Synthesis of dihydroxyphenacyl glycosides for biological and medicinal study: β-oxoacteoside from Paulownia tomentosa

The protected structure of -oxoacteoside (tomentoside A), 2-oxo-2-(3,4-dihydroxyphenyl)ethyl 3-O-(2,3,4-tri-O-acetyl--l-rhamnopyranosyl)-4-O-caffeoyl--d-glucopyranoside 14 was synthesized in 14% overall yield in 11 steps, starting from d-glucose for biological and medicinal studies of phenylpropanoid glycosides. The first step was the preparation of a 3-O-rhamnopyranosyl disaccharide sugar core 2 from a suitably protected rhamnosyl trichloroacetimidate 10 and glucose derivative (diacetone-d-glucose 1) in 71% yield. To the glucose moiety of this sugar core, several protection/deprotection procedures were performed sequentially to obtain a fully acetylated sugar core 7 with a 4-OH group on the glucose moiety, in 57% yield in five steps. Thereafter, to the 4-OH group of the glucose moiety, selective 4-O-caffeoylation was achieved by proton-transfer esterification with 3,4-di-O-allylcaffeic acid 16 to give the caffeoyl disaccharide 11 in 97% yield. Then, it was converted to trichloroacetimidate 13 for a glycosylation donor in 90% in two steps. Finally, anomeric glycosylation was conducted with 2-oxo-2-(3,4-di-allyloxyphenyl)ethyl alcohol 19 with catalytic amounts of BF₃·Et₂O to give 2-oxo-2-(3,4-di-allyloxyphenyl)ethyl 2,6-di-O-acetyl-3-O-(2,3,4-tri-O-acetyl--l-rhamnopyranosyl)-4-O-(3,4-di-allyloxycaffeoyl)--d-glucopyranoside 14 in 60% yield. Deprotected intermediates of compounds 2, 11, 14, and 19 which were obtained in high yield would be useful for biological and medicinal studies of phenylpropanoid glycosides.Part of this study was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April, 2002     

Agroforestry in the arid zones of India

The arid regions of India cover over 300,000 km² and are spread over six States, mostly in the northwestern parts of the country. In spite of the hostile environmental conditions, several indigenous agroforestry practices are being practised in this region. The Central Arid Zone Research Institute (CAZRI) has made considerable progress in improving these indigenous practices and also developing new land use technologies some of which involve agroforestry approaches. Notable among these include sand-dune stabilization, shelterbelt plantations, tree planting techniques in difficult land forms, silvopastoral and agrisilvicultural systems, introduction and improvement of fruit trees and other indigenous trees, etc. Some of these technologies are adopted on a large scale by farmers in the arid zone of India, and have attracted international attention in other arid parts of the world. This paper is a summary of the results of these agroforestry initiatives of CAZRI.     

Crop productivity under differently lopped canopies of multipurpose trees in Central Himalaya, India

Ficus species are multipurpose trees well known by rural populations in Sahelian and Sudanian zones of Africa. Their uses are well documented but their amenability for vegetative propagation has not been extensively studied. This paper compares the rooting ability of stem and aerial root cuttings from thirteen Ficus species found in West Africa. It highlights the differences between species belonging to the sub-genera Sycomorus and Urostigma. The former show no capacity to propagate from cuttings whereas the latter, with epiphytic development, can be propagated by cuttings, although this capacity varies among species. Thus, F. thonningii, F. leprieurii and F. ovata are easily propagated, while F. platyphylla and F. elasticoides are propagated with difficulty. The rooting capacity also varies depending on the cutting material used. It decreases in the following order: long leafless hardwood cuttings (pole) > nodal cuttings > apical cuttings. Rooting potential increases when the cuttings are harvested towards the end of the dry season(March to May). Aerial root can be used for cuttings in all species of the sub-genus Urostigma. The capacity of root cuttings to regenerate is greatest when cuttings are collected at the beginning of the dry season (November). In this case, wound-induced adventitious roots arise at the basal end of the cutting while de novo buds are developed from the cambium at the distal end. The subsequent morphological development is identical to that of a stem cutting. These results clarify and allow the optimal use of the knowledge and methods developed by the indigenous people of the Sahel and could assist and promote fig tree (Ficus sp.) domestication in the dry tropics.This revised version was published online in November 2005 with corrections to the Cover Date.     

