Oxidative Cycloaddition of Aldoximes with Maleimides using Catalytic Hydroxy(aryl)iodonium Species

A mild catalytic procedure for the efficient oxidative cyclization of aldoximes with maleimides mediated by hypervalent iodine(III) active species has been developed. This catalytic cyclization affords the corresponding pyrrolo‐isoxazole products in generally good yields. The catalytic cycle involves active hydroxy(aryl)iodonium species generated in situ from 2‐iodobenzoic acid as precatalyst and m‐chloroperoxybenzoic acid (m‐CPBA) as terminal oxidant in the presence of trifluoromethanesulfonic acid. The presence of active hydroxy(aryl)iodonium species in this reaction has been confirmed by ESI‐mass spectrometry and ¹H NMR spectroscopy.

     

Automatic two- and three-dimensional mesh generation based on fuzzy knowledge processing

This paper describes the development of a novel automatic FEM mesh generation algorithm based on the fuzzy knowledge processing technique.A number of local nodal patterns are stored in a nodal pattern database of the mesh generation system. These nodal patterns are determined a priori based on certain theories or past experience of experts of FEM analyses. For example, such human experts can determine certain nodal patterns suitable for stress concentration analyses of cracks, corners, holes and so on. Each nodal pattern possesses a membership function and a procedure of node placement according to this function. In the cases of the nodal patterns for stress concentration regions, the membership function which is utilized in the fuzzy knowledge processing has two meanings, i.e. the closeness of nodal location to each stress concentration field as well as nodal density. This is attributed to the fact that a denser nodal pattern is required near a stress concentration field. What a user has to do in a practical mesh generation process are to choose several local nodal patterns properly and to designate the maximum nodal density of each pattern. After those simple operations by the user, the system places the chosen nodal patterns automatically in an analysis domain and on its boundary, and connects them smoothly by the fuzzy knowledge processing technique. Then triangular or tetrahedral elements are generated by means of the advancing front method. The key issue of the present algorithm is an easy control of complex two- or three-dimensional nodal density distribution by means of the fuzzy knowledge processing technique.To demonstrate fundamental performances of the present algorithm, a prototype system was constructed with one of object-oriented languages, Smalltalk-80 on a 32-bit microcomputer, Macintosh II. The mesh generation of several two- and three-dimensional domains with cracks, holes and junctions was presented as examples.     

The influence of crystalline morphology on the growth of watertrees in PE

A small amount of phenolphthalein, acting as a nucleating agent, was added to low density polyethylene (LDPE) to modify the size and number of spherulites. The crystalline morphology was observed and analyzed with the aid of a chemical etching method. It was found that the growth of water trees is faster in LDPE samples in which spherulites are larger and the number of the spherulites is lower. In contrast, water trees grow more slowly in other LDPE samples in which spherulites are smaller in size and greater in number. On the other hand, three different kinds of additives, weak electrolyte and hydrophilic or hydrophobic substances, were added to the LDPE materials to investigate the influence of typical spherulite boundary regions on the growth of water trees. It was verified experimentally that during the process of crystallization, these three different additives are rejected and finally settled near the spherulite boundaries. Therefore, three kinds of boundary regions with different characteristics are formed. It has been concluded that hydrophillic boundary regions can strongly inhibit the growth of water trees, while the other two boundary regions (weak electrolyte, hydrophobic) have little influence on the water tree growth     

Thermomechanical heat of deformation studies on cis-polybutadiene

Thermomechanical heat of torsional deformation measurements have been made on crosslinked cis-polybutadiene by means of a Calvet microcalorimeter operated at 30°C. When corrected for volume changes utilizing the Gaussian statistical theory of elasticity, the data gave a value for the relative energy contribution to the torsional couple, $\text{M}{}_{\mathrm{e}}\text{M}$, of 0.14 ± 0.02. Measurements were also made on a sample subjected to simple tensile deformations. The relative energy contribution to the tensile force ($\text{f}{}_{\mathrm{e}}\text{f}$) was found to agree within experimental error with the value obtained for $\text{M}{}_{\mathrm{e}}\text{M}$, and the two results gave an average value for din $\text{〈r}{}^2{}_0\text{〉}\text{d}\text{T}$ of 4.1 × 10^?4 K^?1.     

Surface active N-acylglutamate: I. Preparation of long chain N-acylglutamic acid

Long chain N-acylglutamic acid was prepared in a high yield by a reaction of glutamic acid with fatty acid chloride in a mixed solvent of water and a water miscible organic solvent such as acetone, methyl ethyl ketone, dioxane, tetrahydrofuran,t-butyl alcohol or cyclohexanone. In this reaction the composition of the mixed solvent influenced the yield of N-acylated glutamic acid and the best yield was obtained when the reaction was carried out in the mixed solvent comprising 30–60% v/v of the organic solvent. Long chain N-acylaspartic acid was also obtained in a high yield by the same method. As the other method to obtain N-lauroyl-D L-glutamic acid, it was examined that N-acyl-α-aminoglutarodinitrile which was obtained by a reaction of α-aminoglutarodinitrile with fatty acid chloride was hydrolyzed with an aqueous alkaline solution. The salts of long chain N-acylglutamic acid are known as the surface active agents that react mildly on the human skin.     

