Phenolic constituents ofTaxus cuspidata I: lignans from the roots

The phenolic constituents of the roots ofTaxus cuspidata (Japanese yew) were investigated. Four lignans, [(+)-taxiresinol (1), (+)-lariciresinol (2), (–)-secoisolariciresinol (3), and (+)-pinoresinol (4)] were isolated and identified. The assignment of proton and carbon atoms for the lignans were finally solved by one- and twodimensional-nuclear magnetic resonance spectra. The enantiomeric excess of these lignans were determined by chiral high-performance liquid Chromatographic analyses. (+)-Lariciresinol and (–)-secoisolariciresinol were optically pure; (+)-taxiresinol was also suggested to be optically pure, although (+)-pinoresinol was not (77% enantiomeric excess).     

Erythro/threo ratio ofβ-O-4 structures as an important structural characteristic of lignin. I: Improvement of ozonation method for the quantitative analysis of lignin side-chain structure

Ozonation as a quantitative tool to analyze the stereo structures of arylglycerol--aryl ether linkages was examined using wood meal, milled wood lignin, and a lignin model compound, 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol (veratrylglycerol--guaiacyl ether, VG). The procedure was improved. When mild postreduction was conducted for ozonation products, the total yield of erythronic and threonic acids from this model compound was 74%, which is 15% higher than the yield without postreduction. A decrease in the recovery of these two acids under prolonged ozonation treatment was successfully suppressed by postreduction. Theerythro/threo ratio of VG determined by the ozonation method with postreduction is in good agreement with the ratio determined by¹H-nuclear magnetic resonance. Excellent reproducibility of the yield was obtained by adopting a procedure that included trimethylsilylation of ammonium salts of ozonation products using a dimethylsulfoxide-hexamethyldisilazane-trimethylchlorosilane mixture and subjecting it to gas chromatography analysis. It was concluded that arylglycerol--aryl ether structures comprise at least 35% of the C₃-C₆ structure in birch wood meal, with anerythro/threo ratio of 2.8.This paper was presented at the 43rd Lignin Symposium, Fuchu, Japan, October 1998; and at the 10th ISWPC, Yokohama, Japan, June 1999     

Stereochemistry and biosynthesis of (+)-lyoniresinol, a syringyl tetrahydronaphthalene lignan in Lyonia ovalifolia var. elliptica I: isolation and stereochemistry of syringyl lignans and predicted precursors to (+)-lyoniresinol from wood

Steps leading to the biosynthesis of syringyl lignans and tetrahydronaphthalene and naphthalene lignans, especially the formation of the C2–C7′ linkage, have not been elucidated. Lyoniresinol is a typical syringyl lignan, as well as a tetrahydronaphthalene lignan found in Lyonia ovalifolia var. elliptica. To demonstrate the biosynthetic pathway for (+)-lyoniresinol, three putative biosynthetic intermediates of lyoniresinol, syringaresinol, 5,5′-dimethoxylariciresinol, and 5,5′-dimethoxysecoisolariciresinol, were isolated from wood. The identity of the putative intermediates was confirmed by spectroscopic analyses, as well as by comparison of spectral and chromatographic data with those of authentic samples previously synthesized. The stereochemistry (enantiomeric composition and absolute configuration) of the isolated lignans were determined as (±)-syringaresinol, (8S,8′S)-(−)-5,5′-dimethoxylariciresinol [46% enantiomeric excess (e.e.)], (8S,8′S)-(+)-5,5′-dimethoxysecoisolariciresinol (91% e.e.), and (8R,8′R)-(+)-lyoniresinol (42% e.e.). The absolute configurations of (+)-and (-)-5,5′-dimethoxylariciresinols, and (+)-and (-)-5,5′-dimethoxysecoisolariciresinols were determined by their synthesis (catalytic reduction) from (8R,8′R)-(+)-and (8S,8′S)-(-)-syringaresinols and by subsequent chiral high-performance liquid chromatography analysis. This report was presented at the 55th Annual Meeting of the Japan Wood Research Society, Kyoto, March 2005     

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     

Distribution of lignin interunit bonds in the differentiating xylem of compression and normal woods of Pinus thunbergii