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     

Validation of a small-area method for estimating the spatial distribution of the degree of tree damage

This article presents a validation of a method, proposed in Podlaski (2003), for estimating the degree of tree damage. This method belongs to a group of small-area methods. To estimate the degree of tree damage in individual P₃ sub-blocks of the SINUS system of information on the natural environment, a classification based on the degree of defoliation was used. Spatial distribution of the degree of tree damage was estimated through unrestricted simple random sampling. The maximum total estimation error for proportions of fir and beech with a damage degree of zero, and also with second and third degrees jointly, reached a maximum of 35.6% for fir, and 33.8% for beech. P₃ sub-blocks characterised by the highest proportion of the healthiest trees (at least 15% being undamaged trees) occurred in patches in the case of fir, and in larger, compact areas in the case of beech. Because spatial diversification in the health of fir, and to a smaller degree in the case of beech, occurs at small scales, small-area methods for estimating tree condition are necessary. An analogous scheme, combining small-area with large-area methods (utilising sub-blocks of the network of large-area systems in a small-area inventory, and establishing a common database), could be used on a wider scale; for example, by supplementing the program of estimating tree health carried out by the United Nations Economic Commission for Europe (Lorenz et al. 2002) with local inventories.     

Antioxidative activity of tree phenolic constituents 1: Radical-capturing reaction of flavon-3-ols with radical initiator

The present work was undertaken from the standpoint of radical-capturing ability with regard to the antioxidative ability of flavonoids, especially flavonols distributed widely in woody plants. In regard to the flavonols, six methyl derivatives were initially prepared from quercetin and its litinoside. Their radical-capturing constants were determined strictly by the stopped-flow spectroscopic method. It was proved that the radical-capturing ability of quercetin mainly involves the vicinal C₃. and C₄, hydroxyl groups and the C₃ hydroxyl group. To clarify the reaction mechanism begun at the C₃ hydroxyl group of quercetin, 5,7,3,4-tetramethylquercetin (TMQ), flavon-3-ol (F30) and so on were treated with 2,2-azo-bis-(2,4-dimethylvaleronitrile) (AMVN). Six products (1–6) containing one depside and its two hydrolytic products, two valeronitrile adducts, and others were isolated from the reaction mixture of TMQ and their structures determined by instrumental analyses. Similarly, F30 gave four products, 7–10, which corresponded to the above products 1–3 and 5 (one depside, its two hydrolytic products, and one adduct), respectively. 3,5,7,3,4-Pentamethylquercetin (PMQ) and flavon-3-O-methylate (F3M) gave no products. The quantitative change of the products with reaction time was determined spectroscopically. An initial reaction pathway for the radical-capturing reaction of flavon-3-ols with AMVN was proposed based on the products and their amounts. The main route — formation of depside and its hydrolytic products via ketohydroperoxide (3) or ketohydroperoxy radical (4) - was similar to that of the oxidation reaction of quercetin with quercetinase and light.Part of this paper was presented at the 46th and 47th annual meetings of the Japan Wood Research Society, Kumamoto and Kouchi, April 1996 and 1997     

Specific degradation ofβ-aryl ether linkage in synthetic lignin (dehydrogenative polymerizate) by bacterial enzymes ofSphingomonas paucimobilis SYK-6 produced in recombinantEscherichia coli

Sphingomonas paucimobilis SYK-6 produces unique and specific enzymes, such as-etherases,O-demethylases, and ring fission dioxygenases, for lignin degradation. Cleavage of arylglycerol--aryl ether linkage is the most important process in the lignin metabolic pathway ofS. paucimobilis SYK-6. We reported the genes (ligD, ligE, ligF) for enzymes that cleaved-aryl ether linkage of dimeric compounds in previous studies. In this study we synthesized the fluorescent high-molecular-weight lignin (UBE-DHP) by dehydrogenative polymerization. We investigated the-aryl ether cleavage ability of these enzymes produced in recombinantEscherichia coli. When UBE-DHP was incubated with LigF, 4-methylumbeliferone was released as a result of-aryl ether cleavage of O-methylumbelliferyl--hydroxypropiovanillone (compound III) incorporated in UBE-DHP. Here, we report that-etherase ofS. paucimobilis SYK-6 can be expressed inE. coli and is able to cleave the-aryl ether linkage in synthetic high-molecular-weight lignin.     

