Non-steady state water adsorption of wood

Summary The validity of the following equation of water adsorption into wood substance which was derived in the previous report, is examined: d(W)/dt = k₀(1 – exp(-k₁/t))W(l – W), which can approximately be written as: d(W)/d(logt) = rW(l – W), where W is moisture content; t is time (t > 0); k₀, k₁ and r are constants. After measuring dimensional change with change in time under various relative humidities, the change of moisture content was indirectly calculated from the proportional relationship between dimensional change and moisture content. It was found that the theoretical equation satisfactorily agreed with the experimental results. These results lead to the conclusion that the equation was valid. Furthermore, the properties of the equation, whose constants are determined from experimental results, is discussed. The rate of water adsorption of wood shows interesting and systematical properties, especially near relative humidities corresponding to the fiber-saturation point.     

Suitability of acetylated woods for clarinet reed

The density (), dynamic Young's modulus (E), loss tangent (tan_L) in the longitudinal (L) direction, and the dynamic shear modulus (G), loss tangent (tan_S) in the LT or LR (T, tangential; R, radial) plane of woods and cane (Arundo donax L.) in air-dried and wet conditions were measured. The acoustic converting efficiency (ACE), expressed by E/³/tan_L, and the factors of anisotropy, expressed byE/G and tan_S/tan_L, of woods were compared with those of the canes. Low-density coniferous woods had higher ACE values and were of a more anisotropic nature than the cane. These woods seemed appropriate for clarinet reed owing to their homogeneous cellular structure. The stability in vibrational properties and the anticreep properties of the woods were enhanced by the acetylation treatment. Professional clarinet players suggested that acetylated Glehn's spruce and sitka spruce were suitable for clarinet reeds.Part of this report was presented at the 48th annual meeting of the Japan Wood Research Society at Shizuoka, April 1998     

Influence of moisture content on the vibrational properties of hematoxylin-impregnated wood

The vibrational property of hematoxylinimpregnated wood was investigated from the aspect of moisture content dependence. The specific dynamic Young's modulus (E/) and loss tangent (tan) of hematoxylin-impregnated wood were determined in the relative humidity (RH) range of 0%–97%, and were compared with those of the untreated and some conventional chemically treated woods. The changes in theE/ and tan of wood with increasing RH were suppressed by acetylation and formaldehyde treatment because of a marked reduction in the hygroscopicity of the wood. Although the hematoxylin impregnation did not significantly affect the hygroscopicity of the wood, its influence onE/ and tan were similar to that of formaldehyde treatment at low RH and of acetylation at medium RH. It was supposed that at low to medium RH hematoxylin restrains the molecular motion of amorphous substances in the cell wall because of its bulkiness and rigidity. On the other hand, at high RH it seems to work as a plasticizer with adsorbed water molecules.     

Changes in the physical and chemical properties of six Japanese softwoods caused by lengthy smoke-heating treatment

The effects of prolonged smoke-heating treatments on wood quality were investigated. Six Japanese softwoods were smoke-heated for 100 and 200h at a temperature of 75° ± 5°C, which was recorded inside the log. After smoke heating, wood quality, including moisture content, amounts of chemical components, relative degree of crystallinity (RDC) of cellulose, and sapwood color were examined. Moisture content decreased as a result of smoke heating, especially in sapwood, leading to a uniform distribution of moisture content within a log. Almost no difference was found in the amounts of chemical components between the control woods and the woods that were smoke-heated for 100h. However, in the wood that was smoke-heated for 200h, the amounts of holocellulose decreased, suggesting that thermal deterioration and/or degradation of hemicelluloses had occurred. We assume that the increase in RDC was caused by smoke heating with the crystallization of cellulose and/or thermal degradation of hemicelluloses. Almost no differences were found in sapwood color between the control woods and the woods that were smoke-heated for 100h. In the wood that was smoke-heated for 200h, however, L*decreased, whereas a* and b* increased. As a result, E*ab, showing the total color change, increased, resulting in a deeper color. These results suggest that thermal degradation of hemicelluloses was caused by smoke heating for over 100h. Therefore, smoke heating of softwood logs using a commercial-scale kiln should not exceed 100h.     

