Origin of free radicals produced from the syringyl end groups in lignins

Enzyme lignin was prepared from reed; it was acid-hydrolyzed and reduced with NaBH₄. Spin concentrations of radicals produced by oxidation of the lignins with K₃[Fe(CN)₆] or H₂O₂ were determined from electron spin resonance spectra. The radicals were observed by the oxidation of sinapyl alcohol. It was found that the two radicals observed by the oxidation of dioxane lignins were deprotonated 2,6-dimethoxyp-benzosemiquinone and 6-hydroxy-2-methoxy-p-benzosemiquinone, and that they were produced from syringyl end groups. The production rate of radicals from syringyl end groups possessing an-carbonyl group was greater than that possessing an-hydroxyl group. It was suggested that stilbene-type syringyl end groups were produced from phenylcoumaran moieties in lignins by acidolysis. The radicals produced from guaiacyl end groups were not observed by the oxidation process.     

Phenolization of hardwood sulfuric acid lignin and comparison of the behavior of the syringyl and guaiacyl units in lignin

To study the behavior of hardwood sulfuric acid lignin (SAL) during phenolization, we compared the product yield, average molecular weight, methoxy content, and reactions of simple model compounds with those of softwood SAL, focusing on the difference between syringyl and guaiacyl units. The beech SAL reacted with phenol more readily than red pine SAL and yielded a larger soluble fraction of phenolized SAL. To investigate the difference in the phenolization activity of the syringyl and guaiacyl units in beech lignin, we prepared syringyl-nucleus-rich sulfuric acid lignin (S-rich-SAL) and guaiacyl-nucleus-rich sulfuric acid lignin (G-rich-SAL) from beech, which were subjected to phenolization. The results suggest that the syringyl unit in SAL had greater phenolization activity and its phenolized products were more soluble in acidic aqueous medium and introduced less phenol than the guaiacyl unit. Using model compounds, the study also showed that the syringyl unit had higher phenolization reactivity than the guaiacyl unit.     

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     

Differences of raw cork quality in productive cork oak woods in Sicily in relation to stand density

Differences of raw cork quality, in terms of thickness and porosity, were observed in productive cork oak (Quercus suber L.) stands in the Nebrodi and Iblei mountains of Sicily in relation to stand density. Five study areas were chosen across a range of different stand density satisfying specific sampling requirements among two managed cork oak woods.Analysis of variance using Fisher–Snedecor‘s F test (p < 0.05) were used to identify statistically significant differences of cork quality and sylvicultural, dendrometric and cork stripping parameters between study areas within each stand. Relationships between cork quality and sylvicultural and dendrometric parameters were also tested using Pearson's correlation coefficient (r). Results shown that sylvicultural practices are a key factor influencing cork quality: statistically significant differences in cork thickness and crown area were observed between areas at different stand density; positive correlations were found between cork thickness and crown area in lower density study areas favouring a significant vegetative activity; negative correlations were found between parameters of cork stripping (cork stripping coefficient, cork stripping surface, maximum height of cork stripping) and cork thickness. No correlations were found between cork porosity and dendrometric or sylvicultural parameters, demonstrating the probable genetic origin of cork porosity. Results shown that cork quality parameters and stand attributes may be used in sustainable management models of cork oak forests.     

Reactivity of syringyl quinone methide intermediates in dehydrogenative polymerization I: high-yield production of synthetic lignins (DHPs) in horseradish peroxidase-catalyzed polymerization of sinapyl alcohol in the presence of nucleophilic reagents

It is known that the conventional dehydrogenative polymerization of sinapyl alcohol (S-alc) gave syringyl synthetic lignins (S-DHPs), but in extremely low yields. In this article, to examine the contribution of syringyl quinone methide intermediates (S-QM) on S-DHP production, horseradish peroxidase (HRP)-catalyzed dehydrogenative polymerization of S-alc was carried out in the presence of nucleophilic reagents that promote the rearomatization of S-QM. First, the HRP-catalyzed polymerization of sinapyl alcohol γ-O-β-D-glucopyranoside (isosyringin, iso-S), which allows us to monitor the polymerization process in a homogeneous aqueous phase, was utilized for screening of a nucleophile used as an S-QM scavenger. Monitoring of iso-S polymerization in the presence of various nucleophilic reagents by UV spectroscopy and gel permeation chromatography with photodiode array detection (GPC-PDA) revealed a high ability of azide ion to convert oligomeric S-QM efficiently to S-DHP. Accordingly, azide ion was utilized as an S-QM scavenger in HRP-catalyzed polymerization of S-alc, which resulted in high-yield production of S-DHPs (∼83%), as expected. The ¹H-, ¹³C-, and 2D-HSQC NMR investigations on the resulting S-DHPs clearly demonstrated that azide ion efficiently performed nucleophilic additions to the C-α of S-QM during the polymerization. These results provide experimental proof that the low reactivity of S-QM with nucleophiles (such as water, phenolic, and aliphatic hydroxyl groups) in the conventional polymerization system critically impedes the production of S-DHPs from S-alc.     

