Termiticidal activity of wood vinegar, its components and their homologues

The termiticidal activity of wood vinegar, its components, and their homologues have been studied. Three kinds of wood vinegar made from the mixed chips ofCryptomeria japonlca andPseudotsga menziesii (wood vinegar A),Quercus serrata (wood vinegar B), andPinus densiflora (wood vinegar C) exhibited high termiticidal activities againstReticulitermes speratus. Acetic acid, which is the largest content of wood vinegar, exhibited high termiticidal acitivity. The contents of organic fraction of wood vinegars and acetic acid might be responsible for the differences in termiticidal activities among these wood vinegars. The structure and termiticidal activity relations of phenols were studied. Phenol with some substituents revealed higher termiticidal activity than benzene derivatives, which have no hydroxyl group; an ortho substituent of phenol plays an important role in termiticidal activity. It has become apparent that high termiticidal activity cannot be obtained by a phenolic hydroxyl group alone; it can be obtained, however, by some substituents, especially an ortho substituent in addition to a phenolic hydroxyl group. The bulkiness of the substituent at the ortho position participates in termiticidal activity; activity decreases as the size of an ortho substituent increases. It is thought that the interaction at the receptor site of termites is affected by the increased size of the ortho substituent.     

Chemical changes of kenaf core binderless boards during hot pressing (I): influence of the pressing temperature condition

Self-bonding is the main factor of the performance expression of binderless boards, and therefore its clarification is considered to be an important issue. For this purpose, a series of chemical analyses were conducted on kenaf core binderless boards and their chemical changes during the hot-pressing process are discussed in this article. First of all, binderless boards were prepared from kenaf core powder at different pressing temperatures (without steam-explosion process) and were used for chemical analyses after they were reduced into powders and extracted with methanol. To investigate their chemical changes, lignin, holocellulose, and neutral sugar contents were determined, Fourier transform infrared (FTIR) spectra were recorded, and the nitrobenzene oxidation procedure was applied. As a result, it was found that parts of lignin and hemicelullose were decomposed during the hot-pressing process; however, the contribution of the resulting fractions to selfbonding was not observed. In addition, progress of condensation reactions in lignin and the formation of chemical bonds by low molecular weight conjugated carbonyl compounds in methanol extractives were observed. Thermal softening of lignin is also suggested to play an important role in the expression of board performance.     

Stereochemistry of matairesinol formation by <Emphasis Type="Italic">Daphne</Emphasis> secoisolariciresinol dehydrogenase

Secoisolariciresinol dehydrogenase activity was detected for the first time from Daphne odora and Daphne genkwa (Thymelaeaceae), which are known to produce optically pure (+)-matairesinol. In sharp contrast, (–)-matairesinol was formed selectively over the (+)-antipode by the secoisolariciresinol dehydrogenase preparation from both D. odora callus and D. genkwa shoots.     

Lignan production inDaphne odora cell cultures

Lignan production in callus and cell suspension cultures ofDaphne odora is reported for the first time. The cell suspension culture produced pinoresinol, lariciresinol, secoisolariciresinol, matairesinol, and wikstromol. The production of matairesinol in the cell suspension culture was much higher than that inDaphne odora stem tissues.Part of this report was presented at the 51th annual meeting of the Japan Wood Research Society, Tokyo, April 2001     

New lignan, isoactifolin, fromChamaecyparis obtusa cv. Breviramea

A new lignan isoactifolin was isolated from young shoots (with leaves) ofChamaecyparis obtusa cv. Breviramea. The structure of the compound was determined based on spectroscopic evidence.Parts of this report were presented at the 44th lignin symposium, Gifu, October 1999     

Structural characteristics of cell walls of kenaf (<Emphasis Type="Italic">Hibiscus cannabinus </Emphasis>L.) and fixation of carbon dioxide

 Kenaf (Hibiscus cannabinus) plants are widely known for their contribution to the global and regional environment because of their ability to fix CO₂. On the other hand, some scientists have doubts about CO₂ fixation by kenaf and have misgivings about the effect of kenaf on the ecosystem. We have characterized the structural characteristics of cell walls of bast fibers, cores, roots, and leaves of kenaf during the maturation of plants and investigated the rate of photosynthesis. During maturation of the kenaf plant the cellulose (bast fiber 52–59%, core 44–46%) and lignin (bast fiber 9.3–13.2%, core 18.3–23.2%) contents increased significantly. The aromatic composition of the lignin of bast fiber was significantly different from that of the core lignin and of other plants. The lignin of bast fiber appears similar to pure syringyl lignin. Fixation of CO₂ by kenaf plants and their contribution to the global environment are discussed. A significatly high rate of photosynthesis of kenaf plants was observed compared to that of woody plants in Japan, but the amount of CO₂ fixation depends on the characteristics of the plantation. If the kenaf was planted in high density, about twice as much CO₂ was fixed as was fixed by trees in a tropical rain forest. Received: April 22, 2002 / Accepted: July 24, 2002 Acknowledgments This project was supported by the Science and Technology Agency (STA) fellowship of the Japan International Science and Technology Exchange Center (JISTEC), which has been successfully applied by Dr. Shuji Hosoya, Forestry and Forest Products Research Institute. We thank Dr. Toshio Sumizono and Mr. Masao Sakurai, Forestry and Forest Products Research Institute, for their kind help in determining the rate of photosynthesis and cultivating the kenaf plants, respectively. We also express our appreciation to Dr. Quang Hung Le, College of Agriculture and Forestry, Ho Chi Minh City, Vietnam for offering information about the cultivation of kenaf at Thu Duc District, Ho Chi Minh City.     

