Syntheses of polymerizable dyes and their graft copolymerization to cellulose and polypropylene fibers

Various methacrylic ester derivatives were synthesized from glycidyl methacrylate and aromatic amines or phenol. The homopolymerization and graft copolymerization of these compounds were carried out using azobisisobutyronitrile. These methacrylic derivatives reacted with diazonium salts to give azo compounds which have a double bond. These vinyl azo compounds gave homopolymer and graft copolymer with cellulose or polypropylene fibers.     

Solvent effect on radical polymerization of butyl acrylate

The propagation and termination rate constants k_p and k_t for the radical polymerization of butyl acrylate initiated by biacetyl have been measured by using the rotating-sector method, in various solvents at 30°C. The value of k_p and initiation rate R_i varied with solvents, while the value of k_t did not change with solvents except for benzonitrile. The variation of k_p with aromatic solvents has a trend against Hammett σ_p of the solvent substituents similar to that for methyl methacrylate or phenyl methacrylate except for the value in benzonitrile, when it is larger than the variation for methyl methacrylate or phenyl methacrylate. The larger variation of k_p for butyl acrylate is compatible with the view that the origin of the solvent effect lies in complex formation between the propagating radical and aromatic solvent molecules. The exceptional decrease in k_p and k_t in benzonitrile is explained by a contraction of the poly(butyl acrylate) chain in the poor solvent.     

Medicinal foodstuffs. XXV. Hepatoprotective principle and structures of ionone glucoside, phenethyl glycoside, and flavonol oligoglycosides from young seedpods of garden peas, Pisum sativum L

A new ionone glucoside, pisumionoside, a phenethyl glycoside, sayaendoside, and two acylated flavonol oligoglycosides, pisumflavonosides I and II, were isolated from the young seedpods of garden peas, Pisum sativum L., together with quercetin and kaempferol 3-O-(6-O-trans-p-coumaroyl)-beta-D-glucopyranosyl (1-->2)-beta-D-glucopyranosyl (1-->2)-beta-D-glucopyranosides and quercetin and kaempferol 3-sophorotriosides. The structures of pisumionoside, sayaendoside, and pisumflavonosides I and II were determined on the basis of chemical and physicochemical evidence, respectively. Quercetin 3-sophorotrioside, a principle component, was found to show protective effects on liver injury induced by D-galactosamine and lipopolysaccharide and by carbon tetrachloride in mice.     

Novel dolabellane-type diterpene alkaloids with lipid metabolism promoting activities from the seeds of Nigella sativa

[structure: see text] Four new dolabellane-type diterpene alkaloids, nigellamines A(1) (1), A(2) (2), B(1) (3), and B(2) (4), were isolated from the seeds of Nigella sativa. Their absolute stereostructures were determined on the basis of chemical and physicochemical evidence. Nigellamines A(1) (1), B(1) (3), and B(2) (4) were found to show potent lipid metabolism promoting activity in primary cultured mouse hepatocytes, and their activities were equivalent to that of a PPAR-alpha agonist, clofibrate.     

Biodegradation of poly(lactic acid) powders proposed as the reference test materials for the international standard of biodegradation evaluation methods

The methods for producing reference test materials for biodegradation evaluation tests have been studied. Mechanical crushing at low temperature of polymer pellets using dry ice was selected for the method of producing polymer powder of poly(lactic acid) (PLA). The powders were fractionated using 60 mesh (250 μm) and 120 mesh (125 μm) sieves. The size distributions were then measured. The average diameter of the PLA particles obtained by this method was 214.2 μm. The biodegradation speeds of these PLA polymer powders were evaluated by two methods based on the international standard and one in vitro method based on the enzymatic degradation. First, the degree of biodegradation for this PLA powder was 91% for 35 days in a controlled compost determined by a method based on ISO 14855-1 (JIS K6953) at 58 °C managed by the Mitsui Chemical Analysis and Consulting Service, Inc. (Japan). Second, these polymer powders were measured for biodegradation by the Microbial Oxidative Degradation Analyzer (MODA) in a controlled compost at 58 °C and 70 °C based on ISO/DIS 14855-2 under many conditions. The degree of biodegradation for this PLA powder was approximately 80% for 50 days. In addition, the polymer powders were biodegraded by Proteinase K which is a PLA degradation enzyme. This polymer powder was suitable as a reference material for the evaluation methods of biodegradation.     