Formation and chemical structures of acid-soluble lignin II: reaction of aromatic nuclei model compounds with xylan in the presence of a counterpart for condensation,and behavior of lignin model compounds with guaiacyl and syringyl nuclei in 72% sulfuric acid

To elucidate the formation and chemical structures of water-soluble material in acid-soluble lignin (ASL), lignin aromatic nuclei model compounds of creosol (I) and 5-methoxycreosol (II) were reacted with xylose or xylan in the presence of apocynol as a counterpart for condensation in 72% sulfuric acid (SA). The reaction of I gave mainly condensation product. However, the condensation reaction of II with apocynol was suppressed because of steric hindrance from the methoxyl group, and II yielded a C-xyloside after refluxing in 3% SA together with condensation products. To obtain information on CHCl₃-soluble material in ASL, model compounds of arylglycerol--aryl ethers with guaiacyl (VIII) and syringyl (X) nuclei were treated by the Klason procedure. VIII gave only insoluble polymerized product, while X gave insoluble polymerized product and CHCl₃-soluble low molecular weight products, which were dissolved in 3% SA. These results prove earlier views that water-soluble material in ASL consists of condensation products formed from syringyl lignin and monosaccharide units in hemicellulose. In addition, the CHCl₃-soluble material in ASL appears to be composed of low molecular weight degradation products from SA treatment of Klason lignin with the syringyl nucleus.Part of this report was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001 and at the 47th Lignin Symposium, Fukuoka, October 2002, and was reviewed in Mokuzai Gakkaishi (2002) 48:55–62     

The carboxymethylation of organosolv and kraft lignins

Summary Kraft and ethanol organosolv lignins from Picea abies and Fagus sylvatica were carboxymethylated with bromoacetic acid. Of the total hydroxyl groups in the lignins, 60–70% were carboxymethylated. The reaction led to an increase of the number-average molecular weights. The moisture adsorption of the carboxymethylated products is about one and a half as high as that of the original lignins. There are no remarkable differences between the solubilities of the treated and untreated products.The authors wish to express their appreciation to Mr. Dietrich Meier, Federal Research Organization for Forestry and Forest Products, Hamburg, Federal Republic of Germany, for preparation and donation of lignin samples     

Fire-retarding properties of nano-silver in solid woods

Fire-retarding properties of 200?ppm nano-silver solution, with a size ranging from 20 to 80?nm, on five woody species were studied and compared with Borax and Celcune ^? . Blocks of 150?×?130?×?9?mm3 were prepared and divided into four groups of control samples, nano-silver-, Borax-, and Celcune-impregnated specimens. A special apparatus was designed, and six fire-retarding properties of each specimen were measured, namely ignition, glowing, back-darkening and back-holing times, as well as length and width of burning. Results showed that all three kinds of treatments had improving effects on the fire-retarding properties. Celcune showed the best improvement on glowing time. Cluster analysis showed direct relation between density and fire-retardant properties; also, fire-retarding behaviors of the four hardwoods were quite different to those of the one softwood. Furthermore, there are improvements in some fire-retarding properties of nano-silver-impregnated specimens that are in connection with its heat-transfer property.     

Characterization and antioxidant activity of Amazonian woods

The heartwood and sapwood characteristics of 11 Amazonian trees were investigated. Whereas 7 of the specimens had densities greater than 0.7 g/cm³, the heartwood density of ipê amarelo (Tabebuia serratifolia), maçaranduba (Manilkara huberi), cumaru-ferro (Dipteryx odorata), and guarita (Astronium lecointei) exceeded 1.0 g/cm³. Jatobá contained small amounts of Klason lignin and α-cellulose, and large amounts of holocellulose and alkali extract, suggesting that it has a high polysaccharide content that can be dissolved in an alkaline medium. The difference in the syringyl/guaiacyl (S/G) ratios of the samples before and after alkali extraction suggests that alkali extracts contain syringyl-type polyphenols. In all of the samples, the heart-wood methanol extracts were larger in volume than the sapwood methanol extracts, and the sapwood alkali extracts were larger in volume than the heartwood alkali extracts. The antioxidant activities of the methanol and alkali extracts were assayed by measuring the levels of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity and super oxide dismutase (SOD)-like activity, respectively. The heart-wood methanol extract of jatobá (Hymenaea courbaril) exhibited the highest level of activity (EC₅₀ = 44 mg/l), which exceeded that of α-tocopherol (EC₅₀ = 48 mg/l), and the heartwood alkali extracts of jatobá and ipê amarelo had high SOD-like activity comparable with red wine.     