Absolute configuration of arylglycerol-β-aryl ethers obtained by asymmetric reduction of the correspondingα-ketonic compound with intactFusarium solani cells

When (±)--oxo-guaiacylglycerol--(vanillic acid) ether (1) is degraded byFusarium solani M-13-1, the-ketone is initially reduced to giveerythro andthreo guaiacylglycerol--(vanillic acid) ethers (2), arylglycerol--aryl ethers, both of which are enantiomerically pure. The absolute configuration in each2 was determined by Mosher's method; the products were converted to,-di-(R)--methoxy--trifluoromethylphenylacetates (MTPA esters) (3) oferythro (-)- andthreo (+)-veratrylglycerol--(methyl vanillate) ethers (3), whose¹H nuclear magnetic resonance (NMR) spectra were examined and compared with those of four di-(R)-MTPA ester (3) diastereomers from chemically synthesizederythro (±)-3 andthreo (±)-3. To assign the- and-MTPA-OCH₃ peaks, the¹H NMR scans of several compounds that have substructures of 3 and their 3,4,5-trimethoxyphenyl analogues were examined. When a racemic alcohol reacts with (R)-MTPA to give a pair of (R)-MTPA ester diastereomers, the value was defined as the absolute value of the difference in the¹H chemical shifts of the peak between the diastereomers. It was found that the values of-MTPA-OCH₃ were larger than those of-MTPA-OCH₃ owing to a shielding effect of the veratryl ring located on the-MTPA-OCH₃, and that the-MTPA-OCH₃ peaks in the 3,4,5-trimethoxyphenyl compounds shifted downfield relative to those in the veratryl compounds. On the basis of the¹h NMR data of (R)-MTPA esters, the absolute configuration of the four chemically prepared diastereomers (3) were determined. The catabolicerythro 3 [fromerythro (-)-3] andthreo 3 [fromthreo (+)-3] were identical to (R, S, R)-erythro 3 and (R, S, S)- threo 3, respectively. An hydrogen species in the fungal reduction would attack the-ketone fromre-face of both (R)-1 and (S)-1, givingerythro (S, R)-2 andthreo (S, S)-2, respectively.Part of this paper was presented at the 33rd Lignin Symposium, Tsukuba, November 1988     

Antioxidant activity of extracts from <Emphasis Type="Italic">Calocedrus formosana</Emphasis> leaf,bark, and heartwood

Calocedrus formosana Florin (Cupressaceae) is an endemic tree to Taiwan. To evaluate the antioxidant activity of the plant extracts from heartwood, bark, and leaf of C. formosana, assays for 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical and superoxide anion scavenging activities, as well as prevention of DNA strand cleavage were performed in this study. Similar IC₅₀ values against the DPPH radical were found for the heartwood and bark extracts at approximately 23µg/ml. Moreover, the heartwood extract exhibited the highest inhibitory activity against superoxide radicals among the test samples; a 2.3-fold lower value of IC₅₀ for superoxide radical inhibition was found in the heartwood extract relative to that of (+)-catechin. Much less effect on inhibition of DPPH and superoxide radicals was found from the leaf extract of C. formosana. More than 70% of superoxide radicals were inhibited in the presence of 10µg/ml heartwood extract, whereas only 15% inhibition was obtained from the leaf extract. The heartwood extract, at a dose of approximately 0.5mg/ml, apparently completely prevented the X174 supercoiled DNA cleavage induced by ultraviolet photolysis of H₂O₂, as judged by agarose gel electrophoresis. This report also suggests that the antioxidant activities of the plant extracts of C. formosana are in good correlation with their phenolic contents.     

