Thermal intramolecular cycloaddition of 4-alkenylfulvene; highly regio- and diastereoselective formation of [4+2] adduct

4-Alkenylfulvenes were prepared by the annulation of 1,4-ynediones and allylidenetriphenylphosphorane and subjected to a thermal reaction. Highly regio- and stereoselective [4+2] cycloaddition is accomplished with 4-((R)-3-benzyloxypent-4-en-1-yl)fulvene and the resulting adduct is transformed into bicyclo[3.3.0]octene derivative.     

Chemical release control: Sulfonate esters from perfume and herbicide alcohols and p-styrenesulfonyl chloride

p-Styrenesulfonate esters of primary and secondary perfume alcohols and phenols, including citronellol, 1-menthol, borneol, β-phenethyl alcohol, eugenol, p-anisyl alcohol, cinnamyl alcohol, and geraniol, and herbicide alcohols such as 2,4-dichloro- and 2,4,5-trichlorophenoxy-ethanols were synthesized using p-styrenesulfonyl chloride in the presence of bases such as pyridine, triethylamine, sodium hydrogen carbonate, and sodium hydride. The hydrolytic behavior of sulfonate ester monomers and their copolymers with N-vinyl-2-pyrrolidone to liberate perfume and herbicide alcohols was structure-dependent, thereby affording chemical release control.     

Syntheses and reactions of porphyrin and metalloporphyrin polymers

Various porphyrin functions such as protoporphyrin IX and chlorin a as well as metalloporphyrin functions such as Mg(II)– and Cu(II)–chlorophyllin a and Fe(III)– and Co(II)–protoporphyrin IX were incorporated into vinyl polymers by preparation and polymerization of their p-vinylbenzyl esters. The porphyrin function was also incorporated by reaction of poly-p-chloromethylstyrene with porphyrins or metalloporphyrins or by the reaction of p-aminostyrene polymers with chlorophyll b through Schiff-base formation. Mg(II)–porphyrin polymers were found to be remarkably effective as catalysts in photoredox systems; porphyrin polymers without central metal atoms were also effective to a lesser extent.     

Preparation of cationic nanoparticles by the particle dissolution method from submicron-sized,styrene-butyl acrylate-dimethylaminoethyl methacrylate terpolymer particles

Cationic nanoparticles were prepared from submicron-sized styrene-butyl acrylate-dimethylaminoethyl methacrylate terpolymer (59.2/20.8/20.0, molar ratio) particles in a polyoxyethylene nonylphenylether nonionic emulsifier aqueous solution at pH 2.0 above 150 °C.     

Organic solid photochromism by photoreduction mechanism: Viologen embedded in solid polar aprotic polymer matrix

Reversible photocolor developments of viologens embedded in poly(N-vinyl-2-pyrrolidone) films, a typical polar aprotic solid matrix, were found to be affected by the kinds of viologen cation as well as the paired anion. The color developments in the corresponding low-molecular-weight solvents are connected closely to the solubility of viologens in these solvents; viologens are highly sensitive in the polar aprotic solvents in which they have poor solubilities, such as N-methyl-2-pyrrolidone and hexamethyl phosphoric triamide. These facts confirm the color-development mechanism consistings of electron transfer to the photoexcited viologen cation from the paired anion in polar aprotic solid matrices such as poly(N-vinyl-2-pyrrolidone).     

Reduction behavior of Ru/CeO2 catalysts and their activity for wet oxidation

Three kinds of Ru/CeO₂ catalysts were prepared. The mobility of the oxygen on Ru and their catalytic activity in the wet oxidation of acetic acid was investigated. Ru was present in the form of RuO₂, and TPR experiment showed that the reaction, RuO₂ + 2H₂ Ru + 2H₂O, took place in different temperature ranges depending upon the kind of the catalysts. The catalyst with easily reducible oxygen on Ru had high activity in wet oxidation, and the importance of the release of oxygen from Ru to the reactant was suggested.     

Monolithic silica column for in-tube solid-phase microextraction coupled to high-performance liquid chromatography

In-tube solid-phase microextraction (SPME) has successfully been coupled to capillary LC, and further an automated in-tube SPME system has been developed using a commercially available HPLC auto-sampler. However, an open tubular capillary column with a thick film of polymer (stationary phase) is unfavorable because the ratio of the surface area of coating layer contacted with sample solution to the volume of the capillary column is insufficient for mass transfer. A highly efficient SPME column is. therefore, required. We introduced a C18-bonded monolithic capillary column that was used for in-tube SPME. The column consisted of continuous porous silica having a double-pore structure. Both the through-pore and the meso-pore were optimized for in-tube SPME, and the optimized capillary column was connected to an HPLC injection valve for characterization. The results demonstrated that the pre-concentration efficiency is excellent compared with the conventional in-tube SPME. The novel method for both introduction and concentration of the samples was effective. satisfactory and suitable for use in the SPME medium.     

Preparation and characterization of highly dispersed V2O5/SiO2prepared by a CVD method

Highly dispersed V₂O₅/SiO₂(CVD catalyst) was prepared by the reaction of vaporized VO(OPrⁱ)₃ with silica at 293 K, whose process was followed by an IR technique. The rate of propylene photooxidation increased with an increase in V₂O₅ loading for CVD catalysts, but leveled off for impregnated ones. The CVD catalysts were characterized by XAFS and photoluminescence spectroscopy.