Migration of 4-nonylphenol from polyvinyl chloride food packaging films into food simulants and foods.

Migration of 4-nonylphenol (NP) from polyvinyl chloride (PVC) films for food packaging into food simulants and foods has been studied in domestic applications such as wrapping of food and reheating in a microwave oven. The migration of NP from the PVC films was determined by high-performance liquid chromatography with electrochemical coulometric-array detection (LC/ED). Twelve PVC films intended for commercial use and ten for domestic applications (total: 22 samples) were analysed. Some of the PVC films (two home-use and ten retail-use) contained NP at concentrations of between 500 and 3300 microg/g. Migration of NP from the films was influenced by the test conditions (n-heptane at 25 degrees C for 60 min, distilled water at 60 degrees C for 30 min and 4% acetic acid at 60 degrees C for 30 min). The amount of NP migrating from the PVC films into n-heptane (0.33-1.6 microg/cm2) was higher than the amount migrating into distilled water or 4% acetic acid (up to 9.7 ng/cm2) for the 11 films in which NP was detected. Up to 0.23% of the NP migrated into distilled water and 4% acetic acid and up to 62.5% into n-heptane. In addition, we investigated NP migration into cooked rice samples wrapped in PVC film. Using spiked samples the method gave an average recovery of 83.7% (n = 5) with a standard deviation of 2.5%. Migration of NP ranged from not detectable (< 1.0 ng/g) to 410.0 ng/g by reheating samples in a microwave oven for 1 min and from not detectable to 76.5 ng/g by keeping samples at room temperature for 30 min.     

Self-organized lightwave network based on waveguide films for three-dimensional optical wiring within boxes

This paper presents core technologies for a self-organized microoptical system (SELMOS) within optoelectronic computers; mass-productive fabrication processes of waveguide films and new types of self-organized lightwave networks (SOLNETs) for three-dimensional (3-D) optical wiring with optical Z-connections. Waveguide films are fabricated by the built-in mask method, which is reusable and can construct surface-normal mirrors/filters at one time within photolithographic accuracy. Beveled core edge walls are made by the tilted ultraviolet (UV) exposure through the built-in mask using a photodefinable material. Near- and far-field patterns reveal that the walls act as micromirrors for optical Z-connections. SOLNET is a network consisting of self-organized coupling waveguides between misaligned optical devices. The self-organization is generated in a photorefractive material by self-focusing of the two write beams from the two devices. Direct SOLNET, where wavelengths of the write beam and the signal beam are the same, is demonstrated using a laser diode. Reflective SOLNET, where one of the two write beams is replaced with a reflected write beam from the edge of the coupled device, realizes two-beam-writing SOLNET in a one-beam-writing configuration. It is especially effective when the coupled device cannot transmit write beams. The proof-of-concept is demonstrated both theoretically and experimentally. These results indicate a possibility to form 3-D optical wiring simply in SELMOS.     

Low-loss polymeric optical waveguides fabricated with deuteratedpolyfluoromethacrylate

Deuterated polyfluoromethacrylate which has high transparency, low birefringence and good processability was newly synthesized for use as optical waveguide materials, and both single-mode and multimode optical waveguides were fabricated using the polymer. The propagation loss and waveguide birefringence of the single-mode waveguides were as low as 0.10 dB/cm and -5.5×10^-6 at 1.31 μm, respectively. The propagation losses of the multimode waveguides were less than 0.02 dB/cm at both 0.68 and 0.83 μm, and 0.07 dB/cm at 1.31 μm     

Solar energy transmittance of translucent samples: A comparison between large and small integrating sphere measurements

Optical transmittance and reflectance of a translucent plastic PTFE film have been measured over the solar wavelength range using different integrating spheres. The same sample has been measured with small and large spheres and the total solar transmittance has been obtained from both broad band measurements and from integration of spectral data. The fact that the sum of reflectance and transmittance often exceeds 100% shows that all types of spheres tend to overestimate the transmittance of this highly scattering sample. This error can be attributed to the sphere geometry in combination with the light scattering properties of the sample, and unless proper correction of recorded data is carried out the error may be as large as 5–10%. Some specific errors are presented and an approximate correction procedure is suggested.These results show that there is a need for a transmittance standard which can be used to calibrate integrating spheres. Such a standard with negligible thickness would be especially useful for measurements with large, broadband integrating spheres, but would also be helpful for the correct handling of data from small spectral instruments.