Distribution of added chemicals in the cell walls of high temperature dried and green wood of Swedish pine, Pinus sylvestris

High temperature dried and green wood of Swedish pine was impregnated with glycerate and silver nitrate. TEM and STEM/EDS on ultramicrotomed specimens was used to reveal the location of silver in the cell wall. The silver was precipitated by a new method using silver nitrate impregnated after which the wood had been impregnated with potassium glycerate. A significant difference in the distribution of the silver was observed. In the green wood, there was a homogenous distribution of the impregnant compared to the dried specimens. The inhomogenous distribution in the dried specimens is believed to be the result of damage inside the wood cell walls which in turn will have a negative effect on dimensional stabilizing results. The darker compound middle lamella observed is believed to be an artefact. Received 19 November 1998     

Weathering of chemically modified wood surfaces

Summary Scots pine wood veneers were acetylated to weight gains of 5, 10, 15 or 20% and exposed to natural weathering. Veneers acetylated to low weight gains of 5 and 10% and exposed to the weather showed greater losses in mass and tensile strength due to increased delignification and depolymerisation of cellulose than similarly exposed, untreated controls. Acetylation to 20% weight gain restricted the loss of veneer mass and holocellulose during exposure. Initially it also slightly reduced the depolymerisation of cellulose, and this was reflected in lower losses in veneer zero-span tensile strength after 35 days exposure. However, the photoprotective effects of acetylation, with the exception of veneer mass, were lost with prolonged exposure of veneers to the weather. Acetylation of wood blocks to 20% weight gain caused a bulking of the wood cell wall, particularly the S₃ layer of the secondary wall, and reductions in lumen size. Acetylated latewood cells maintained their shape and radial orientation during exterior exposure, but acetylation did not prevent erosion of the middle lamella. Mechanisms to explain how acetylation may affect the weathering resistance of wood are suggested. Received 26 May 1998     

A study of lignification in loblolly pine tracheids by the SEM-EDXA technique

Summary The lignification process in different morphological regions of loblolly pine tracheids was studied by the SEM-EDXA technique. Prior to S₂ layer formation, lignification was initiated in the cell corner middle lamella and compound middle lamella regions. Subsequently a rapid lignin deposition was observed in both regions, whereas secondary wall lignification was a more gradual process and initiated when the middle lamella lignin concentration was approximately 50% of maximum. Within the secondary wall, the S₁ layer is lignified first. Then, lagging just behind cell wall formation, lignification of the S₂ layer is initiated adjacent to the S₁ layer and extends toward the lumen. Finally, the S₃ layer lignified. Upon completion of lignification, the cell walls had a higher concentration of lignin in both the S₁ and S₃ layers than in the S₂ layer.This Paper is an excerpt from the Ph.D. dissertation of Shiro Saka     

Heterogeneity in formation of lignin

Summary The formation of lignin in the cell wall of compression wood of Pinus thunbergii was examined by selective radio-labeling of specific structural units in the lignin and visualization of the label in the different morphological regions by microautoradiography. Deposition of lignin in the tracheid cell wall of compression wood occurred in the order: p-hydroxyphenyl, guaiacyl and syringyl lignin, which is the same order as observed in normal wood. However, the period of lignification in the compression wood was quite different from those of normal and opposite woods. The p-hydroxyphenyl units were deposited mainly in the early stage of cell wall formation in compound middle lamella in normal and opposite woods, while in compression wood, they were formed in both the compound middle lamella and the secondary wall. The most intensive lignification was observed during the formation of the S₂ layer, proceeding from the outer to inner S₂ layers for a long period in compression wood. In the normal or opposite woods, in contrast, the lignification became active after formation of S₃ had begun, then proceeded uniformly in the secondary wall and ended after a short period.A part of this report was originally presented at the 1989 International Symposium on Wood and Pulping Chemistry at Raleigh, NC, U.S.A.     