The effect of strain, growth stage, and cultivating condition of Ganoderma lucidum on 5α-reductase inhibition

The inhibitory effects of 102 methanol extracts of 40 mycelia, 9 culture fluids, and 53 fruiting bodies of 40 strains of Ganoderma lucidum on 5-reductase were investigated. The methanol extract of the fruiting body of each strain was found to show the strongest 5-reductase inhibitory activity among the extracts tested.     

花吊丝竹居群遗传多样性的ISSR分析

[目的]研究花吊丝竹居群遗传多样性和遗传结构,为种质资源有效利用和良种选育提供理论指导。[方法]利用12条ISSR引物对48份种质(共3个居群)花吊丝竹居群进行遗传多样性和遗传距离分析。[结果]共检测到124个位点,其中,多态性位点为102个,种质和居群水平上的多态位点百分比(PPB)分别为82. 26%和50. 27%,Ne’基因多样性指数(He)分别为0. 220 4和0. 206 6,Shannon’s信息指数(I)分别为0. 349 4和0. 300 5,表明花吊丝竹居群间存在中等水平的遗传变异。根据Nei’s遗传多样性计算出不同居群间分化水平(Gst)=0. 163 3,表明16. 33%的遗传变异存在于居群间,居群内的遗传变异为83. 67%。居群间的基因流Nm为2. 562 1,表明花吊丝竹居群间存在较大基因流,很大程度减少居群间遗传差异。基于遗传距离的UPGMA聚类结果表明,48份种质可分为3组,3个居群可分为2组,居群间地理距离与亲缘关系无显著相关性。[结论]虽然花吊丝竹主要靠营养生殖来繁衍后代,其居群遗传多样性较丰富,且居群内遗传多样性大于居群间。此外,福建居群遗传多样性明显高于广西和广东地区居群。     

Semi-quantitative method to evaluate the α-carbonyl content in lignin

A method to estimate the content of -carbonyl structures in lignin was developed. This method consists of two successive treatments: NaBD₄ treatment of pulp to reduce an -carbonyl structure in lignin, and nitrobenzene oxidation. NaBD₄ was used to convert an -carbonyl structure to a deuterium-labeled hydroxymethine structure. The ratio of D-vanillin [(HO)(H₃CO)C₆H₃CDO] to H-vanillin [(HO)(H₃CO)C₆H₃CHO] or that of their syringyl analogues obtained by nitrobenzene oxidation was used as the measure of the content of -carbonyl structure. Model experiments demonstrated that when sodium hydroxide was used as alkali for the nitrobenzene oxidation, the retention of deuterium at the side chain -position was very low due to the displacement of deuterium with hydrogen by an unknown reaction mechanism. In order to depress this unexpected displacement, the reaction conditions of the nitrobenzene oxidation were modified. The modified nitrobenzene oxidation employs 0.5mol/l of lithium hydroxide as a reaction medium instead of 2.0mol/l sodium hydroxide. By this modification, this method could successfully trace the formation and the degradation of the -carbonyl structure in milled wood lignins.This paper was presented in part at the 11th International Symposium on Wood and Pulping Chemistry, Nice, France, June 2001 and at the 46th Lignin Symposium, Kyoto, Japan, November 2001     

