature of ZnPor–PAM was lower than that of the N‐isopropyl acrylamide homopolymer. Most interestingly, the ZnPor–PAM possessed remarkable photocatalytic activity for the oxidative degradation of methylene blue in the presence of hydrogen peroxide under visible‐light radiation. Moreover, ZnPor–PAM could be reused through the uncomplicated procedure, which exploited the thermoresponsive properties of ZnPor–PAM without any significant loss in activity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40523.     

Reliability-based design for earth-fill dams against severe natural disaster events

The maintenance of geotechnical structures, such as earth-fill dams, is required as a countermeasure against severe natural disasters, particularly earthquakes and heavy rains. The reliability-based analysis introduced here is in response to the recent demand for low-cost improvements.First, a statistical model of N values was determined from Swedish weight sounding (SWS) tests to present the spatial variability of the soil strength. Then, a reliability-based analysis of embankments was conducted by considering the variability of the internal friction angle derived from N value, and the seismic hazard for the Nankai Trough. The next step was to evaluate the probability of the overflow of earth-fills during heavy rains. The rainfall intensity was considered as a probabilistic parameter, and the various rainfall patterns were tested by the proposed method. Finally, the total risk due to both earthquakes and heavy rains was evaluated for an earth-fill site. As a result, the possibility for the practical use of the proposed method in making plans for the maintenance of deteriorated earth-fill dams was verified.     

Structural effect of a series of block copolymers consisting of poly(N-isopropylacrylamide) and poly(N-hydroxyethylacrylamide) on thermoresponsive behavior

Well-defined diblock and triblock copolymers consisting of poly(N-isopropylacrylamide) (PNIPAM) and poly(N-hydroxyethylacrylamide) (PHEAA) were prepared using the atom transfer radical polymerization (ATRP) method. The number-average molecular weight and fraction of each segment were precisely controllable by adjusting the monomer/initiator ratio in feed. The lower critical solution temperature (LCST) of a series of block copolymers with different compositions was examined using a turbidimetry analysis. The copolymers with a relatively lower molar fraction of HEAA units in the polymer chain exhibited phase transition phenomenon, in which the LCST depended on the fraction in the copolymer. On the other hand, the LCST disappeared for the copolymers with higher HEAA unit molar fractions. The ¹H NMR measurement clarified that the disappearance of the LCST was attributed to the formation of the water-soluble micelle. Furthermore, the thermoresponsive property of the series of block copolymers was elucidated on the basis of the structural effect of the copolymer, which includes the order and length of the block segments.     

An increased ratio of interleukin-1 receptor antagonist to interleukin-1alpha in inflammatory skin diseases

IL-1 receptor antagonist (IL-1ra) is a cytokine that competitively binds the IL-1 receptor to antagonize IL-1 activity without any agonist function. Previous experiments indicated that the ratio of IL-1ra to IL-1alpha in the normal stratum corneum (SC) was much higher in the sun-exposed face than in the sun-protected area, upper arms. It was also reported by another laboratory that IL-1ra is increased in the lesional skin of psoriatic patients. This study was designed to measure the contents of IL-1alpha and IL-1ra in non-lesional and pathological SC obtained from inflammatory skin diseases including psoriasis and non-psoriatic dermatoses such as atopic dermatitis. The SC materials were obtained with a non-invasive tape-stripping method. Their soluble fractions were prepared and assayed for IL-1alpha and IL-1ra by enzyme-linked immunosorbent assays. As a result we confirmed the previous findings that the ratio of IL-1ra to IL-1alpha in the normal SC was much higher in the face than in the sun-protected sites, the trunk as well as extremities. Next, we found that IL-1alpha contents were significantly reduced in the SC samples obtained from inflammatory skin regardless of whether their IL-1ra contents increased or unchanged. Moreover, we noted that an increased ratio of IL-1ra to IL-1alpha in the SC was not specific to psoriasis, but was also found in other inflammatory skin diseases including atopic dermatitis. This ratio was found to become lower after successful treatment of these skin lesions with topical glucocorticoids. We conclude from these observations that the increased ratio of IL-1ra to IL-1alpha in the SC is a non-specific phenomenon that can occur in any inflammatory skin diseases regardless of the inflammatory pattern, probably reflecting a skin regulation process against various kinds of inflammation.     

Atrazine sensor based on molecularly imprinted polymer-modified gold electrode

Molecularly imprinted polymers (MIP) have been elucidated to work as artificial receptors. In our present study, a MIP was applied as a molecular recognition element to a chemical sensor. We have constructed an atrazine sensor based on a MIP layer selective for atrazine and its electrochemical reduction on gold electrode. The atrazine sensor was fabricated by directly polymerizing the atrazine-imprinted polymer composed from methacrylic acid and ethylene glycol dimethacrylate onto the surface of a gold electrode. By introducing LiCl into the MIP, atrazine was reduced below -800 mV vs Ag/AgCl reference electrode, at pH 3. The cathodic current of atrazine depended on the concentration of atrazine at the range of 1-10 microM. The sensor exhibited a selective response to atrazine. A nonimprinted polymer-modified electrode did not show selective response to atrazine, thus implying that the imprinted polymer acts as recognition element of atrazine sensor.     