The lignification process and lignin distribution at different stages of cell wall differentiation in the secondary xylem of compression and normal woods of Pinus thunbergii were investigated by thioacidolysis and subsequent desulfuration. We prepared 50-µm-thick, contiguous tangential sections of pine shoots, cut from the cambial zone through to mature xylem. In compression wood, uncondensed guaiacyl (G) and p-hydroxyphenyl (H) lignins were deposited simultaneously from early to late stages of lignification. The various types of G-G, G-H, and H-H dimers were detected in compression wood, and the ratio of G-H and H-H dimers to total dimers increased as lignification proceeded. In contrast, uncondensed and condensed H units were detected in trace amounts in normal wood. Significant differences in the relative distributions of lignin interunit linkages were not observed between compression and normal woods or between differentiating and mature xylems in either compression or normal woods.Part of this report was presented at the 10th International Symposium on Wood and Pulping Chemistry, Yokohama, June, 1999     

Isolation and enzymatic formation of lignans ofDaphne genkwa andDaphne odora

Four lignans — pinoresinol, lariciresinol, secoisolariciresinol, matairesinol — were isolated from each ofDaphne odora andDaphne genkwa (Thymelaeaceae). Matairesinol isolated from both plants was optically pure (>99% e.e.) and dextrorotatory. Pinoresinol and lariciresinol isolated from the plants were not optically pure, and their enantiomeric compositions ranged from 88% to 95% e.e. in favor of (–)-enantiomers. As for secoisolariciresinol, the one fromD. odora was optically pure [(+)-enantiomer, >99% e.e.], and that fromD. genkwa was 97% e.e. in favor of the (+)-enantiomer. Lignan-synthesizing enzyme activity was detected from a Thymelaeaceae plant for the first time; cell-free extracts fromD. genkwa catalyzed the formation of (–)-lariciresinol (23% e.e.) from racemic (±)-pinoresinols. The stereochemistry of the enzymatic reaction is discussed in relation to the stereochemical features of the isolated lignans.Parts of this report were presented at the 42nd Lignin Symposium, Sapporo, October 1997; 48th Annual Meeting of the Japan Wood Research Society, Shizuoka, April 1998; and 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999     

Possibility of improvement in fundamental properties of wood of acacia hybrids by artificial hybridization

Growth, specific gravity, and wood fiber length of Acacia mangium, Acacia auriculiformis, artificial acacia hybrid clones, and combinations, which were planted in a trial forest in Bavi, Vietnam, in July 2001, were examined. The radial variations from pith to bark were investigated to clarify the effect of genetic factors on these traits. Superiority of hybrids over their parents ranged from 36.3% to 41.6% for diameter, from 20.0% to 25.3% for height, from 6.9% to 20.7% for specific gravity, and from 6.1% to 12.8% for wood fiber length. The hybrid possessed heterosis in diameter, height, specific gravity, and wood fiber length regardless of whether the female parent was A. mangium or A. auriculiformis. The profiles of wood fiber length and specific gravity in the radial direction were similar for all the trees investigated. Wood fiber length was initially 0.5–0.6 mm near the pith and then increased slowly, finally reaching 1.0–1.2 mm near the bark. The specific gravity of acacia increased from 0.49–0.58 near the pith to 0.63–0.74 near the bark. From a relative distance of 30% from the pith, the specific gravity increased slightly and seemed to be stable. The relations among tree diameter, specific gravity, and wood fiber length were fair and could be represented by positive linear regression formulas. Hybrids for which A. auriculiformis was the female parent and A. mangium was the male parent had a faster growth rate and longer wood fibers than the inverse hybrids. Part of this report was presented at the 6th Pacific Regional Wood Anatomy Conference, Kyoto, Japan, December 2005     

Effect of volatile matter from wood chips on the activity of house dust mites and on the sensory evaluation of humans