小陇山锐齿栎天然林结构动态分析

[目的]为了解锐齿栎天然林群落动态变化过程。[方法]采用每木定位监测样地重复观测的方法,对甘肃小陇山林区百花林场王安沟营林区内的锐齿栎天然林进行研究,从树种组成及多样性结构、径级结构、空间结构等几方面分析了锐齿栎天然林群落的结构动态特征。[结果]表明:2次调查群落树种组成和优势树种的重要值排序变化不大,有2个稀少种退出群落,死亡林木40株,死亡率8.3%;群落乔木层的物种丰富度和树种空间多样性下降,优势树种的集中性变大,物种个体数目分配的均匀程度下降。林分径级结构由典型的反"J"型分布变化为左偏的单峰状曲线;群落的空间结构没有发生显著变化,林木分布格局仍为随机分布,中林层和上林层林木个体增加,垂直结构更趋复杂;树种隔离程度下降,建群种锐齿栎的优势度增强,膀胱果、白桦和青榨槭种群的优势度下降。[结论]锐齿栎天然林群落组成和结构变化是一个复杂和缓慢的过程,6年间仅发生了一些微小的波动。     

沙地樟子松天然纯林的结构特征

[目的]为了解红花尔基地区沙地樟子松天然纯林的结构特征,指导沙地樟子松的保护与经营。[方法]在红花尔基地区设置2块100 m×100 m的樟子松天然纯林固定样地,利用样地内每木定位调查数据和分析统计软件进行一元分布及二元分布特征分析。[结果](1)樟子松天然林纯林直径分布为单峰或多峰山状分布,垂直结构简单,只有乔木层和草本层。(2)樟子松天然纯林的林木分布格局为均匀分布,接近随机分布,林木分布格局类型与林分密度无关;林分中樟子松个体竞争激烈,多数单元中林木呈较密集状态。(3)2块样地中随机分布状态下的林木多数为中等密集或比较密集,不同分布状态下的林木优劣性差异较小;低密度樟子松天然纯林中多数密集状态的林木为绝对优势木或优势木,而高密度林分中林木密集度分布与林木大小无关。[结论]红花尔基沙地樟子松天然林结构不合理,应选择病腐木及聚集分布的个体作为潜在调整对象,进行密度调整和结构优化。     

基于MaxEnt模型的毛红椿适生区预测

[目的]了解环境因子对毛红椿适生区分布的影响,为其资源保护、引种及其人工林的发展提供参考。[方法]基于MaxEnt模型能利用现存不完整、小样本、离散型分布数据构建物种适生区预测模型,用受试者工作曲线线下面积(AUC)检验预测模型的精度,面积越大精度越高等优点,本研究应用毛红椿在云南的分布数据及1个地型因子和6个气候因子,来构建其适生区分布模型。[结果]毛红椿适生区分布MaxEnt模型平均训练AUC和平均测试AUC分别为0.891、0.885,说明对毛红椿适生区的预测是可靠的;降水量变异系数和最干季度降水量是决定毛红椿适生区分布的主要因子,年均气温变化范围、最冷季度平均气温、最湿季度降水量、最冷季度降水量是次要因子。在当代和未来(2050S、2070S)气候变暖条件下(RCP2.6情景),云南省和全国适生区面积计算结果直观、定量的反应了全球变暖对毛红椿适生区变迁的影响。[结论]预测云南省及全国的毛红椿适生区随全球变暖而小幅萎缩。     

草木樨中华根瘤菌CHW10B溶磷特性及其对南方红豆杉的促生作用

[目的]探讨南方红豆杉根际微生物草木樨中华根瘤菌(Sinorhizobium meliloti)CHW10B的溶磷特性及促生作用。[方法]利用液体发酵试验比较不同时间、碳源、氮源、碳氮比、培养温度等条件下CHW10B菌株的溶磷量,采用温室盆栽法研究该菌株对南方红豆杉生长的影响,并分析该菌株产嗜铁素、精氨酸脱羧酶、ACC脱氨酶及有机酸等成分的能力。[结果]该菌株分别在培养时间4 d、磷酸钙5.00 g·L~(-1)、初始p H值7.0、装液量1/2、NaCl为0.0 g·L~(-1)、温度30℃、碳源为葡萄糖、氮源为硫酸铵、碳氮比100∶1时溶磷能力最强。将该菌株接种于1年生南方红豆杉实生苗360 d后,苗木的地径、苗高、生物量比对照分别增长了19.53%、20.14%、25.39%。该菌株能够产嗜铁素、精氨酸脱羧酶、ACC脱氨酶(0.922 U·mg~(-1))和IAA(8.908 mg·m L~(-1)),并可分泌大量有机酸—葡萄糖酸(5 704.92μg·L~(-1))。[结论]草木樨中华根瘤菌CHW10B溶磷能力强,对南方红豆杉促生作用显著,适用于多种不同酸碱性土壤,可高效应用于南方红豆杉的人工栽培,具有被开发为生物肥料的潜力。     

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.     

