3-(10-Phenyldecyl)catechol was synthesized by the reaction of catechol and 1-phenyl-10-iododecane, followed by de-protection of the hydroxyl groups of catechol; it was then polymerized into synthetic lacquer film by laccase enzyme, and characterized using pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) in order to reveal the polymerization mechanism of Melanorrhoea usitata lacquer. The molecular weight and molecular structure information for each peak in the total ion chromatograms (TIC) were obtained from the mass spectra analysis. In addition, the synthesized 3-(10-phenyldecyl)catechol monomer and its lacquer films were also investigated by IR and NMR measurement. The results showed that quinone produced by the laccase formed a CO bond not with the phenyl group but with the catechol ring of 3-(10-phenyldecyl)catechol, and 3-(10-phenyldecyl)catechol is only polymerized by the laccase to produce a lacquer film.

Six kinds of Ryukyu lacquerwares were analyzed using pyrolysis–gas chromatography/mass spectrometry to determine the identity of the lacquer source. 3-Heptylcatechol (MW=208) and 3-heptylphenol (MW=192) due to the pyrolysis product of urushiol were detected in four kinds of lacquer pieces. In the other two lacquer pieces, 3-nonylcatechol (MW=236) and 3-nonylphenol (MW=220) were obtained due to the pyrolysis of laccol, suggesting that the Ryukyu lacquerware was made from Rhus vernicifera and Rhus succedanea, respectively. In addition, the conservation and restoration of valuable ancient lacquerware also is discussed.

In situ microscopic measurements showed that rhombic microdomains of diprotonated 5,10,15,20-tetraphenylporphine aggregates were formed at a dodecane/aqueous H2SO4 interface. The size and thickness of the microdomains were about 10-100 mu m and a monolayer level, respectively. The microscopic absorption anisotropy of individual microdomains revealed that they had an ordered structure, like single crystals.

The lipid component of Melanorrhoea usitata lacquer sap isolated by acetone was analyzed and compared to synthesized ω-phenylalkylcatechols and ω-phenylalkylphenols. In addition, laccol and urushiol analogues synthesized in our laboratory were used as standard materials to analyze the lipid component of the Myanmar lacquer sap. The GC and GC/MS measurements confirmed the results of Kumanotani and Du that neither ω-phenylalkylcatechol nor ω-phenylalkylphenol exist in the lacquer saps from Rhus vernicifera and R. succedanea.

Ancient lacquer film, a Nanban lacquer film, an old lacquer-ware object imported from an Asian country, and the Baroque and Rococo lacquer films were analyzed by pyrolysis-gas chromatography/mass spectrometry. Compared with the results of the natural lacquer film, it was revealed that the ancient lacquer film and Nanban lacquer film were made from Rhus vernicifera, and the old lacquer-ware imported from an Asian country was made from Melanorrhoea usitata. However, the Baroque and Rococo lacquer films obtained from the Doerner Institute in Munich, Germany were made from natural resins. 3-Pentadecylcatechol (MW=320) (urushiol), 3-heptadecylcatechol (MW=348) (laccol), and 4-heptadecylcatechol (MW=348) (thitsiol) were the main products of the pyrolysis of R. vernicifera, Rhus succedanea, and M. usitata.

Laccol, a major component of lacquer sap from Rhus succedanea, was synthesized by a Witting reaction, and then mixed with acetone powder separated from raw lacquer sap to synthesize lacquer films. The resulting lacquer films were analyzed by pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), and the results were compared with that of natural lacquer film to evaluate the polymerization mechanism and film structure. The results showed that saturated and monoenyl laccol components were present only in the natural lacquer film, but not in the synthesized lacquer films. Meanwhile, alkylphenols, alkebulphenols, alkanes, and alkenes having longer carbon chains than the side chains were detected in the synthesized laccol, suggesting that the polymerization of synthetic laccol proceeds through the laccase-catalyzed nucleus-side chain CO coupling and autoxidative side chain to side chain CC coupling like natural lacquer film. The synthesized laccol films showed shallow color and hardness, which would make them useful as good preservative surface-coating materials.

Three lacquer saps (Rhus vernicifera, Rhus succedanea and Melanorrhoea usitata lacquer saps) are used for a surface coating in Asia. We previously reported the identification of urushiol components in Rhus vernicifera lacquer sap (Japan, China and Korea). In this study, laccol components in Rhus succedanea lacquer sap (Vietnam and Taiwan) were synthesized by Wittig reaction of ylides derived from alkyl- and alkenylphosphonium iodides with aromatic parts such as 3-(10-oxo-1-decyl)catechol diacetate and 3-(10-oxo-1-decyl)phenol acetate, followed by removal of acetate groups. Identification of natural laccol components from Rhus succedanea lacquer saps was carried out by GC and GC/MS and comparison with synthesized laccol components. Stereostructures and constituent of all laccol components in Rhus succedanea lacquer sap were clarified. By quantitative analysis using GC, the most abundant component was 3-[(10Z, 13E, 15E)-10, 13, 15-heptadecatrienyl]catechol except for red lacquer sap, but the abundance of trienyl components was not higher than that in the Japanese lacquer sap such as Rhus vernicifera. The amount of monoenyl components were higher than in Japanese lacquer sap.