Gas chromatographic and mass spectrometric (GC-MS) analysis of lignin-derived products from <Emphasis Type="Italic">Cryptomeria japonica</Emphasis> treated in supercritical water

Sugi (Cryptomeria japonica D. Don) wood was treated with supercritical water (374°C, 22.1MPa), and fractionated into the water-soluble portion, the methanol-soluble portion, and the methanol-insoluble residue. The methanol-soluble portion mainly consisted of the lignin-derived products. To characterize the compounds in the methanol-soluble portion, gel permeation chromatographic (GPC) and gas chromatographic-mass spectrometric (GC-MS) analyses were performed. The GPC analysis indicated that the methanol-soluble portion contained lignin-derived monomeric and dimeric products. GC-MS analysis detected 31 products which were expected to be monomeric compounds, and 18 of these were identified to be guaiacol, methylguaiacol, ethylguaiacol, vinylguaiacol, eugenol, propylguaiacol, vanillin, cis-isoeugenol, homovanillin, trans-isoeugenol, acetoguaiacone, propioguaiacone, guaiacylacetone, 2-methoxy-4-(1-hydroxypropyl)phenol, homovanillic acid, 2-methoxy-4-(prop-1-en-3-one)phenol, coniferyl aldehyde, and ferulic acid. In addition, 22 dimeric products were detected, and 4 of these were believed to be compounds with biphenyl type (5-5), diphenylethane type (-1), stilbene type (-1), and phenylcoumaran type (-5) structures. These results clearly indicated that the methanol-soluble portion included various monomeric and dimeric compounds produced as a result of the cleavage of ether linkages and propyl chains of lignin.     

Structural changes in lignin of tropical woods during digestion by termite, <Emphasis Type="Italic">Cryptotermes brevis</Emphasis>

Wood samples of apitong (Dipterocarpus grandiflorua) and ilang-ilang (Ilang-Ilang C. dadloyi) and feces of termites [Cryptotermes brevis (Walker)] fed on these woods were collected from University of the Philippines, Los Baňos. Lignin of each sample was isolated by Björkman’s procedure. There was no significant difference in ¹H nuclear magnetic resonance (NMR) spectra or in the methoxyl content between Björkman lignins from original woods and termite feces. Differences were detected in the contents of aliphatic and unconjugated phenolic hydroxyl groups, suggesting minor structural changes of lignin during digestion by termites. In addition, the ratio of syringyl to guaiacyl nuclei of Björkman lignin from termite feces determined by ¹H NMR spectra was higher than those from the original woods. The molar ratio of syringyl to guaiacyl nuclei of termite feces was higher than those from the original woods as determined by alkaline nitrobenzene oxidation. These results suggest that the structural changes of lignin in the termite gut are due to the insignificant formation of C-C linkages in guaiacyl nuclei. It was concluded that there were minor changes in the structural features of lignin under mostly anaerobic conditions, in contrast to the significant changes that occur through biological modification under aerobic conditions.     

GC-MS and IR spectroscopic analyses of the lignin-derived products from softwood and hardwood treated in supercritical water

Softwood (Cryptomeria japonica) and hardwood (Fagus crenata) were treated in supercritical water (380°C, 100 MPa) for 8 s. The treated woods were fractionated to the water-soluble portion, methanol-soluble portion, and methanol-insoluble residues. For the methanol-soluble portion, which mainly consisted of lignin-derived products, gel permeation chromatography (GPC) and gas chromatographic-mass spectrometric (GC-MS) analyses were conducted to clarify the molecular weight distribution and to identify the monomeric products, respectively. GPC analysis revealed that the methanol-soluble portion contains monomeric and some oligomeric products. GC-MS analysis identified 19 guaiacyl compounds in the methanol-soluble portion from softwood, and 15 syringyl monomeric compounds in the methanol-soluble portion from hardwood. The structures of identified products included not only phenyl propane (C₆—C₃) units but also C₆—C₂ and C₆—C₁ units. In addition, the infrared spectra suggested that the methanol-soluble portion maintains the typical structure of lignin, although it is rich in condensed-type linkages with some changes in the propyl side chain. These results indicate that the supercritical water treatment cleaves not only ether linkages but also part of the propyl chains in lignin to give various aromatic compounds.     

Decomposition behavior of woody biomass in water-added supercritical methanol

The chemical conversion of Japanese beech (Fagus crenata Blume) in water-added supercritical methanol was studied for a wide range of water content using a batch-type reaction vessel to obtain chemicals from lignocellulosics. It was consequently found that addition of water enhanced the decomposition of wood cell wall components; cellulose, hemicelluloses, and lignin. In cases of high water content, however, it resulted in low solubility of lignin-derived products causing an increase in the mass of the residue. The water content was thus optimized to be around 10% (v/v) for the decomposition of wood. Concomitantly, the yields and selectivity of the chemicals from wood could be regulated by the addition of water, especially for the lignin-derived products. As a result, the monomeric compounds of lignin, coniferyl alcohol and sinapyl alcohol, were recovered as their γ-methyl ethers in the presence of water in higher yields than those obtained without addition of water.