木材白腐菌对木质素生物降解机制的初步研究

通过测定6种白腐菌火木层孔菌Phellinus igniarius及粗毛盖菌Funalia gallica、三色革裥菌Lenzites tricolor、冬拟多孔菌Polyporellus brumalis、偏肿拟栓菌Pseudotrametes gibbosa和血红密孔菌Pycnoporus sanguineus分解山杨材一定时间后的木质素含量，研究木材白腐菌对山杨材木质素生物降解机制。测定结果表明，按照木质素的减少百分率，这6种白腐菌对山杨材木质素的分解能力依次为血红密孔菌、偏肿拟栓菌、三色革裥菌、冬拟多孔菌、冬拟多孔菌、火木层孔菌；6种白腐菌对山杨材木质素及综纤维素的分解量X1、X2及分解时间Y这3个量之间存在多元回归关系；冬拟多孔菌是较多分解木质素、较少分解纤维素的木材白腐菌。     

Effects of heartwood extractive fractions of Thuja plicata and Chamaecyparis nootkatensis on wood degradation by termites or fungi

The effect of selective removal of extractives on termite or decay resistance was assessed with matched samples of Thuja plicata Donn ex D. Don and Chamaecyparis nootkatensis (D.Don) Spach heartwood. Samples were extracted using a variety of solvents and then exposed to the subterranean termite Coptotermes formosanus Shiraki in a no-choice feeding test or to the brown-rot fungus Postia placenta (Fr.) M. Larsen & Lombard in a soil bottle test. At the same time, the effect of naturally occurring variations in heartwood extractives on termite or decay resistance was evaluated by testing samples from the inner and outer heartwood of five trees of each species against C. formosanus and P. placenta and analyzing matched wood samples for their extractive content. The results suggest that the methanol-soluble extractives in T. plicata and C. nootkatensis play an important role in heartwood resistance to attack by C. formosanus and P. placenta. Total methanol-soluble extractive content of the heartwood was positively correlated with both termite and decay resistance; however, there was much unexplained variation and levels of individual extractive components were only weakly correlated with one another. Further studies are under way to develop a better understanding of the relationships between individual extractive levels and performance.     

不同x射线源测定木材微密度的研究

本文比较分析了三种x射线源(~(55)Fe、~(238)Pu和x光管)对木材进行微密度测定的精度,并对不同树种木材的质量衰减系数进行了测定和研究。     

Relationship between degradation of wood and production of H2O2-producing or one-electron oxidases by brown-rot fungi

Summary The one-electron oxidation activity of brown-rot fungi was determined by measuring ethylene production from KTBA. Ethylene production was related to degradation of lignin, cellulose, and wood itself. Extracellular protein that catalyzed oxidation of KTBA was isolated from wood-containing cultures. This protein required H₂O₂ for KTBA oxidation. It was also found to oxidize NADH, producing H₂O₂ via in the presence of O₂. The protein showed little phenol-oxidase activity under conditions giving high activity against KTBA. The results indicate that partially reduced oxygen may play a role in the initial degradation of the cellulose and lignin in wood in cultures of brown-rot fungi.     

Analysis of birch wood lignin by oxidative degradation

Summary The lignin in birch wood has been subjected to analysis by oxidative degradation after milling of wood samples in a Wiley mill and in a rotatory ball mill. For comparison milled wood lignin from birch has also been analysed. It was found that the type of milling affects both the total yield of degradation acids and their relative frequency of occurrence. These findings are interpreted as being due to a cleavage of aryl ether linkages during the milling procedure. The oxidative degradation analysis gave rise to a total of 30 different acids which were tentatively identified on the basis of their mass spectral fragmentation patterns. Among the acids some were found having either a phenoxyacetic acid or a phenoxypropionic acid structure. The possible origin of these is discussed. A grant to one of us (R.A.N.) from Jacob Wallenbergs Forskningsstiftelse is gratefully acknowledged. Thanks are due to Kristina Gustafsson for skilful experimental assistance     

Ultrastructural aspects of beech bark degradation by fungi

The degradation of beech bark by three wood-decaying fungi has been analyzed at the ultra-structural level and the micromorphological changes occurring in the walls of the diverse cell types compared with the decay pattern in wood cells.     

