No abstract

Tropolone (1, Chart 1), a compound with aromatic seven membered ring in the molecule was firstly presented by Dewar in the year 1945. 1) After several years, the chemical structure of 1 was confirmed by the synthesis of four groups of worker [2][3][4][5] and it was also found to be the metabolites of Pseudomonas sp.6) From the unique chemical structure of 1, a great number of its derivatives have been synthesized. [7][8][9][10] Hinokitiol (2, Chart 1), the main constituent of Thujopsis dolabrata SIEB. et ZUCC. hondai MAKINO 11) has been used as a comparative agent, because it has the skeleton in common with 1. It has been found that 2 showed the following six kinds of biological activities; antimicrobial activity, 12,13) cytotoxic effects on various human and murine tumor cell lines, [14][15][16] phytogrowth-inhibitory activity, 17) insecticidal effect, 18,19) metalloprotease inhibitions, 13) and antifungal activity on wood rotting fungi. 19,20) With regard to the biological activity of 1 and its derivatives, there are papers about the antitumor activities, 21) phytogrowth-inhibitory activity, 17) and its preventation of the spread of termites on logs.22) However, no work has been done on such broad spectrum of biological activity of 1 in comparison with 2.Therefore, in this work, to expand the range of biological activity of 1, the inhibitory activity of this compound on metalloproteases such as carboxypeptidase A, collagenase and thermolysin and its insecticidal activity on Tyrophagus putrescentiae, Dermatophagoides farinae and Coptotermes formosanus was investigated. The antifungal activity of 1 on plant-pathogenic fungi was also examined. MATERIALS AND METHODS ChemicalsCompound 2 was isolated from acid oil obtained by distillation of the wood of T. dolabrata SIEB. et ZUCC. var hondai MAKINO, according to the method of Nozoe 23) Compound 1 was also obtained from Wako Pure Chemical Industries, Ltd., Osaka, Japan. Both compounds were used for the various biological tests. Metalloproteases such as carboxypeptidase A, collagenase and thermolysin were purchased from Sigma Chemical Co. (U.S.A.). 1,10-Phenanthroline (a positive control for inhibition of metalloprotease) was purchased from Nacalai Tesque, Inc. (Kyoto, Japan). N,N-Diethyl-m-toluamide (DEET, a positive control for insecticidal activity test on Tyrophagus putrescentiae and Dermatophagoides farinae) was obtained from Yoshitomi Pharmaceutical Industries, Ltd., Osaka, Japan. Chloropyrifos (a positive control for insecticidal activity test on Coptotermes formosanus) was purchased from Hoechst Schering Agro Evo, Japan, Ltd., Osaka, Japan.Microorganisms Plant-pathogenic fungi used for the antifungal activity test were as follows: Pythium aphanidermatum IFO-32440 ICR Building 2F, 6-6-3 Minamiyoshinari, Aoba-ku, Sendai 989-3204, Japan. Received June 6, 2003; accepted July 28, 2003 Tropolone (1) showed strong insecticidal activity on Tyrophagus putrescentiae and Dermatophagoides farinae. The insecticidal effect of 1 on both insects was stronger than that of...

Bacteria capable of assimilating cellulose acetate, strains SB and SC, were isolated from soil on a medium containing cellulose acetate as a carbon source, and identified as Neisseria sicca. Both strains degraded cellulose acetate membrane filters (degree of substitution, DS, mixture of 2.8 and 2.0) and textiles (DS, 2.34) in a medium containing cellulose acetate (DS, 2.34) or its oligomer, but were not able to degrade these materials in a medium containing cellobiose octaacetate. Biodegradation of cellulose acetate (DS, 1.81 and 2.34) on the basis of biochemical oxygen demand reached 51 and 40% in the culture of N. sicca SB and 60 and 45% in the culture of N. sicca SC within 20 days. A decrease in the acetyl content of degraded cellulose acetate films and powder was confirmed by infrared and nuclear magnetic resonance analyses. After 10-day cultivation of N. sicca SB and SC, the number-average molecular weight of residual cellulose acetate decreased by 9 and 5%, respectively. Activities of enzymes that released acetic acid and produced reducing sugars from cellulose acetate were mainly present in the culture supernatant. Reactivity of enzymes for cellulose acetate (DS, 1.81) was higher than that for cellulose acetate (DS, 2.34).

