Reactivity of secondary hydroxyl groups in methylβ-d-xylopyranoside toward aβ-o-4-type quinone methide

Methyl-d-xylopyranoside was allowed to react with-O-4-type quinone methide without a catalyst to elucidate the reactivities of secondary hydroxyl groups at the C2, C3, and C4 positions. Benzyl ether-type lignin-carbohydrate complex (LCC) compounds linked at the C2 and C4 positions were predominant, at a ratio of 23. However, the reactivity of the hydroxyl group at the C3 position was quite low. These results strongly suggest that the reactivity of the C2 hydroxyl group in xylan toward quinone methide intermediate is higher than that of the C3 hydroxyl group during biosynthesis of LCCs.     

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     

Effect of the ethylene/vinyl acetate ratio of ethylene-vinyl acetate emulsion on the curing behavior of an emulsion polymer isocyanate adhesive for wood

We investigated the curing behavior of an emulsion polymer isocyanate adhesive for wood with different ethylene-vinyl acetate (EVA) emulsions, because it was found that the ethylene/vinyl acetate weight composition (E/VA ratio) of EVA could control the volume of gas emitted from the adhesive. EVA with higher VA content reduced the volume of gas emitted at the initial stage, which was caused by the extent of the reaction between the NCO groups and water. The reaction scheme of NCO could not be determined because the broad infrared (IR) absorptions due to CaCO3 and water masked the information of the NCO products in IR spectra. Examination of the degree of swelling suggested that the adhesive films stored for 3 weeks had the same degree of cross-linking structure in spite of the variation of EVA. This result was supported by IR spectroscopy, which showed the same amounts of NCO remained in these films. All the adhesives prepared in this study had satisfactory bond performance. The findings indicate that the E/VA ratio affects the curing behavior of the adhesive in the initial curing stage, whereas the cross-linking structure and the bond performance were independent of the E/VA ratio after storage for 3 weeks. Part of this report was presented at Wood Adhesives 2005, November 2–4 2005, San Diego, CA, USA     

Simultaneous evaluation of bending and shear moduli of wood and the influence of knots on these parameters

Summary This paper presents a method of simultaneous evaluation of bending and shear moduli of wooden beams. The method, which is based upon the measurement of two natural frequencies of a beam, is simple to perform. Existing techniques for determining shear moduli of wood based materials are either too cumbersome to carry out or prone to measurement errors. Using this method tests were conducted on matched groups of clear and knotty specimens. It was found that for clear specimens a value of 20 can be assumed for the E to G ratio. For specimens which contain knots the variation was so large that no corresponding figure can be suggested with confidence. But the ratio for knotty materials is though to be higher than 20.Symbols A cross sectional area - E modulus of elasticity in bending - G shear modulus - I second moment of area - K shear shape factor - L span - P load - m mass per unit lenght - t time - x distance along the length of a beam - v transverse displacement - angular natural frequency This work was undertaken with financial support from the Natural Sciences and Engineering Research Council of Canada under Special Support for Forestry Grant No. FRP0030800. Thanks are also due to Dr. I. Smith for his contructive comments and permission to use the test facilities at the Wood Science and Technology Centre, and to Miss L. J. Hu for conducting the tests.     

Chemical composition and antioxidant capacity of the aqueous extract of <Emphasis Type="Italic">Phellodendron amurense</Emphasis>

The aqueous extract of Phellodendron amurense Rupr. (Amur Cork Tree) provides a rich source of antioxidants and chemical compounds, and can be used for food and wood preservative materials. In this study, we characterized the chemical composition of this extract by GC and GC/MS. The antioxidant capacity was evaluated using a variety of antioxidant assays (superoxide radical, hydroxyl radical, nitric oxide radical, and DPPH radical scavenging activity). Additionally, total polyphenolic content was determined. Phenolic acids and acetone derivatives were major compounds of the extract capable of scavenging the DPPH free radical and reducing ferric ions. DPPH and ferric ion reduction results were strongly correlated with total phenolic content of the extract which also exhibited strong nitric oxide, hydroxyl radical scavenging and superoxide anion radical scavenging activities.     

Monomolecular adsorption and crystallite diameters of cellulose from structural and adsorption considerations

Calculations of the monomolecular water vapor adsorption by three different celluloses (cotton, wood pulp and cellophane) from structural considerations are in agreement with the BET determined values for crystallite diameters of 16 to 200 on the basis of adsorption being confined to the fraction f of the three hydroxyl groups per anhydroglucose unit that are available on the surface of the crystallites and within the amorphous zones, when f ranges from 0.16 to 0.29. These low values of f are compatible with the fact that the void volume of the amorphous zones does not exceed about 6%. More exact values for f are needed before more definite values for the crystallite diameters can be estimated. A modified fringe micelle diagram containing a considerable amount of chain association in the amorphous zones is given that meets the requirement dictated by the calculations. Another approach, involving direct estimation of the adsorbing surface areas of crystallites and amorphous zones, on the basis of adjacent surfaces being shared by water molecules adsorbed between them, gives surface areas somewhat larger than the BET values using the same f values. Agreement with values from the former approach is obtained if only 75% of the surface per anhydroglucose unit is considered effective for adsorption.     