几种木材中硅石的研究

要实现木材-无机质复合材的人工模拟,其关键还是在于研究和探讨木材生物矿化的机理,因此要对木材中无机物的情况进行研究,从而获取生物矿化所形成的木材/无机质复合材料的形成机理,以此来指导木材的生物改性或木材/无机复合材的仿生合成。本文采用光学显微镜对几种木材/二氧化硅生物矿化复合材中硅石的分布进行观察发现:硅石主要分布在木射线细胞中,大量的晶体在木射线细胞以及轴向薄壁细胞中均有分布;采用重量法对几种木材/二氧化硅生物矿化复合材中二氧化硅含量情况进行测定表明:子京、山油柑、柚木、柠檬桉、山竹子等5种木材/二氧化硅生物矿化复合材中二氧化硅含量分别为1.5106%、0.8941%、0.8654%、0.2155%、0.1676%。     

Behavior of the cellulose microfibril in shrinking woods

We measured the longitudinal and tangential shrinking processes in wood specimens from Chamaecyparis obtuse Endl. with different microfibril angles (MFAs). The shape of the shrinking curve was compared with the MFA. Only the longitudinal shrinking process of specimens with a small MFA clearly showed nonlinearity, and the degree of nonlinearity increased as the MFA decreased. In contrast, the tangential shrinking process and the longitudinal shrinking process of compression wood with a large MFA were linear. The nonlinearity is probably caused by the longitudinal shrinkage of the noncrystalline region of the cellulose microfibril (CMF) in regions of low moisture content during water desorption. When the moisture content is high, the matrix substance in the cell wall begins to dry; however, the shrinkage in the chain direction is restrained by the rigid CMF. As the wood dries further, the noncrystalline region of the CMF embedded in the matrix substance begins to shrink. Because the longitudinal mechanical behavior of wood with a small MFA is greatly affected by a rigid CMF, longitudinal shrinkage increases suddenly at about 10% moisture content; as a result, the shrinking process shows nonlinearity.     

GREUNEISEN FORM OF STATE EQUATION OF WOODS

THEBASICTHERM0-DYNAMICFUNCTI0NOFW0ODThephysicalcharactersofwoodaremainlydependentonthecompositionofcellwall.Andthecelluloseisthemaincomponent,aswellastheframeworkma-terialofcellwall.Thecrystallinestructureofthecellu1osebe1ongstomonoclinicsys'tem.Regardingthewoodflbersasmo1ecu-larcrysta1swhichhavethecomp1exlattice,bystatistictheoryatheoreticalformulaofwoodtherma1capacitywasderivedatcon-stantvo1ume.C.=28RnD(H./T)(l).'Where:R--gasconstantn--molarnumberT-thermodynamictemperatureHD…     

Orientation distributions of cellulose crystallites in Pinus densiflora woods

Summary Pole figures were described for (101), (101), (002) and (040) crystallographic planes of cellulose crystallites in opposite, normal and compression woods of Pinus densiflora. The orientation functions for these planes were plotted on the equilateral triangular coordinate. The orientation factors were calculated from the functions. It was found that the cellulose crystallites in the S₂ layer contributed to the orientation distribution although those in the other layers also contributed to some extent. From the equilateral triangular coordinate plots it was found that the orientation distributions of cellulose crystallites in wood varied in some kind of regular fashion. This was more clearly confirmed by the variations of the orientation factors.The authors are indebted to Dr. Keizo Okamura, Faculty of Agriculture, Kyoto University, Kyoto, Japan, and Dr. Misato Norimoto, Wood Research Institute, Kyoto University, Uji, Kyoto, Japan, for their valuable discussions and comments on this paper     

灌木林有害生物发生危害现状与治理对策

灌木林是我国生态系统中不可或缺的重要组成部分,是生态安全的重要保障,而且具有极其重要的经济价值。文中根据相关资料和灌木林有害生物调查结果,对我国灌木林的发展现状、灌木林有害生物的发生与危害情况进行扼要概述,并提出我国灌木林有害生物的可持续控制建议。