examined the repetitive "KUROME" of raw urushi in a reaction vessel for the purpose of refining the polymerized urushi liquid that has a natural drying property in a low humidity environment. Namely, we evaluated the polymerization apparatus of the urushi liquid as a simple experiment. The raw urushi was polymerized by the repetitive "KUROME" process in a traditional method. We also examined the change in urushiol and the drying property in a low humidity environment (20-25 degreesC, 45-55%RH).Raw urushi undergoes enzymic oxidization by repetitive "KUROME" and decreases the urushiol monomer. Also, in this reaction, we developed a relation formula because there is a correlation in the area of the reaction vessel base, processing quantity and also processing time. Furthermore, with these changes, it was determined that the hydroxy value and anti-oxidization power decrease and the autoxidation of the side chain more easily occurs.

We conducted a basic experiment for the purpose of developing polymerized urushi that has a natural drying property in a low humidity environment, and examined the hardening process of the coating film with time as the urushi liquid dried by the enzymic oxidization using laccase in a constant temperature and humidity chamber (URUSHI MURO).We postulated that the auto-oxidation of the side chain easily occurs in the urushi liquid due to the enzymic polymerization based on the change in the infrared absorption spectra during the drying process and anti-oxidation property of raw and sugurome urushi. And, as a result, the change in the progress time of the drying property and degree of polymerization of the urushi coating film and liquid thin phase were measured. The molecular weight distribution of the urushiol in the time that naturally dries in a low humidity environment was admitted that the monomer component decreased to 27% or less.From that it was found out possibility that the polymerized urushi that naturally dries in a low humidity environment can be obtained by stirring with additional moisture raw urushi in the reaction vessel of shallow bottom and decreasing urushiol monomer.

An efficient method for synthesizing unsaturated urushiol components in urushi sap, was established, Wittig reaction of ylides derived from alkyl-and alkenyltriphenylphosphonium iodides, as side chain parts of urushiol, with 3-(8-oxo-1-octyl) catechol diacetate or 3-(10-oxo-1-decyl) catechol diacetate, as aromatic part of urushiol. Quantitative analysis of urushiol components in the urushi sap was done using GC for comparison with synthesized urushiol components as reference. In this manner, we proved the structures of most urushiol components and established percentage compositions of urushiols in the sap of Rhus vernicifera of Japan, Korea and China. (approximately 95%), by quantitative analysis of urushiol derived from Rhus vernicifera, the most abundant constituent was triene urushiol (approximately 71%) and the next abundant were mono (14-16%) and diene (5-8%) urushiol. Content was found to depend on growth conditions of the Rhus vernicifera tree and on the particular season for obtaining sap.

The trienyl urushiols, which are major urushiol components, were synthesized via the Wittig reaction. The synthesized urushiols were then polymerized into synthesized lacquer films by laccase-catalyzed oxidation. The resulting lacquer films were characterized using Pyrolysis-GC/MS, and the results were compared with that of a natural lacquer film in order to evaluate their polymerization mechanism and molecular structure. Based on these results, it was found that natural lacquer films are terminated with the monoenyl and saturated urushiol, and that the polymerization of synthesized urushiol proceeds through the laccase-catalyzed nucleus-side chain C-O coupling and autoxidative side chain-side chain C-C coupling, like the natural lacquer film.

An efficient method for synthesizing 3- [(8Z, 11E, 13Z) -8, 11, 13-pentadecatrienyl] catechol, the main component in urushiol, was established. Good yield was attained via the Wittig reaction of ylides derived from (3E, 5Z) -3, 5-heptadienyltriphenylphosphonium iodide with 3- (8-oxo-1-octyl) catechol diacetate in a stepwise procedure of repeated protection and deprotection of the hydroxyl group of catechol. Quantitative analysis of the triene urushiol of saps from of different origin was conducted for comparison with the synthesized triene urushiol as reference. In this manner, sap performance could be assessed best, since each sap with good performance as lacquer coating material was high in triene urushiol content. This content was found to depend on the growing conditions of the Rhus vernicifera tree and on the particular seasons for obtaining sap.

An apparatus for outputting a pitch data corresponding to a relative distance between a pair of movable members or a position of a second movable member relative to a first movable member. Data indicating the output relative distance or data indicating the output relative position is converted to corresponding pitch data in accordance with one of a plurality of conversion characteristics selected by a selection section. A pitch corresponding to the converted pitch data is determined. An electronic musical instrument outputs a musical tone having the determined pitch. The musical tone is controlled in accordance with a flow state of air passing through a mouthpiece or a bite pressure.