Preparation of novel reagents 4-alkoxytrityl chlorides and their reaction with methyl Α-d-glucoside

A series of novel 4-O-alkoxytrityl chlorides (1) with different chain lengths was synthesized as a novel reagent for obtaining 6-O-alkylated cellulose with high regioselectivity via trityl groups in one reaction step without the use of any protective groups. These chlorides were reacted with methyl -d-glucoside, which was used as a model compound, to examine the reactivities toward the primary hydroxyl groups of cellulose to afford a series of 6-O-alkylated methyl -d-glucosides in high yields. The product compounds were found to have interesting solubilities and thermal properties. Thus, newly prepared trityl chloride derivatives were found to be useful regioselective derivatization reagents on the primary hydroxyl group in carbohydrates, especially in cellulose.     

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.     

Fracture characteristics of PARALLAM® PSL in comparison to solid wood and particleboard

Summary Typical fracture characteristic values like load-displacement curve and specific fracture energy of the new wood laminate compound PARALLAM® PSL were determined by using the wedge splitting technique. Comparison with the values of solid wood and particleboard showed the superiority of this wood composite in both weak transverse orientations. This result is explained by the favourably oriented wood strands in PARALLAM® PSL with a length up to 2.6 m, which give rise to crack arresting mechanisms. In addition the influence of specimen geometry on the critical load and corresponding loadpoint-displacement at crack initiation was calculated for both isotropic and orthotropic materials using linear elastic FE-models.The authors thank Trus Joist McMillan for supplying the testing material and especially Dir. Donald Sharp for his helpful cooperation. Financial support by the Austrian National Bank (project no. 4917) is gratefully acknowledged.     

Examination of within-tree variations and the heights representing whole-tree values of derived wood properties for quasi-non-destructive breeding of Eucalyptus camaldulensis and Eucalyptus globulus as quality pulpwood

Within-tree variations of derived wood properties of Runkel ratio, Luces shape factor, slenderness ratio, and solids factor were examined for Eucalyptus camaldulensis and Eucalyptus globulus trees and the tendency difference in the within-tree variations between individuals and between species, in both radial and axial directions by statistical data analysis. These properties are important for quality breeding of pulpwood. In both species, within-tree variations were generally observed as higher values in the upper and outer parts compared with other parts of the trunk for Runkel ratio and Luces shape factor. In E. camaldulensis, within-tree variations were observed as higher values in the upper and outer parts compared with other parts of the trunk for slenderness ratio and solids factor. In E. globulus, within-tree variations were observed as higher values in the outer parts compared with other parts for slenderness ratio and solids factor. However, significant difference of tendency was observed in radial variation between individuals of E. globulus for Runkel ratio and in both radial and axial variations between species for solids factor. Furthermore, within-tree variations of derived wood properties were analyzed to determine a sampling height in the trunk which can be used to represent whole-tree values. Representative heights of derived wood properties from two trees were found to be 2.8m in E. camaldulensis (except for Runkel ratio and Luces shape factor) and 1.8m in E. globules (except for Runkel ratio), regardless of differences in tree height (growth rate) and in tendency of within-tree variation of derived wood properties.     

木质室内装饰材料的环境湿度调节功能Ⅲ

本研究测定了在水蒸汽流入流出过程中壁纸、椴木三合板、柞木地板块、两面光ＭＤＦ这４种室内装饰材料的环境湿度调节参数ｘ和ｙ与气积比Ａ／Ｖ、试材初含水率及环境温度之间的关系曲线。在此基础上,得到了在水蒸汽流出条件下室内装饰环境的湿度设计诺谟图,为科学、全面地进行居住空间的湿度设计奠定了理论基础。     

Collapse,volumetric shrinkage,specific gravity and extractives in Eucalyptus and other species

Summary The influence of extractive content on the shrinkage behaviour in eucalypts was shown by mathematical extraction after making certain assumptions with respect to available data. The slope of the volumetric shrinkage/specific gravity (S/) ratio changed from negative to positive after the theoretical removal of alcohol/benzene/water soluble or NaOH soluble extractives. Statistical analysis of available data suggested that collapse was positively related to the encrusting and extraneous materials and negatively related to the polysaccharide cell wall component. Conversely, normal volumetric shrinkage was positively related to the polysaccharides and negatively related to lignin and extractive content. Mechanisms by which extractive content might influence collapse development were discussed. R-values (change in external volume during shrinkage or swelling per change in weight of equivalent volume of water) appeared to be negatively correlated with extractive content in eucalypts and calculations for other species showed that R progressively increased with cold and hot water extraction. Further analysis suggested that the apparent change in lumen dimensions suggested by particular R-values was mitigated by the bulking effect of extractives in the cell wall. A possible role for R as an indicator of dimensional stability was postulated.     