5<Emphasis Type="Italic">Α</Emphasis>-Reductase inhibitory tannin-related compounds isolated from <Emphasis Type="Italic">Shorea laeviforia</Emphasis>

Five tannin-related compounds – gallic acid, flavogallonic acid dilactone, valoneic acid dilactone, gallagyldilactone, ellagic acid – were isolated from the heartwood of Shorea laeviforia, and the inhibitory activity of each against rat liver 5-reductase was evaluated. Valoneic acid dilactone and gallagyldilactone exhibited positive inhibitory activity, but gallic acid and ellagic acid did not. Flavogallonic acid dilactone stimulated 5-reductase activity, even though this compound is structurally similar to valoneic acid dilactone. The kinetic study of valoneic acid dilactone and gallagyldilactone indicated that the inhibitory behavior of 5-reductase were not competitive against the substrate (testosterone) and were partially competitive against the cofactor (NADPH). Additionally, double inhibition analysis of valoneic acid dilactone and NADP⁺ showed synergetic inhibition. These results suggested that neither valoneic acid dilactone nor gallagyldilactone can affect the binding of testosterone but that either compound could interact with an enzyme–NADP⁺ complex to inhibit 5-reductase.     

Estimation of evaporation rate from the forest floor using oxygen-18 and deuterium compositions of throughfall and stream water during a non-storm runoff period

Rainwater, throughfall, stream water during a non-storm runoff period, and soil water were sampled about every 10 days at six nested basins within the Hitachi Ohta Experimental Watershed in Japan from 1998 to 2001. Basins HA and HB are covered with an 80-year-old artificial forest of Japanese cypress and Japanese cedar. HC and HV are covered with 12-year-old forest of the same species. HO and HX are covered with various aged stands of the same species. The samples were analyzed for the isotopic compositions of ¹⁸O and deuterium (D). The weighted means of ¹⁸O (D) in HA and HB were –7.35 (–46.7) and –7.38 (–46.8), while they were –7.51 (–48.1) and –7.57 (n/a) in HC and HV, respectively. They were –7.50 (–47.6) and –7.41 (–47.1) in HO and HX, respectively. There was a relative difference of 0.2 (1.4) in ¹⁸O (D) between 80-year-old and 12-year-old forest. The stream water during a non-storm runoff period is considered to reflect the effect of evaporation from the forest floor. The evaporation rates from the forest floor were estimated using values in throughfall and stream water using the Rayleigh distillation equation under equilibrium conditions. They were estimated to be 5.5 (9.1), 5.2 (9.0), and 4.9 (8.7)% of annual throughfall in HA, HB, and HX (mature forests), respectively, using ¹⁸O (D), and 4.0 (7.6), 4.1 (8.1), and 3.5 (n/a)% of annual throughfall in HC, HO, and HV (young forests), respectively.     

Working mechanism of adsorbed water on the vibrational properties of wood impregnated with extractives of pernambuco (Guilandina echinata Spreng.)

To clarify the lowering mechanism of loss tangen (tan) of sitka spruce (Picea sitchensis Carr.) wood impregnated with extractives of pernambuco (Guilandina echinata Spreng. synCaesalpinia echinata Lam.), we examined the vibrational properties of the impregnated wood in relation to the adsorbed water. The results obtained were as follows: (1) The equilibrium moisture content (EMC) of impregnated sitka spruce decreased to some extent compared with untreated wood. (2) Frequency dependencies of tan a about 400–8000Hz showed that impregnated wood has much lower tan than untreated wood at around 9% mois ture content (MC), except for the high-frequency region. At high relative humidity, impregnated wood has a minimum tan (at around 4000Hz); and at other frequency ranges the tan of impregnated wood did not differ considerably from that of untreated wood. (3) The apparent activation energy of the mechanical relaxation process (E) concerned with adsorbed water molecules was higher for impregnated specimens than for untreated ones at moderately high relative humidity, whereas at high relative humidity the difference was not observed. Based on these results, it is thought that the tan of impregnated wood decreased at low rela tive humidity because of the formation of direct hydrogen bonds between impregnated extractives and wood components. However, when the specimen is at higher relativePart of this work was presented at the 48th annual meeting of the Japan Wood Research Society, Shizuoka, April 1998 humidity, the formation of direct hydrogen bonds are disturbed by the existence of a large number of water molecules, and some extractives act as a plasticizer.     