5α-Reductase inhibitory component from leaves ofArtocarpus altilis

The inhibitory effects of 17 samples prepared from Thailand plants on 5-reductase activity were examined. The acetone extract of leaves ofArtocarpus altilis showed potent 5-reductase inhibitory activity. Fractionation guided by 5-reductase inhibition led to the isolation of 2-geranyl-2,3,4,4-tetrahydroxydihydrochalcone from the acetone extract of leaves ofA. altilis. This compound showed more potent inhibitory effect (IC₅₀=38M) than-linolenic acid known as a naturally occurring potent inhibitor.     

Preparation of liquid polyesterpolyols from glucose and its methyl derivative

Preparation of liquid polyols from d-(+)-glucose (Glc) and its derivative, methyl--d-glucoside (m-Glc), has been studied. Direct reaction of -caprolactone (CL) with Glc (CL:Glc = 2:1–5:1 in weight ratio) at 150°C using tin(II) 2-ethyl hexanoate (SnEht₂) (series A), in which melted Glc was suspended in CL, resulted in a dark-brown coloration of the reactants. The reaction was accompanied by formation of high molecular weight resins, a pH drop, production of water, and a considerable decrease in the hydroxyl value from the theoretically expected one. In the case of Glc/ethylene glycol (EG)/CL reaction system with SnEht₂ catalyst at 150°C (series B), in which the weight ratio of Glc to EG was fixed at 1:1, Glc dissolved in the EG/CL mixture, but the brown coloration of the reactant mixture still occurred. In this case, the formation of water was enhanced, but the other effects found in series A were suppressed to a considerable extent. In the m-Glc/CL/SnEht₂ reaction system (series C), in which m-Glc reacted with two to five times weight amounts of CL under the same conditions adopted in series A, development of the color, the production of high molecular weight materials and water, and the changes in pH and hydroxyl value were not observed. These results are discussed based on the chemical structural differences: Glc exists mostly in the hemiacetal form, but tautomerizes to the aldehyde, whereas m-Glc is an acetal and is protected from reversion to the aldehyde.     

The effects of sulfometuron on the root growth of loblolly pine

The effect of sulfometuron (Oust) on the root growth of loblolly pine (Pinus taeda L.) seedlings was studied in the field and in two soil types in the greenhouse. In the greenhouse study sulfometuron was applied to the foliage only, the soil only, and to both foliage and soil at the rates of 0.10, 0.21, and 0.42 kg ai/ha. Twenty-eight days after application root growth significantly decreased for all methods of application and with increasing rates e.g., 0.10, 0.21, and 0.42 kg ai/ha sulfometuron reduced new root length by 42%, 53%, and 64%, respectively. Application in the field at the rate of 0.30 kg ai/ha resulted in a 68% reduction in root growth. However, by the end of the growing season treated seedling root and shoot biomass were 115% and 64% greater, respectively. To ensure earlier season survival the rate of sulfometuron applied should be kept at a minimum level that will allow both weed control and adequate root growth. Low rates would be particularly important during a dry planting season.     

我国樟子松人工林天然更新研究进展

樟子松人工林天然更新问题的研究一直在进行,但人工林内幼苗数量过少及难以发育为幼树的问题一直难以彻底解决。文中综述了影响我国沙地樟子松人工林天然更新能力的因素,如光照、温度、水分、土壤环境、生物因子及人工营林技术等的研究概况。在研究过程中发现,樟子松人工林的遗传多样性与土壤微生物对樟子松人工林天然更新影响方面的研究尚少有报道,或可以为解决樟子松人工林天然更新问题提供更深入的思路。