Damage to and recovery of coastlines polluted with C-heavy oil spilled from the Nakhodka

The damage to and recovery of the Japanese coastline from Suzu, Ishikawa Prefecture to Mikuni, Fukui Prefecture was investigated visually over three years after a C-heavy oil spill from the Russian tanker "Nakhodka" in the Japan Sea on January 2, 1997. The beached C-heavy oil tended to remain for a long time on coasts of bedrock and boulder/cobble/pebble but it was removed rapidly from coasts of gravel/sand and man-made structures such as concrete tetrapods. On the coasts of the latter type, wave energy appeared to be the main force removing the oil. One year after the spill, C-heavy oil tended to remain strongly on the sheltered coasts of bedrock and boulder/cobble/pebble. Even on coasts of this type, the contamination was remarkably absent by 2 years after the spill. The concentration levels of polycyclic aromatic hydrocarbons (PAHs) in oil lumps, sand and seawater were monitored during 3 years following the spill. The concentrations of PAHs having 2 or 3 rings decreased more quickly than did those of PAHs having 4 or more rings, suggesting that volatilization was the main cause of the decrease. On the other hand, the concentrations of PAHs having 4 to 6 rings did not start to decrease until 7 months after the spill. The main cause of the decrease seemed to be photolysis. The concentration of BaP in seawater off the polluted coasts was high 1 month after the spill and then decreased. Three years after the spill, the level fell to the sub ng/L level, which was as low as the level in seawater along unpolluted clean coasts in Japan. The concentration of BaP in greenling was higher than the normal level only during the first two months after the spill. These results suggest that the coastlines in Ishikawa and Fukui Prefectures that were polluted with C-heavy oil recovered in 3 years.     

Minute particle detection using a light-wave-guide incorporated optical total analysis system

An optical sensor combined total analysis system (TAS) is thought to be one of the most effective functional elements in realizing a ubiquitous human healthcare system. In accordance with this concept, we have proposed a fundamental structure of a light-wave-guide incorporated TAS and have developed a micro fluidic channel fabricated chip, where two light waveguides having approximately 10-??m cores were facing each other across a fluidic channel with a width of 12???m. By passing 5-??m-diameter polystyrene particles across the portion where a light-wave-guide and the fluidic channel intersect at a right angles, we confirmed that changes to transmitted light and scattered light were detectable even with an extremely low laser source power of 5???W, and they increased proportionally as the introduced laser power became higher. Increasing the introduced laser power clearly increased the correlation between the transmitted and scattered light change. Here we discuss in detail the two different correlation tendencies that appeared in the correlation maps.     

Illumination and scattered light detection using a light source consisting of sub-micrometer defect arrays formed on a extremely flat light waveguide core

We have previously argued that an optical sensor combined total analysis system (TAS) is one of the indispensable functional components needed to realize a “ubiquitous human healthcare” system. To achieve this goal, we have proposed a fundamental structure for illuminating a minute cell or particle running along a microfluidic channel using a flat waveguide construction. It is desirable that the TAS light source should be arranged as close to the specimen flow as possible in order to acquire the necessary optical properties; hence, artificial defects formed on the surface of a flat light waveguide are considered to be a promising candidate for realizing the arbitrary-shaped light source for a highly functional optical TAS structure. Based on this idea, we fabricated a structure, constructing a flat and square light source consisting of rectangular solids, sub-micrometer in size, with a 1-μm thick and a 12-μm wide light waveguide core. We successfully trial-manufactured an optical TAS chip with a fluidic channel containing a 14 × 10-μm cross section, and an extremely flat light waveguide core. We repeatedly confirmed that the defect array could function as an approximately square light source when a 650-nm wavelength laser power was carefully introduced. Furthermore, we developed a hybrid numerical calculation method base on the finite-difference, time-domain method together with the beam propagation method. Utilizing this hybrid method, we evaluated the optical response when a particle runs across the light source while changing the aperture length of a shading mask to obtain signals with both higher intensity and shorter full width at half maximum. The numerical results were compared with experimental results obtained using an image acquisition system, and demonstrated good qualitative accord.     

Flow regimes and vertical solids conveying in a spout‐fluid bed with a draft tube

Pressure fluctuation data were obtained in a semi‐cylindrical spout‐fluid bed with draft tube, and statistical analyses of them were employed to recognise flow regimes. Also, the effects of spouting‐gas and auxiliary‐gas velocities, and length of entrainment zone on solids loading ratio in a draft tube were examined. As a result, five flow regimes appeared by changing spouting‐gas and auxiliary‐gas velocities and it was found that the simplest method to determine flow regime is to measure pressure fluctuations in a draft tube. Moreover, solids loading ratio could be controlled flexibly by auxiliary‐gas velocity and length of entrainment zone.     

Formation of electroless barrier and seed layers in a high aspect ratio through-Si vias using Au nanoparticle catalyst for all-wet Cu filling technology

An all-wet process was achieved using electroless deposition of barrier and Cu seed layers for fabrication of a high aspect ratio through-Si via (TSV). Formation of a thin barrier metal layer of Ni–B, Co–B and Co–W–B is possible using a Au nanoparticle (AuNP) catalyst, which is densely adsorbed on the SiO₂ of the TSV sidewall. A silane coupling agent of 3-aminopropyl-triethoxysilane is effective for enhancement of the density of adsorption for AuNP. A conformal electroless Cu layer is deposited on the barrier layer by displacement plating without a catalyst. The adhesion strength between the electroless barrier layer and the SiO₂ substrate is increased by annealing at 300 °C. These results strongly suggest that an all-wet process for the formation of Cu-filled TSV with a high aspect ratio is practically possible.