Investigation of wood properties that influence the final moisture content of air-dried sugi (Cryptomeria japonica) using principal component regression analysis

Sugi (Cryptomeria japonica D. Don) lumber is known to have a large variability in final moisture content (MC_f) and is difficult to dry. This study investigated the variability in MC_f of sugi in relation to wood properties. The wood property variables included initial moisture content (MC_i), basic density (BD), annual ring orientation (ARO), annual ring width (ARW), heartwood ratio (HR) and CIE L ^* color (L ^*). Sugi samples were cut from flat-sawn lumbers and air-dried; a principal component regression (PCR) model for predicting MC_f was developed with the wood property variables. The wood properties that contributed to the prediction of MC_f were evaluated by PCR analysis. Significant positive regression coefficients of the PCR model were observed in the MC_i, BD, ARO and HR, whereas negative ones in the L ^*. There were no significant regression coefficients in the ARW. These results suggest that the MC_i, BD, ARO and HR had a positive influence, the L ^* had a negative influence, and the ARW had little influence on the MC_f of air-dried sugi wood. This finding is in line with the general view on the drying characteristics in relation to these wood properties.     

Locating and identifying sound knots and dead knots on sugi by the rule-based color vision system

Knowledge of the occurrence of sound and dead knots on the surface of sugi is important for the classification and application of the material. This study examined a color vision system for detecting sound and dead knots on sugi. The system can be conceptually divided into three components: a CCD-camera scanning system, an image-segmenting module, and a rule-based defect identifying module. The results showed that the potential defect regions could be located by Otsus threshold algorithm in conjunction with t-test analysis. The accuracies of locating sound knots and dead knots were 92.6% and 97.1%, respectively. The rule-based approach was used to identify sound and dead knots and the identifying accuracies for sound knots and dead knots were 92.0% and 94.1%, respectively. The overall detection accuracy of the system was 87.6%. The results indicated that the rule-based color vision system is an efficient means of detecting sound knots and dead knots on sugi.     

Characteristic Raman bands for <Emphasis Type="Italic">Artocarpus heterophyllus</Emphasis> heartwood

The Raman spectrum of Artocarpus heterophyllus heartwood, which proved to be a rich source of flavonoids, exhibited two characteristic bands, at 1247cm^–1 and 745cm^–1. The bands also appeared in the Raman spectrum of the yellow-brown needles extracted from the heartwood with methanol. Based on the Raman measurements of flavones and related compounds, it was predicted that the Raman band at 1247cm^–1 may be attributed to flavonoid-type compounds. No vibrational band corresponding to the characteristic Raman bands was observed by diffuse reflectance infrared spectroscopy. Thus, it was suggested that observation of the characteristic bands is an advantage of Fourier transform-Raman spectroscopy for nondestructive analysis of wood.     

Methods to estimate the length effect on tensile strength parallel to the grain in Japanese larch

To find a desirable method for estimating the length effect on tensile strength ( _t), we used three methods to analyze the _t data from a Japanese larch (Larix kaempferi) small, clear specimen. These methods included a nonparametric method, the projection method of Hayashi, and a proposed method. The estimated length effect parameters (g) by the nonparametric method were 0.0237 and 0.0626 for 50th and 5th percentile _t distributions, respectively. The projection method requires a standardE _f level (E ^*: dynamic Young's modulus), arbitrarily chosen for calculating theg value. Theg values from the projection method were 0.1122 for lowE ^*, 0.0898 for averageE ^*, and 0.0759 for highE ^*. The estimatedg values by the proposed method using selected _t data were 0.1020 and 0.1838 for the 50th and 5th percentiles, respectively. Among the three methods, the nonparametric method did not consider the different distribution of Young's modulus among specimens, and the estimated length effect parameters (g) by this method were small. The projection method reduced the influence of Young's modulus, but the length effect parameters varied with theE ^* level. The proposed method minimized the dependence onE _f distributions among specimens. we believe the latter method is desirable for estimating the length effect on tensile strength.     