The effect of volatile matter from various wood chips on house dust mites and their influence on human comfort were measured. To investigate the effect of volatile matter on the mite speciesDermatophagoides pteronyssinus, the activity of the mites was observed after exposure to volatile matter from six species of wood chips. The degree of activity of the mites was classified into two categories: (1) walking or moving and (2) immobilized. To measure their influence on human comfort, the smells of those wood chips were evaluated by the subjects. Among softwoods, volatile matter fromChamaecyparis obtusa andThujopsis dolabrata var.hondai chips suppressed the activity of the mites highly and made the subjects feel refreshed and unexcited.Cryptomeria japonica showed slight suppression of the mites and was considered to be refreshing, natural, and unexciting by the subjects. Among hardwoods,Cinnamomum camphora highly suppressed mites activity and was considered to be non-refreshing and exciting by the subjects. Part of this paper was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999     

Enantiomeric compositions and biosynthesis ofWikstroemia sikokiana lignans

Thymelaeaceae plants produce dextrorotatory dibenzylbutyrolactone lignans, which are opposite enantiomers to the lignans isolated from other plants (e.g.,Forsythia spp.). In our previous paper, (–)-pinoresinol (74% enantiomer excess), (+)-matairesinol (optically pure), and (+)-wikstromol (optically pure) were isolated fromWikstroemia sikokiana (Thymelaeaceae). In the present investigation, a survey of lignans and the determination of their enantiomeric compositions were continued. Four lignans, (–)-lariciresinol, (–)-secoisolariciresinol, (+)-kusunokinin, and (+)-methyltrachelogenin, were isolated from MeOH extracts ofW. sikokiana stem. To our knowledge, we have isolated (+)-methyltrachelogenin from plants for the first time. Chiral high-performance liquid chromatographic analysis showed that (+)-kusunokinin and (+)-methyltrachelogenin were optically pure, whereas (–)-lariciresinol and (–)-secoisolariciresinol were not (39% and 45% enantiomer excess, respectively). Feeding experiments with deuterium-labeled substrates demonstrated conversion of coniferyl alcohol to the lignans and interconversion of lignans. These reaction sequences are similar to the sequence catalyzed byForsythia enzymes. However, predominant enantiomers of the lignans, except for secoisolariciresinol isolated fromW. sikokiana, have absolute configurations opposite to those of the corresponding lignans isolated fromForsythia spp. Based on the results of the isolation and the feeding experiments, several differences betweenW. sikokiana andForsythia spp. are pointed out regarding stereochemical mechanisms for lignan biosynthesis.Parts of this report were presented at the 46th annual meeting of the Japan Wood Research Society, Kumamoto, April 1996; and the 47th annual meeting of the Japan Wood Research Society, Kochi, April 1997     

卵巢线虫(Contortylenchus genitalicola)在中国松褐天牛上的分布与作用研究

[目的]日本学者Kosaka与Ogura发现松褐天牛成虫除携带松材线虫外,雌成虫卵巢内还携带有另一种线虫,他们将其命名为卵巢线虫,并认为这种线虫是松褐天牛成虫的寄生性线虫。我国对该种线虫的研究迄今未见报道。为了证明这种线虫在我国是否存在和分布,开展了本项研究。[方法]分期分批捕获刚羽化的松褐天牛雌雄成虫,采用解剖松褐天牛成虫松树木质部及感病的松褐天牛幼虫等方法,调查卵巢线虫的存在与分布。[结果]通过调查研究,发现我国的松褐天牛成虫体内有该卵巢线虫存在,分布于松褐天牛成虫、幼虫体内和松树木质部3个部位;在松褐天牛成虫体内的卵巢线虫通过松褐天牛雌成虫产卵而接种、进入寄主树木木质部中。同时,木质部的卵巢线虫也有一部分进入松褐天牛幼虫体内寄生,另一部分仍在木质部生活,当松褐天牛幼虫再次发育为成虫时,在木质部中的卵巢线虫和已被寄生的松褐天牛幼虫体内的卵巢线虫再次进入松褐天牛成虫体内,完成循环。卵巢线虫在松褐天牛雌、雄虫体内均有分布,携带率为44.4%,其中松褐天牛雌成虫携带率为43.8%,松褐天牛雄成虫携带率为45.0%,两者间无显著差异;每头松褐天牛成虫平均携带卵巢线虫574条,其中雌成虫平均携带816条,雄成虫平均携带308条,具显著差异。初步研究表明,卵巢线虫在松褐天牛成虫体内只能完成产卵到1~4龄的幼虫阶段,不能完成一个完整的世代;在松褐天牛幼虫体内寄生和在木质部生活的卵巢线虫能完成一个完整世代,但具体过程尚不清楚;调查中未观察到卵巢线虫对松褐天牛成虫有寄生致病或致死的现象,但对松褐天牛幼虫有寄生致死的能力;卵巢线虫常与松材线虫同时存在,而且侵入松树及离开松树的方式与松材线虫相同。[结论]我国松褐天牛体内也发现有卵巢线虫存在;目前尚不能证明该线虫对松褐天牛成虫具有寄生致死性,但对松褐天牛幼虫具有一定的寄生致死性;卵巢线虫的生活史与松材线虫相似,是否与松材线虫一样对松树具有危害性以及其病理作用还有待于进一步研究。     