A bacterium capable of assimilating 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), strain BP-7, was isolated from offshore seawater samples on a medium containing bisphenol A as sole source of carbon and energy, and identified as Sphingomonas sp. strain BP-7. Other strains, Pseudomonas sp. strain BP-14, Pseudomonas sp. strain BP-15, and strain no. 24A, were also isolated from bisphenol A-enrichment culture of the seawater. These strains did not degrade bisphenol A, but accelerated the degradation of bisphenol A by Sphingomonas sp. strain BP-7. A mixed culture of Sphingomonas sp. strain BP-7 and Pseudomonas sp. strain BP-14 showed complete degradation of 100 ppm bisphenol A within 7 d in SSB-YE medium, while Sphingomonas sp. strain BP-7 alone took about 40 d for complete consumption of bisphenol A accompanied by accumulation of 4-hydroxyacetophenone. On a nutritional supplementary medium, Sphingomonas sp. strain BP-7 completely degraded bisphenol A and 4-hydroxyacetophenone within 20 h. The strain degraded a variety of bisphenols, such as 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, and 1,1-bis(4-hydroxyphenyl)cyclohexane, and hydroxy aromatic compounds such as 4-hydroxyacetophenone, 4-hydroxybenzoic acid, catechol, protocatechuic acid, and hydroquinone. The strain did not degrade bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfone, or bis(4-hydroxyphenyl)sulfide.

In our previous paper, 1) antimicrobial activity, phytogrowth-inhibitory effect, cytotoxic activity and metalloprotease inhibition have been found as biological activities of athujaplicin (Chart 1), a minor component of Thujopsis dolabrata SIEB. et ZUCC. var. hondai MAKINO. At the same time, as the yield of a-thujaplicin was too small to permit examination of various biological activities, it was also reported to be chemically synthesized.1) As reported already, in addition to a-thujaplicin, hinokitiol-related compounds such as 4-acetyltropolone, hinokitiol (b-thujaplicin), b-dolabrin and g-thujaplicin have also been isolated from this plant. 2)As regards the biological activities of hinokitiol-related compounds, it has previously been reported by the authors that hinokitiol, b-dolabrin, g-thujaplicin and 4-acetyltropolone have antimicrobial activity, 1,3,4) metalloprotease inhibition, 1,3,4) cytotoxic effect, 1,4,5) phytogrowth-inhibitory activity 6,7) and an insecticidal effect. 8) However, no work has yet been done on other biological tests, except for the abovementioned activities of a-thujaplicin, because of its low yield.In this work, to determine the range of biological activity of hinokitiol-related compounds, the antifungal activity on plant-pathogenic fungi, antibacterial effect on Legionella species and acaricidal and insecticidal activities against Dermatophagoides farinae and Reticulitermes speratus of a-thujaplicin were investigated. The cytotoxic effect on the murine P388 lymphocytic leukemia cell line in vitro of a-thujaplicin was also examined. MATERIALS AND METHODSChemicals a-Thujaplicin, which was synthesized according to the method of the previous paper, 1) was used for various biological activities. Hinokitiol, isolated from T. dolabrata SIEB. et ZUCC. var. hondai MAKINO, was used for tests of insecticidal and acaricidal effects and antifungal activity on plant-pathogenic fungi as a comparative agent. N,NDiethyl-m-toluamide (DEET, a positive control for insecticidal activity testing on Dermatophagoides farinae) was obtained from Yoshitomi Pharmaceutical Industries, Ltd., Osaka, Japan. Chloropyrifos (a positive control for insecticidal activity testing on Reticulitermes speratus) was purchased from Hoechst Schering Agro Evo, Japan, Ltd., Osaka, Japan. Vinblastine and vincristine were also obtained from Sigma Chemical Co. (U.S.A. Sciences; 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan: c Aomori Industrial Research Center; 4-11-6 Daini-tonyamachi, Aomori 030-0113, Japan: d Japan: e Fumakilla Ltd.; Japan: f Osaka Municipal Technical Research Institute; Japan: and g The Sendai Institute of Microbiology; ICR Building 2F, ). At 24 h after treatment, a a-thujaplicin at 0.63 m mg/ml inhibited the cell growth of murine P388 lymphocytic leukemia by 78%, and its cytotoxic activity at a concentration higher than 0.63 m mg/ml was as high as that of vincristine, used as a positive control. On the other hand, the cytotoxic effect of a a-thujaplicin at 0.63 m mg/ml was weaker than that of vi...