Structure of xylan from culms of bamboo grass (Sasa senanensis Rehd.)

Xylan prepared from culms of kumaizasa (Sasa senanensis Rehd.), a representative species of bamboo grass, was hydrolyzed with-xylanase ofStreptomyces olivaceoviridis E-86. Four arabinoxylo-oligosaccharides and two glucuronoxylo-oligosaccharides were isolated from the enzymatic hydrolysate of the xylan by chromatography on a charcoal column, a Dowex 1-x8 column, a Toyo-pearl HW-40S column, and a LiChrospher 100 NH₂ column and on preparative paper chromatography. The results of the structural analyses of the saccharides showed that the isolated oligosaccharides had the structures of 3²--l-arabinofuranosyl-xylobiose, 3²--l-arabinofuranosyl-xylotriose, 3²--[-d-xylopyranosyl-(1 2)-l-arabinofuranosyl]-xylobiose, 3³--[-d-xylopyranosyl-(1 2)-l-arabinofuranosyl]-xylotriose, 2³--4-O-methyl-d-glucuronosyl-xylotriose, and 2³--d-glucuronosyl-xylotriose. From the structural analysis of the oligosaccharides derived from the xylan, kumaizasa xylan was concluded to be a kind of arabinoglucuronoxylan having not only stubs of singlel-arabinose and singled-glucuronic acid but also stubs of disaccharide units such as-d-xylopyranosyl-(1 2)-l-arabinofuranose.     

Vibrational property changes of spruce wood by impregnation with water-soluble extractives of pernambuco (Guilandina echinata Spreng.)

Sitka spruce (Picea sitchensis Carr.) was treated with water-soluble extractive components of pernambuco (Guilandina echinata Spreng. syn Caesalpinia echinata Lam.) by two methods: impregnation under evacuation using an aspirator and repetitive surface application using a brush. The influence of these treatments on the vibrational properties were examined. The loss tangent (tan ) of the impregnated specimen decreased, up to nearly a half of its original value, with increasing weight gain. It is suggested that the decrease in tan results from impregnation of the extractive components into the amorphous region of cell walls, forming secondary bonds between matrix substances. The surface application of the extractive components, on the other hand, hardly brought about the desirable change in vibrational properties.Part of this work was presented at the 47th annual meeting of the Japan Wood Research Society, Kochi, April 1997, and the 48th annual meeting of the Japan Wood Research Society, Shizuoka, April 1998     

Potassium distribution in black heartwood of sugi (Cryptomeria japonica) I: Localization in axial parenchyma cells

This is the first report to ascertain potassium location in black heartwood of sugi (Cryptomeria japonica). The objective of this study was to understand the distribution of potassium in sugi black heartwood in connection with anatomical morphology. Scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDXA) was used to investigate the distribution of inorganic elements, especially potassium. In black heartwood, potassium was detected in all tissues (tracheids, ray parenchyma, and axial parenchyma), but its concentrations were different in each xylem tissue. Potassium was particularly accumulated in the droplets in axial parenchyma cells. In addition, calcium was also detected in all tissues. Phosphorus sometimes existed in the granules in ray parenchyma cells. From optical microscopy, the axial parenchyma cells were observed to be arranged in a tangential direction on transverse section and the droplets in these cells were distributed in areas of high ash and green moisture content. For red heartwood, potassium detected by SEM-EDXA was far lower in all tissues than in the black heartwood, while the trend for calcium was the converse. Potassium in axial parenchyma cells was more abundant in black heartwood than in typical pale red heartwood.     