Contribution of active defense responses in the limitation of fungal spread in the sapwood of living sugi (Cryptomeria japonica) tree

The participation of active defense responses in the limitation of fungal spread in the sapwood of living sugi tree was determined. Isolates ofGuignardia cryptomeriae were inoculated to living trees, fresh logs, frozen and thawed logs and autoclaved logs, and the spread of wood discoloration and fungal hyphae was assessed. In autoclaved logs and freeze-treated logs, wood discoloration and reaction zone formation were not observed, and fungal hyphae of both of virulent and avirulent isolates grew rapidly in the wood. In fresh logs, wood discoloration and the formation of a pale reaction zone and transition zone were observed. Virulent isolates spread rapidly, but the spread of avirulent isolates was inhibited. In living trees, wood discoloration was observed and reaction zones were formed at lesion margins. These results indicated that constitutive defense mechanisms had no effect on the spread of both of virulent and avirulent isolates, and that active defense responses were important in the limitation of spread of fungal hyphae, hence in the limitation of wood discoloration. Further, it appeared that avirulent, but not virulent, races ofG. cryptomeriae were easily inhibited even by weak host responses. This study was presented at 105th and 106th Annual Meeting of the Japanese Forestry Society.     

Walnut hoarding by the Japanese wood mouse,Apodemus speciosus Temminck

Walnuts,Juglans ailantifolia Carriere, are large and the shell is difficult to open. Thus, seed predators in Japan are restricted mainly to the Japanese squirrel (Sciurus lis Temminck) and the wood mouse (Apodemus speciosus Temminck), which can shave away the hard shells with their sharp incisors. Previous work indicated that the squirrels are not only predators, but also disperse walnuts. In this study, 95 walnuts in Period1 (September 1996–February 1997) and 80 walnuts in Period 2 (September 1999–February 2000) each attached to a miniature radio transmitter, were placed in a feeding box, and 93 and 53 of them were transported by free-living wood mice in the respective periods. Most of the walnuts provided from September to November were scatter-hoarded in the litter layer, while from December to February, the mice fed immediately and seldom scatter-hoarded on the ground surface. In all, 66 walnuts were hoarded and 80 were eaten soon after discovery, although walnuts were eaten more frequently in Period 1 than in Period 2, which may be related to annual differences in seed crop size in the study site. The mean transport distance of hoarded seeds was 6.2 ± 5.0 m (mean ± SD,n=66). The fate of hoarded walnuts was followed from September 1996 to May 1997; 21 (75%) of the scatter-hoarded walnuts were recovered, but 7 (25%) were left uneaten. Consequently, the Japanese wood mouse also plays a role in seed-dispersion of the walnut, but the transport distance for mice was shorter than that for squirrels.     

Feeding activities of Coptotermes formosanus Shiraki and Reticulitermes speratus (Kolbe) as affected by moisture content of wood

The relationship between the moisture content (MC) of wood blocks and the feeding activities of two Japanese subterranean termites, Coptotermes formosanus Shiraki and Reticulitermes speratus (Kolbe), was investigated with two choice tests. When three wood blocks with low MC (6%–12%), middle MC (79%–103%), and high MC (140%–182%) were exposed to workers of C. formosanus and R. speratus in a choice test, the feeding preferences were found in the middle MC blocks for C. formosanus, and the middle and high MC blocks for R. speratus, although wood blocks of low MC were also attacked. In a second choice test, wood blocks consisting of five pieces with water-impregnated (MC: 133%–191%) top, middle, or bottom piece were exposed to workers of both species. Higher consumptions were generally obtained in water-impregnated wood pieces and bottom pieces.     