A new method for the synthesis of novel 6-quinoxalinylpyrazolo[5,1-c][1,2,4]triazines

The reaction of the quinoxaline 1 with 4-ethoxycarbonyl-1H-pyrazole-5-diazonium chloride 7 at room temperature gave 3-[α-(4-ethoxycarbonyl-1H-pyrazol-5-ylhydrazono)methoxycarbonylmethyl]-2-oxo-1,2-dihydroquinoxaline 8. The pmr spectrum of 8 in deuteriodimethylsulfoxide supported the presence of two tautomers 8-I and 8-II. Refluxing of 8 in N,N-dimethylformamide or acetic acid resulted in cyclization to afford 8-ethoxycarbonyl-4-oxo-3-(3-oxo-3,4-dihydroquinoxalin-2-yl)-1,4-dihydropyrazolo[5,1-c][1,2,4]triazine 9. Compound 9 was also obtained directly by the reaction of 1 with 7 under reflux in better yield. The reaction of 9 with hydrazine hydrate provided the hydrazinium salt 10 , while the reactions of 9 with triethyl and trimethyl orthoformates in the presence of 1,8-diazabicyclo[5,4,0]-7-undecene produced 8-ethoxycarbonyl-4-ethoxyl-3-(3-oxo-3,4-dihydroquinoxalin-2-yl)pyrazolo[5,1-c][1,2,4]triazine 11a and 8-ethoxycarbonyl-4-methoxyl-3-(3-oxo-3,4-dihydroquinoxalin-2-yl)pyrazolo[5,1-c][1,2,4]triazine 11b , respectively. The chlorination of 11a with phosphoryl chloride gave 3-(3-chloroquinoxalin-2-yl)-8-ethoxycarbonyl-4-ethoxylpyrazolo[5,1-c]-[1,2,4]triazine 12 , whose reaction with morpholine afforded 8-ethoxycarbonyl-4-ethoxyl-3-[3-(morpholin-4-yl)-quinoxalin-2-yl]pyrazolo[5,1-c][1,2,4]triazine 13.     

Medicinal flowers. XXIII. New taraxastane-type triterpene, punicanolic acid, with tumor necrosis factor-alpha inhibitory activity from the flowers of Punica granatum

The methanolic extract from the flowers of Punica granatum L. (Punicaceae) was found to show inhibitory effect on tumor necrosis factor-alpha (TNF-alpha, 1 ng/ml)-induced cytotoxicity in L929 cells. By bioassay-guided separation, a new taraxastane-type triterpene, punicanolic acid (1), was isolated from the active fraction (ethyl acetate-soluble fraction) together with four triterpenes (2--5), two galloyl glucoses (6, 7), two flavones (8, 9), and beta-sitosterol. Among the constituents, 1, oleanolic acid (2), maslinic acid (4), 1,2,6-tri-O-galloyl beta-D-glucopyranoside (6), 1,2-di-O-galloyl-4,6-O-(S)-hexahydroxydiphenoyl beta-D-glucopyranoside (7), and luteolin (8) significantly inhibited TNF-alpha-induced cytotoxicity in L929 cells at 30 microM.     

Simple and quick chemical aminoacylation of tRNA in cationic micellar solution under ultrasonic agitation

A simple and quick method for direct aminoacylation of a tRNA with a non-natural amino acid was developed by using an N-protected amino acid cyanomethyl ester as a substrate solubilized in CTACl micelle under ultrasonic agitation.     

Levitation of metallic melt by using the simultaneous imposition of the alternating and the static magnetic fields

This study developed a new levitation method, which used the simultaneous imposition of static and alternating magnetic fields. Dynamic behavior was measured for pure Cu and pure Ni melts levitated by the proposed method. The oscillation due to surface tension and convection in levitated Cu melts were hardly observed at static magnetic fields exceeding 1 T. Only the rotation of this axis parallel to the static magnetic field was observed under high static magnetic fields. The proposed method demonstrated that metallic melt could be statically levitated like a solid sphere. It was also found that stable levitation of paramagnetic Ni melt was rather difficult at static magnetic fields exceeding 5 T, because of the magnetization force.