Relationships between blacking phenomenon and norlignans of sugi (Cryptomeria japonica) heartwood III: Coloration of norlignans with alkaline treatment

We investigated norlignan coloration with alkaline treatment to clarify the relationship between the blackening of sugi (Cryptomeria japonica D. Don) heartwood and norlignans in the heartwood. Of the four main norlignans (agatharesinol, sequirin-C, sugiresinol, hydroxysugiresinol) of sugi heartwood, only sequirin-C was clearly colored with alkaline treatment (0.4% potassium hydrogencarbonate solution, pH 8.6). Sequirin-C changed color to deep purple with alkaline treatment. The absorbance spectrum of colored sequirin-C had two peaks (450 and 525nm) and one shoulder (626nm). Coloration began at pH 6.2.). The spectrum of blackened sugi heartwood was similar to that of sequirin-C treated with alkali. A catechol nucleus and a double bond conjugated with a benzene nucleus play important roles in norlignan coloration with alkaline treatment. The number of hydroxyl groups is related to solubility in alkaline solution, and, therefore, whether a norlignan changes color also depends on the number of hydroxyl groups. Based on these results, we concluded that sugi heartwood turns black because sequirin-C, which is readily soluble in alkaline solution and can form a large intramolecular conjugation system when alkalized, is converted to products with a deep purple color as the heartwood is basified.     

Effects of impregnation of simple phenolic and natural polycyclic compounds on physical properties of wood

The impregnation of various simple phenolic and natural polycyclic compounds into wood was investigated from the viewpoints of vibrational property and dimensional stabilizing effect. When simple phenolic compounds were impregnated, the loss tangent (tan ) in the longitudinal direction increased linearly with increasing weight gain. Meanwhile, among the natural polycyclic compounds hematoxylin decreased the tan drastically by impregnation. It was suggested that the five hydroxyl groups and the pyran ring oxygen in the hematoxylin molecule contribute to formation of the crosslinkage-type hydrogen bonds between wood components. The rigidity of hematoxylin molecules may also be important. By impregnation of about 10% catechol, resorcinol, and saligenin, a 40% level of antiswelling efficiency (ASE) was attained, although a significant dimensional stabilizing effect was not observed after impregnation of natural polycyclic compounds.Part of this work has been published as a Rapid Communication inMokuzai Gakkaishi 43(12). It was also presented at the 48th annual meeting of the Japan Wood Research Society, Shizuoka, April 1998     

Profile of bordered pit aspiration in Cryptomeria japonica using confocal laser scanning microscopy: pit aspiration and heartwood color

Nine trees of Cryptomeria japonica from six elite tree clones with a broad range of heartwood colors were selected. The profiles of pit aspiration percentage (ASP) of earlywood and latewood from pith to bark for green and air-dry conditions were determined to study the relationship between heartwood color and pit aspiration. Confocal laser scanning microscopy (CLSM) observations showed that the ASP of earlywood was low in sapwood and high in heartwood in the green condition. Pit aspiration increased in intermediate wood when compared with sapwood. On the other hand, latewood pits did not aspirate during heartwood formation. Comparing the air-dry condition with the green condition, sapwood pits aspirated during drying in both earlywood and latewood; however, there was no significant difference in pit aspiration of heartwood. There was no significant difference between samples with red and black heartwoods for ASP. The difference in ASP between individual trees was larger than that by heartwood color. The general advantage of CLSM over light microscopy is that serial optical sections along the Z axis can be obtained for any moisture condition, without the need for thin sectioning or embedding.     

Compounds inhibitory to rat liver 5α-reductase from tropical commercial wood species: resveratrol trimers from melapi (Shorea sp.) heartwood

5-Reductase inhibitory activity of methanol extracts of the heartwood of 13 tropical wood species were examined. Strong 5-reductase inhibitory activity was observed withShorea species. From melapi (Shorea sp.), two known resveratrol trimers, vaticanol A and ampelopsin C, and two novel trimers were isolated as active compounds. The structures of the two novel resveratrol trimers were elucidated by one- and two-dimensional nuclear magnetic resonance spectroscopic analyses, including¹H-¹HCOSY, HMQC, and HMBC. The compounds were named melapinol A and melapinol B. There were no significant differences among the 5-reductase inhibitory activities of the four resveratrol trimers, which were significantly stronger than those of-linolenic acid and epigallocatechin gallate, known 5-reductase inhibitors.