Color development of proanthocyanidins in vanillin-hydrochloric acid reaction

The influence of proanthocyanidin (PA) structures contained in bark on color development in the vanillin-hydrochloric acid (V-HCl) method used widely as a quantitative method for measuring PA were examined. The maximal absorption wavelength was different in terms of the bark from which the PA was obtained. Phenyl nucleus (resorcinol, phloroglucinol) constituting the A-ring of PA reacts with vanillin to produce the color. The maximal absorption wavelengths of the solutions from synthesized procyanidin and profisetinidin were 500 and 540 nm, respectively, indicating that the color tone differs in the V-HCl method based on the hydroxylation patterns of the A-ring. The colored solution of (+)-catechin with vanillin was dialyzed, and the resulting product (C-VC) was analyzed by gel permeation chromatography and ¹H nuclear magnetic resonance. It was found that C-VC was a polymer complex consisting of 9mol (+)-catechin moieties and 10mol vanillin moieties. It was presumed that the cationized vanillin molecules that do not combine with (+)-catechin play an important role on color development in the presence of C-VC.This study was presented at the 44th and 45th Annual Meetings of The Japan Wood Research Society, Nara and Tokyo, April 1994 and April 1995     

Chemical changes in terpenes of sugi (<Emphasis Type="Italic">Cryptomeria japonica</Emphasis>) wood during steam drying in kiln at high temperature

Sawdusts of sugi (Cryptomeria japonica) wood prepared before and after steam drying at 120°C in a kiln were extracted with n-hexane and ethyl acetate to give n-hexane extracts and ethyl acetate extracts. From gas chromatography-mass spectrometry analysis of the ethyl acetate extracts from woods before and after steam drying, the components of 4-epi-cubebol, cubebol, and 2,7(14),10-bis-abolatrien-1-ol-4-one, which existed in the raw sugi wood, were proved to disappear in the steam-dried wood. These components were also absent in the ethyl acetate extract of the steam-condensed solution of waste steam from the kiln outlet. When these three components were treated with 0.2% (v/v) acetic acid solution at 120°C, δ-cadinene was produced as a major product from both 4-epi-cubebol and cubebol by dehydration and cleavage of the cyclopropane ring, and cryptomerone from 2,7(14),10-bisabolatrien-1-ol-4-one by hydration. The chemical changes of the three components presumably occur during steam drying of the sugi wood. This study was presented in part at the 85th Spring Meeting of the Chemical Society of Japan, Kanagawa, Japan, March 26–29, 2005     

Chemical structural elucidation of total lignins in woods I: fractionation of the lignin in residual wood meal after extraction of milled wood lignin

Residual wood meal after extraction of milled wood lignin (WMEM) ofEucalyptus globulus was extracted with alkali and LiCl/N,N-Dimethylacetamide (DMAc). These agents dissolve mainly hemicellulose and cellulose, respectively. The extractability of WMEM in alkali solutions was influenced by the degree of swelling of the cellulose. Under good swelling conditions, considerable amounts of cellulose and lignin were extracted with the hemicellulose. Maximum extractability was about 60% of the WMEM under optimum conditions (3 M or 5 M LiOH or 3M NaOH solution). Some portion of cellulose was extracted with LiCl/DMAc at room temperature. Thus, lignin inE. globulus WMEM was divided into three fractions: hemicellulose-lignin fraction, cellulose-lignin fraction, and insoluble-lignin fraction.Part of this work was presented at the 49th annual meeting of the Japan Wood Research Society, Tokyo, April 1999; and at the 50th annual meeting of the Japan Wood Research Society, Kyoto, April 2000     

