Crosslinked acrylic pressure‐sensitive adhesives. II. Effect of humidity on the crosslinking reaction

The effect of humidity during storage on the crosslinking reactions of isocyanate groups was investigated with attenuated total reflectance Fourier transform infrared spectroscopy with pressure‐sensitive adhesives composed of poly[ethyl acrylate‐co‐(2‐ethylhexyl acrylate)‐co‐(2‐hydroxyethyl methacrylate)] as a base resin and polyisocyanate as a crosslinker. A peak‐resolving analysis of the amide II region revealed four bands. According to an analysis of the Fourier transform infrared spectra of the model compounds, these four bands were assigned to free urethane linkages, hydrogen‐bonded urethane linkages, free urea linkages, and hydrogen‐bonded urea linkages. As expected, storage under humid conditions led to the formation of free and hydrogen‐bonded urea linkages corresponding to the promotion of isocyanate consumption. Peak resolution of the amide II region was found to be a reasonable way of monitoring urethane and urea linkages during crosslinking reactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3039–3045, 2003     

ASYMPTOTIC PROPERTIES OF THE SAMPLE AUTOCORRELATIONS AND PARTIAL AUTOCORRELATIONS OF A MULTIPLICATIVE ARIMA PROCESS

Abstract. We shall investigate the asymptotic behaviour of the sample autocorrelations and partial autocorrelations of a multiplicative ARIMA process and derive their limiting distributions. Some simulations are presented to illustrate the results obtained.     

Photoresponsive peptide and polypeptide systems: part II. Photochromism of poly(l-ornithine) containing various azo-contents in side chains

Poly(L-ornithine)s having various azo-contents in the side chains were synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the polypeptides poly[N^δ-p-(phenylazo)benzoyl-L-ornithine] (PPABLO) containing 3–77 mol% azobenzene were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP) or water, and in HFIP-water or methanol-water solvent mixtures. The photochromism of the dichroic bands of the PPABLOs containing 20–77 mol% azobenzene in the visible and ultraviolet wavelength regions was found to be mostly reversible as a function of irradiation time at different wavelengths due to the photostationary state (above 80% trans-cis photoisomerization) of the azo aromatic moieties. The PPABLO containing 3.2 mol% azobenzene in water exhibited conformational changes from random coil to helix by the addition of methanol or sodium dodecyl sulphate (SDS). The photo-induced conformational change was observed in HFIP-water-SDS solvent mixtures, while no conformational change was seen in water and HFIP-water solvent mixtures.     

Formation of Small-Sized CdSxSe1-x Crystals in Sol-Gel-Derived SiO2 Glasses

Silica glasses doped with small-sized CdS_x-Se_1-x crystals were prepared by the sol-gel method. Gels synthesized by the hydrolysis of Si(OC₂H₅)₄, in the presence of CdSeO₄ with NH₄SCN dissolved in HNO₃ or NH₄OH, were heated in H₂-N₂ atmosphere. The pH value of solutions for CdSeO⁴ and NH⁴SCN primarily determined the fraction of anions in CdS^xSe^1-x crystals. The anion content in crystals was dependent on the pH value of the solvent and/or heat-treatment temperature, and the sulfur fraction changed from 0.1 to 0.6. The optical absorption spectra were red-shifted as the selenium content and the crystal size increased, and the emission spectra showed a sharp band near the absorption edge position and a broad tail extending into the long wavelength. The optical band gap energies increased reciprocally proportional to the square of the crystal size.     

Increased hepatic β-oxidation of docosahexaenoic acid, elongation of eicosapentaenoic acid, and acylation of lysophosphatidate in rats fed a docosahexaenoic acid-enriched diet

Rats were fed a diet supplemented with corn oil (n-3 deficient), soy oil, or a mixture containing 8% 22∶6n-3 ethyl ester for 6 wk. The hepatic capacities for the β-oxidation and synthesis of 22∶6n-3, in addition to the acylation of lysophosphatidate, were tested in vitro. In rats that were fed a 22∶6n-3-enriched diet, both the β-oxidation of 22∶6n-3 and elongation of 20∶5n-3 were enhanced compared to those in rats fed the other diets. Acylation of lysophosphatidate was also enhanced in rats fed a 22∶6n-3-enriched diet, while the rate of dephosphorylation of phosphatidate was not changed. The amount of 22∶6n-3 in the liver was much less than that consumed in a docosahexaenoic acid-enriched diet. These results suggest that a significant amount of dietary 22∶6n-3 was degraded via β-oxidation, and that a portion of the retroconverted 20∶5n-3 was recycled for the synthesis of 22∶6n-3. The recycling of 20∶5n-3 might contribute to the low level of 22∶6n-3 in rats fed an n-3-deficient diet.     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