Image analysis to measure strain in wood and paper

Summary A fast and accurate strain measurement method was developed to quantify microscopic deformation in wood and paper using video images. Two or more video images, one of which was undeformed and the others of which were deformed, were digitized and compared using the image correlation technique. This digital computer pattern recognition technique permitted the displacement of any point in the image to be measured. Then, strain between any two points in this observation field could be calculated and, hence, normal, shearing strains and Poisson's ratio could be measured directly. Independent strain measurements showed that the method using video images provided accurate strain measurements and could be applied to complex materials like wood and wood products. The strain measurements using the image analysis produced not only normal strains but strain profiles of the normal strains. From the strain profiles, it was possible to detect local areas of strain concentration which might be beyond the elastic range. As it measures displacements and strains from a set of video images using the image correlation technique, the method is non-contact and the observation field can be adjusted easily by changing magnifying power of the optical devices. Thus, the method can be applied to mechanical testing of wood and wood products from the cellular level to full size lumber and will no longer be limited by the fragile nature of the material being tested, industry standards, or equipment restrictions.Authors are grateful to U.S.D.A. for supporting this investigation which is a part of the USDA funded project Initiation and Propagation of Failure in Wood. Authors are also grateful to N. C. Brown Centre for Ultrastructure Studies, CESF, SUNY, Syracuse and Empire State Paper Research Institute, Syracuse for providing research facilities     

Creep in chipboard

Summary Matched samples to those used in a previously reported investigation (under constant environments employing eight board materials and solid wood) were subjected to five different levels of stress under four different cyclic environments for periods of six months. Relative creep increased slightly and linearly with respect to stress within the range of stress levels adopted, as well as increasing with severity of the environment. All materials showed greater sensitivity to alternating humidity than to alternating temperature. The effects of the three prinicipal variables (stress level, environment, material), and the strong interactions among them, were quantified using analysis of variance and found to be similar to those under constant environments: the effect of environmental condition was found to be far greater on relative creep than that of either stress level or material. Averaging over all conditions and stress levels, relative creep increased progressively among timber, plywood, waferboard, chipboard and fibreboard, though this ranking order varied at different stress levels and environments due to the presence of strong interactions. At a stress level of 30% and a time of 43,200 minutes, the relative creep under alternating humidity of 3090% was on average fourteen times greater than that under a constant humidity of 65% (averaging across the nine materials); however, there was considerable divergence among the materials in this ratio. At the same level of stressing, the mean relative creep for all materials under an alternating temperature of 1030 °C was 1.6 times higher than at a constant temperature of 20°C. The ranking order of materials in their sensitivity to alternating temperature was different to that under alternating humidity.The statistical analyses in this paper were performed under contract to Building Research Establishment by Laura New of the Statistical Services Centre, Reading University     

Thermal properties of interior decorating material and the sensation of cold/warm by contact II: the relations among heat flux, temperature change of material, and sensation of cold/warm by contact

The main purpose of this study was to investigate the changes in heat flux and temperature after the subject's palm was in contact with interior decorating materials. The relations among heat flux, temperature, and sensation of cold/warm during contact were studied. Ten men and ten women were selected and introduced to 21 materials for the contact test. They were in contact with the specimens for 30min without seeing them in a climate-controlled room at 25°±1°C and 65% RH. Changes in the heat flux and temperature of the specimens were determined by a heat flux meter. A sensory evaluation test was applied to evaluate the cold-warm contact. Results indicated that the heat flux and temperature increased with increasing time after the subject's palm was in contact with the specimens. The heat flux (Q ₃₀) and temperature (T ₃₀) 30min after the subject's palm contacted the specimens were greater for male subjects than for female subjects. A positive linear regression equation existed between the values for Q₃₀ andT ₃₀, whereas a negative linear regression formula existed the sensation of cold-warm by contact (5) and the values of ln(Q ₁·). Therefore, the sensation of cold/warm by contact could be estimated simply by using the thermal physical properties of the interior decorating materials.Part of this report was presented at the International Conference on Effective Utilization of Plantation Timber, Chi-Tou, Taiwan, ROC, May 1999     

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.     