In situ measurement of wood moisture content in high-temperature steam

Changes in moisture content of sugi (Cryptomeria japonica D. Don) wood during high-temperature saturated and superheated steam treatments were investigated. A system for in situ weighing of specimens was used, and the reduction of wood substance by heating was taken into consideration. At 160°C the loss of wood substance due to heating was significant and influenced the moisture content values, but it was almost negligible at 120°C. Treatment time and temperature affected the moisture content in saturated steam but not in superheated steam. Excess water in a saturated closed system appears to promote the decomposition of wood and condensation in or on specimens.Parts of this work was presented at the 49th, 50th, and 52nd Annual Meetings of the Japan Wood Research Society in Tokyo, April 1999; Kyoto, April 2000; and Gifu, April 2002     

广西融水特色红心杉木优树材质性状变异规律研究

[目的]通过测定和分析广西融水种源红心杉木优树材质性状指标,以了解该地区红心杉木材性状变异规律。[方法]以广西融水种源60株20年生的红心杉木优树为研究材料,测定单株材积、红心率、基本密度、组织比量、管胞性状、微纤丝角等10个材质性状指标,分析各材性性状指标分布和变异规律及性状间的相关关系。[结果]表明:红心率、基本密度、木射线比量、管胞比量、管胞长、管胞宽、管胞长宽比等性状数据分布服从正态分布。融水两个地区红心杉优树轴向薄壁细胞比量的变异系数分别为35.08%和44.97%,变异较大。管胞比量变异系数分别为3.28%和3.56%,变异较小。红心率、木射线比量、管胞长、管胞宽、微纤丝角等性状差异极显著(P0.01),轴向薄壁细胞比量差异显著(P0.05)。10个材质性状间存在12对表型显著相关。[结论]测定的10个性状均是连续性数量性状。早、晚材的管胞长度、管胞宽度和管胞长宽比等性状数据呈从心材至边材逐渐增加的规律。作为重要经济性状的红心率与木射线比量呈极显著正相关(P0.01),单株材积与轴向薄壁细胞比量呈显著正相关(P0.05),而单株材积与基本密度的相关性不显著,这使红心杉木生长量与材性相结合的遗传改良成为可能。     

Lignification and peroxidase in tension wood ofEucalyptus viminalis seedlings

Seedlings ofEucalyptus viminalis were grown for 50 days with their stems bent so tension wood would form. Every 10 days the lignin content, monomeric composition, and peroxidase activity in the tension wood were compared with those in the lower side (opposite wood) and in vertically grown controls. The lignin content in the developing tension wood started to decrease after 10 days of bending and kept decreasing for 50 days, whereas those in control plants and opposite wood remained almost unchanged. The yields of syringaldehyde from tension wood by nitrobenzene oxidation increased, and consequently the syringyl/ guaiacyl ratio of the lignin was higher in tension wood than in opposite wood and control plants. The peroxidase ionically bound to the cell walls (IPO) catalyzed oxidation of guaiacol and syringaldazine. The syringaldazineoxidizing activity of IPO from tension wood increased, whereas the activities of IPO from opposite wood and control plants did not show any marked change. In tension wood the increase in syringaldazine-oxidizing activity of IPO was consistent with an increase in the syringaldehyde yield. This suggests that IPO contributes to syringyl lignin deposition as other enzymes involved in the monolignol biosynthesis do in tension wood formation.This study was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000     

Clonal variation of carbon content in wood of Larix kaempferi (Japanese larch)

Variations in carbon content in wood among 102 clones, selected from almost the entire natural distribution area, were investigated in Larix kaempferi. The average carbon content was 50.50%, 50.94%, and 50.80% in sapwood, heartwood, and whole wood, respectively. The difference in carbon content between clones was significant. The clonal repeatabilities were 0.46, 0.38, and 0.44 in heartwood, sapwood and whole wood, respectively. The coefficients of variation in the clonal mean carbon content were only 0.43%, 0.42%, and 0.41% in heartwood, sapwood, and whole wood, respectively. This small genetic variation and resulting small relative genetic gain of carbon content indicate that the genetic improvement of carbon content by selection has a small effect on the genetic improvement of carbon sequestration capacity by selection in L. kaempferi.