LC GRIN lens mode with wide viewing angle for rotatable 2D/3D tablet

To widen the vertical and horizontal angular ranges where the lens performs well, the off‐axis performance of a liquid crystal gradient index (LC GRIN) lens is analyzed by the combined simulation system of an LC director simulator and a ray‐tracing simulator. We found that the angular difference between an LC alignment direction and an electrode array direction of the LC GRIN lens is one of significant parameters, and detailed conditions of structure are established. The measurement result shows that the developed structure reduces the degradation ratio in a luminance profile from 61% to 3.2%. We have applied a user tracking system for the rotatable 3D display, equipped with a detection of a panel orientation and a face position. As a result, we have developed a rotatable 2D/3D tablet whose 3D viewing azimuth angle is over 30° in both landscape and portrait orientations.     

Radical polymerization of butyl acrylate and random copolymerization of styrene and butyl acrylate and styrene and methyl methacrylate mediated by monospiro- and dispiropiperidinyl-N-oxyl radicals

Radical polymerization of butyl acrylate (BA) and random copolymerizations of styrene (St) and BA and St and methyl methacrylate (MMA) in the presence of 7-aza-15-hydroxydispiro[5.1.5.3]hexadecane-7-yloxyl (1) and 1-aza-2,2-dimethyl-4-hydroxyspiro[5.6]dodecane-1-yloxyl (2) were carried out. Radical polymerization of BA at 120 °C in the presence of 1 gave poly(BA) with M_n=20200 and M_w/M_n=1.30 at 23% conversion. The termination of polymerization observed around ∼20% conversion was solved to a certain extent by an addition of small amounts of dicumyl peroxide, and poly(BA) with M_n=37400 and M_w/M_n=1.33 was obtained in 46% yield. Random copolymerizations of St and BA and St and MMA in the presence of 1 and 2 at 80 °C gave the corresponding random copolymers with narrow polydispersities of 1.12-1.38 at the molar fraction above 0.30 of St in feed. The kinetic study for the NO-C bond homolysis of the corresponding alkoxyamines prepared from 1 and 2 were carried out, and evaluation of the preexponential factors (A_act) and the activation parameters (E_act) showed that the steric factors of the nitroxides are reflected mainly on E_act.     

Bright-field scanning confocal electron microscopy using a double aberration-corrected transmission electron microscope

Scanning confocal electron microscopy (SCEM) offers a mechanism for three-dimensional imaging of materials, which makes use of the reduced depth of field in an aberration-corrected transmission electron microscope. The simplest configuration of SCEM is the bright-field mode. In this paper we present experimental data and simulations showing the form of bright-field SCEM images. We show that the depth dependence of the three-dimensional image can be explained in terms of two-dimensional images formed in the detector plane. For a crystalline sample, this so-called probe image is shown to be similar to a conventional diffraction pattern. Experimental results and simulations show how the diffracted probes in this image are elongated in thicker crystals and the use of this elongation to estimate sample thickness is explored.     

Fine two-phase routing over shortest paths with traffic matrix

This paper presents an IP finely-distributed load-balanced routing scheme based on two-phase routing over shortest paths, where the traffic matrix is given. It is called the fine two-phase routing (F-TPR) scheme. F-TPR more finely distributes traffic from a source node to intermediate nodes than the original TPR. F-TPR determines the distribution ratios to intermediate nodes for each source–destination node pair independently. To determine an optimum set of distribution ratios, a linear programming (LP) formulation is derived. We compare the F-TPR scheme against the TPR scheme and the sophisticated traffic engineering (TE) scheme of Multi-Protocol Label Switching (MPLS-TE). Numerical results show that F-TPR greatly reduces the network congestion ratio compared to TPR. In addition, F-TPR provides almost the same network congestion ratios as MPLS-TE, the difference is surprisingly less than 0.1% for the various network topologies examined. In addition, considering the practical implementation of F-TPR for routers, we also investigate the case that traffic from a source node to a destination node is not allowed to be split over multiple routes. The non-split problem is formulated as an integer linear programming (ILP) problem. As it is difficult to solve the ILP problem within practical time, two heuristic algorithms are presented: Largest Traffic Demand First (LTDF) and a Random Selection (RS). The applicability of LTDF and RS are presented in terms of network size. We find that non-split F-TPR also matches the routing performance of MPLS-TE within an error of 1%, when network size is large enough.