A study of the structure of wood cells by x-ray diffraction

Summary An x-ray diffraction method was used to determine the values of the mean microfibrillar helical angles and to estimate quantitatively the amount of crystalline cellulose in the various cell wall layers of wood fibers. To interprete the intensity variation along the diffraction arcs a new curve fitting method based on Gaussian pairs was developed. As an application results are given for Scots pine (Pinus sylvestris) and Norway spruce (Picea abies).the authors acknowledge the financial support by the National Research Council for Science, Finland     

Characterization of acetylated wood decayed by brown-rot and white-rot fungi

The objective of this study was to characterize the decay of acetylated wood due to brown-rot and white-rot fungi by analysis of chemical composition, X-ray measurements, and¹³C-NMR spectroscopy. The decay by brown-rot fungus became inhibited at a weight percent gain (WPG) due to acetylation of more than 10%, and the mass loss (LOSS) due to decay became zero at a WPG of about 20%. The LOSS due to white-rot fungus decreased slowly with the increase in WPG, reaching zero at a WPG of about 12%. The losses of lignin by brown-rot decay increased initially with the decrease in LOSS owing to the progressing acetylation and then decreased at a LOSS of less than 60%. Polysaccharides were more easily decomposed than lignin during the decay of acetylated wood due to brown-rot fungus. The losses of both components due to white-rot decay decreased as the LOSS decreased with progressing acetylation. The white-rot fungus tended to preferentially decompose the lignin during the decay of acetylated wood. The brown-rot fungus decomposed the cellulose in the crystalline region to a large degree when the LOSS was more than 40%, whereas the white-rot fungus decomposed the crystalline region and the noncrystalline region in acetylated wood to the same degree. The brown-rot fungus preferentially decomposed unsubstituted xylose units in acetylated wood and partly decomposed the mono-substituted xylose units. It was suggested that the mono- and disubstituted cellulose were partly decomposed by brown-rot fungus.This paper was presented at the 46th and 47th annual meetings of the Japan Wood Research Society at Kumamoto and Kochi in April 1996 and April 1997, respectively     

Polyethylene degradation by lignin-degrading fungi and manganese peroxidase

Degradation of high-molecular-weight polyethylene membrane by lignin-degrading fungi, IZU-154, Phanerochaete chrysosporium, and Trametes versicolor, was investigated under various nutritional conditions. IZU-154 showed the most significant polyethylene degradation among the three lignin-degrading fungi under nitrogen- or carbon-limited culture conditions. Furthermore, for T. versicolor and P. chrysosporium, the addition of Mn(II) into nitrogen- or carbon-limited culture medium enhanced polyethylene degradation. These results suggest that polyethylene degradation is related to ligninolytic activity of lignin-degrading fungi. Treatment of polyethylene membrane with partially purified manganese peroxidase (MnP) caused significant degradation in the presence of Tween 80, Mn(II), and Mn(III) chelator. This result demonstrates that MnP is the key enzyme in polyethylene degradation by lignin-degrading fungi.This study was presented in part at the 9th International Symposium on Wood and Pulping Chemistry, Montreal, Canada, June 9–12, 1997     

Changes in structural and chemical components of wood delignified by fungi

Summary Cerrena unicolor, Ganoderma applanatum, Ischnoderma resinosum and Poria medulla-panis were associated with birch wood that had been selectively delignified in the forest. Preferential lignin degradation was not uniformly distributed throughout the decayed wood. A typical white rot causing a simultaneous removal of all cell wall components was also present. In the delignified wood, 95 to 98% of the lignin was removed as well as substantial amounts of hemicelluloses. Scanning and transmission electron microscopy were used to identify the micromorphological and ultrastructural changes that occurred in the cells during degradation. In delignified areas the compound middle lamella was extensively degraded causing a defibration of cells. The secondary wall, especially the S₂ layer, remained relatively unaltered. In simultaneously white-rotted wood all cell wall layers were progressively removed from the lumen toward the middle lamella causing erosion troughs or holes to form. Large voids filled with fungal mycelia resulted from a coalition of degraded areas. Birch wood decayed in laboratory soil-block tests was also intermittently delignified. Selective delignification, sparsely distributed throughout the wood, and a simultaneous rot resulting in the removal of all cell wall components were evident. Scanning electron microscopy appears to be an efficient technique for examining decayed wood for fungi with the capacity to selectively delignify wood.The authors would like to thank Kathy Zuzek for technical assistance and Dr. M. Larsen, Forest Prod. Lab., Madison, for identifying the sporophores of Poria medulla-panis. This research was founded in part by a grant from the USDA Forest Service, Forest Products Laboratory and from the Graduate School, University of Minnesota     

Kinetics of acid-catalysed delignification of Eucalyptus globulus wood by acetic acid

Summary The kinetics of HCl-catalysed delignification of Eucalyptus globulus wood by 70% (w/w) acetic acid solution were satisfactorily explained by a model in which 5% of the lignin fraction could not be eliminated and the remaining 95% was eliminated by a single process which, in view of the activation energy calculated from the data was attributed to the hydrolysis of -aryl ether bonds. The selectivity of the process was effectively independent of HCl concentration and operating temperature for pulp yields >50%. At high temperature (160 °C) and catalyst concentration (0.027 MHCl), lignin condensation and precipitation became significant and the data were better fitted by a model comprising two consecutive processes: lignin solubilization followed by lignin condensation.The authors are grateful to the CICYT for financial support of this work (Project AGF93-0605) and also to the DGICYT for a research grant awarded to J. González     