Screening of heterozygous DNA markers in shiitake (Lentinula edodes) using de-dikaryotization via preparation of protoplasts and isolation of four meiotic monokaryons from one basidium

A suitable screening method for heterozygous DNA markers in shiitake,Lentinula edodes (Berk.) Pegler, is reported. Monokaryons were derived from a dikaryon by de-dikaryotization via protoplast formation. Compatibility of the monokaryons was determined by pairwise culture on agar plates. We selected the primers to amplify polymorphic fragments among the original strain (Hokken600H600) and two monokaryons (H600PP-39 and H600PP-67) showing compatibility. A total of 135 fragments were selected as specific random amplified polymorphic DNAs (RAPDs) resulting from 56 primers of the 147 primers tested. Furthermore, we tested whether the polymorphic fragments segregated into 22 among four strains isolated from a basidium. Most of the polymorphic fragments (about 97.8%) showed 22 segregation among the four strains. We concluded that the polymorphic fragments were heterozygous if they were detected in either of the monokaryons (H600PP-39 and H600PP-67) and segregated to 22 among four meiotic strains (H600B-1,-2, -3, and -4). A total of 132 heterozygous DNA markers were therefore selected from a dikaryon of shiitake (Hokken600H600).Part of this report was presented at the 8th Annual Meeting of Mushroom Science and Biotechnology and the 47th Annual Meeting of the Japan Wood Research Society, Kochi, 1997     

Collapse,volumetric shrinkage,specific gravity and extractives in Eucalyptus and other species

Summary An examination of shrinkage behaviour in a range of tree species has demonstrated clear differences between eucalypts and other species with respect to the volumetric shrinkage (S)/specific gravity () ratio. The equation S=f proposed by Stamm (1935a, 1952) to relate this ratio to the fibre saturation point (f) was inapplicable in eucalypts, both before reconditioning, where a highly negatively significant linear correlation was observed between S and , and after reconditioning where the correlation was not significant and the regression line indicated S to be nearly constant. Collapse was found to be highly negatively correlated with specific gravity in the eucalypt species and evidently was primarily responsible for the negative S/ relationship before reconditioning.In non-eucalypts S and were highly positively correlated, but the regression line did not pass through the origin and the slope was 10 to 14% less than the value of 28% suggested by Stamm for f. Only when the regression line was artificially forced through zero did the slope approach postulated fibre saturation point values. A power function was proposed as representing a more reasonable fit of the data.In line with these analyses, unit shrinkage (S_u) was shown not to be equivalent to . This lack of equivalence was expressed as S_u divided by basic density () which was termed the R-ratio and which was shown to be equal to the change in volume during shrinkage (or swelling) divided by the associated change in the weight of an equivalent volume of water. R was seldom equal to one, as required by the Stamm formula, and was negatively correlated with specific gravity in both eucalypts and non-eucalypts. A comparison of regression equations showed R values for eucalypts to be significantly different from those of non-eucalypts. Possible uses for the R-ratio were considered.     

Simple method for synthesizing phenolicβ-O-4 dilignols

A modified synthetic method for phenolic-O-4 lignin substructure model dimers was developed involving protection of the phenolic hydroxyl group of acetophenons with benzoyl chloride, bromination with 4-dimethylaminopyridiniumbromide perbromide, condensation with phenols in the presence of 18-crown-6-ether, condensation with paraformaldehyde, reduction with NaBH₄ and debenzoylation. This method results in shorter reaction times and increasing yields without the application of strict anhydrous and drastic conditions or chloric solvents. This alternative route could be applied to the-O-4 dilignol syntheses of four combinations of guaiacyl and syringyl derivatives.     

Antifeedant activity of flavonoids and related compounds against the subterranean termiteCoptotermes formosanus Shiraki

Antifeedant activity of some flavonoids and their related compounds against the subterranean termiteCoptotermes formosanus Shiraki was examined with nochoice tests and two-choice tests. The activities of these compounds were evaluated in relation to their chemical structures. All flavonoids tested showed antifeedant activity, whereas catechinic acid, possessing no A-ring or pyran ring in the molecule, showed feeding-preference activity. For the structure-activity relations, it was found that compounds containing two hydroxyl groups at C-5 and C-7 in A-rings showed high antifeedant activity. Furthermore, the presence of a carbonyl group at C-4 in the pyran rings of the compounds was necessary for the occurrence of high activity. 3-Hydroxyflavones and 3-hydroxyflavanones with 3,4-dihydroxylated B-rings exhibited higher activity than those with 4-hydroxylated B-rings.Part of this paper was presented at the 49th annual meeting of the Japan Wood Research Society, Tokyo, April 1999