Biodegradation of new quaternary ammonium compounds in treated wood by mould fungi

The degradation of seven potential wood preservatives based on imidazolium compounds (ICs) and quaternary ammonium compounds (QACs) with a modified anion structure by mould fungi was determined using soil-block method. Experiments were carried out on Scots pine (Pinus sylvestris L.) wood. Two-phase titration and high-performance liquid chromatography (HPLC) method were used to detect and quantify the degradation products. The performed soil-block tests showed that the ICs and QACs with alkoxymethyl substituents were leached from the experimental wood when in contact with moist soil and revealed their fungal detoxification by mould fungi, especially by Gliocladium roseum. The degree of biological decomposition of new compounds was higher than didecyldimethylammonium chloride and didecylmethylpoli(oxyethyl)ammonium propionate. The observations of the colonization by mould fungi were made using the scanning electron microscope (SEM). Decay of treated wood by mould fungi showed its tolerance to QACs.     

Alkaline degradation of spruce and beech wood

Summary The alkaline delignification of spruce and beech wood is accomplished in three phases. The first phase results in a decrease of yield down to 83...80%, the second one in a decrease from 83...80% to 64...61% and the third one in a yeld drop from 64...61% to 50...46%. The amount of polysaccharides removed in the first phase was 22%, in the second phase 5...6% and in the third phase 10% of the total polysaccharides in the original wood. The amount of lignin removed in the first phase of delignification was 9...11% in the second phase 53...54% and in the third phase 28% of the total lignin in the original wood. The polysaccharides extracted in the second and third phase amounted to 70...78% of the polysaccharides removed in the first delignification phase. For an entire characterization of the delignification reaction not only the course of lignin removal is of importance but also the course of the polysaccharide extraction. The results show that for a two-stage alkali-oxygen-cooking technology the optimum yield after initial partial alkaline delignification lies in the range of 64...61%.     

Detection of early stages of wood decay by acoustic emission technique

Acoustic emissions of pine wood samples (Pinus sylvestris L.) previously infected with the soft-rot fungi (Chaetomium globosum Kunze) and brown-rot fungi (Coniophora puteana (Schum. ex Fr.) Karst.) were measured in the perpendicular to grain compression test, in the radial direction. It was found that even a minimum mass loss (below 1%) caused by enzymatic deterioration of the wood substance resulted in an increase in acoustic emission level in the compression test measured perpendicular to grain in the radial direction. A particularly sensitive indicator of wood enzymatic destruction were cumulative counts of acoustic emission related to the value of the applied compression load. Received 4 March 1997     

Study on low mass thermal degradation products of milled wood lignins by thermogravimetry-mass-spectrometry

Summary Thermogravimetry-mass-spectrometry (TGMS) as a sophisticated analytical instrument is described for the thermal analysis of milled wood lignins from spruce (Picea abies L.), beech (Fagus sylvatica L.) and bamboo (Bambus sp.). The samples were heated on the thermobalance in an inert gas atmosphere (Ar) with 20°C/min heating rate. The weight loss curves (TG) and their 1st derivatives (DTG) were recorded. The evolution of 10 low mass degradation products with m/z below 44 was monitored as a function of the temperature by means of a quadrupol mass spectrometer. Thus the intensity profiles of H₂, CH₃ , H₂O, CO, CHO, HCHO, CH₃O, CH₃OH, CH₃CO and CO₂ were recorded and interpreted in terms of lignin structure and the course of carbonization. The results are in agreement with the results of differencial scanning calorimetry (DSC) and pyrolysis-gas-chromatography mass-spectrometry (PyGCMS) of the phenolics.     

Improved methodology of measuring moisture content of wood by a vibrational technique

Abstract

A method of measuring moisture content of wood is introduced. This method uses a vibrational technique. A shaker driven by swept sine signals was used for the accurate generation of vibration. A cylindrical wood sample was used to verify the method of measuring the moisture content. Resonance frequencies of the wood sample decreased as its moisture content increased. An experiment was performed by measuring the vibration of a tree to explore the feasibility of applying the method to the measurement of the moisture content of trees. The circumferential mode, which is independent of the height of a tree, was identified using a white oak tree.     

Improved methodology of measuring moisture content of wood by a vibrational technique

A method of measuring moisture content of wood is introduced. This method uses a vibrational technique. A shaker driven by swept sine signals was used for the accurate generation of vibration. A cylindrical wood sample was used to verify the method of measuring the moisture content. Resonance frequencies of the wood sample decreased as its moisture content increased. An experiment was performed by measuring the vibration of a tree to explore the feasibility of applying the method to the measurement of the moisture content of trees. The circumferential mode, which is independent of the height of a tree, was identified using a white oak tree.