Lignin distribution in spruce (Picea abies) determined by mercurization with SEM-EDXA technique

Summary The lignin distribution between the middle lamella and the cell wall of spruce fibers has been determined by a new technique based on a mercurization of the lignin and a concomitant determination of mercury by the SEM-EDXA technique. The ratio of lignin in the middle lamella at the cell corners to the lignin in the secondary wall was 2.5±0.6 for latewood and 2.4±0.6 for earlywood. This gives a lignin content of 55–58% in the true middle lamella in the cell corners. The reactivity to mercuric acetate of different wood elements was determined in separate experiments. Fractions enriched in ray cells, middle lamella, and compression wood all reacted at the same rate as the whole wood; about one mole of mercury was incorporated per mole of lignin (C₉-unit).     

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     

Ultraviolet microspectrophotometric investigation of the distribution of lignin in Prunus jamasakura differentiated on a three-dimensional clinostat

To examine the effect of gravity on lignin content and deposition in plant cells, we used ultraviolet (UV) microspectrophotometry and chemical methods to investigate the secondary xylem of Prunus jamasakura grown on a three-dimensional (3D) clinostat, which simulates microgravity. The stem of the 3D-clinostat specimens elongated with bending and the width of their secondary phloem increased. The UV absorbance of the 3D-clinostat specimens at 278 nm was higher than that of the control specimens, which were grown on the ground, in the wood fiber cell corner middle lamella, compound middle lamella, and fiber secondary wall; the UV absorbance in the vessel secondary wall did not differ between the specimens. The lignin content in the stem, including the bark, of the 3D-clinostat specimens, as determined using an acetyl bromide method, was less than that of the control specimens. In the specimens that differentiated on a 3D clinostat, the amount of lignin in the wood fibers increased, while the proportion of the lignified xylem in the stem decreased relative to control values.     

Immunogold labeling of an extracellular substance producing hydroxyl radicals in wood degraded by brown-rot fungusTyromyces palustris

A fraction containing low-molecular-weight peptides that catalyzes redox reactions between electron donors and O₂ to produce ·OH, was partially purified from wood-decaying cultures of the brown-rot fungusTyromyces palustris. Polyclonal antibodies raised to the fraction were used for immunogold labeling of transverse sections of sapwood of spruce in various stages of degradation byT. palustris to demonstrate the cellular localization of the ·OH-producing substance. Initially, the wood cell wall was attacked primarily by fungal hyphae growing in the cell lumen. During the early stages of degradation, the gold label was localized in the fungal cytoplasm and cell wall and in the extracellular slime sheath surrounding the fungal cell wall. The gold label also was found throughout the wood cell wall, although the cell wall remained almost intact so long as the fungal hyphae remained in the lumen. Thus, the ·OH-producing substance is secreted by the hyphae into the lumen, and it diffuses through the S3 layer into the S2 layer and the middle lamella. The role of this ·OH-producing system in wood degradation byT. palustris is discussed.     

Cellular UV-microspectrophotometric investigations on pine wood ( Pinus taeda and Pinus elliottii) delignification during biopulping with Ceriporiopsis subvermispora (Pilát) Gilbn. & Ryv. and alkaline sulfite/anthraquinone tr

Scanning UV-microspectrophotometry was used to investigate the topochemistry of lignin removal from pine wood (Pinus taeda and P. elliottii) chips during biopulping involving wood treatment with Ceriporiopsis subvermispora (Pilát) Gilbn. & Ryv. followed by alkaline sulfite/anthraquinone delignification. A delignification front starting from the lumen towards the compound middle lamella was clearly observed in micrographs recorded from individual cell wall layers of wood samples biotreated for 30 days. Lignin was removed without cell wall erosion. UV-micrographs of wood samples cooked for a short time (90 min pulping) showed that the S2 of biotreated samples are more homogeneously delignified compared to the S2 of the undecayed controls. Similarly, the compound middle lamella and cell corners are also more delignified in biotreated samples. On the other hand, UV-micrographs of samples cooked for a long time (150 min pulping at 170°C) showed that there are no significant differences in the contents of residual lignin retained in the S2 of undecayed and biotreated wood samples.     

Tensile growth stress and lignin distribution in the cell walls of black locust (Robinia pseudoacacia)

Seven specimens that contained a continuous gradient of wood from normal to tension wood were collected from an inclined black locust (Robinia pseudoacacia), and the released strain of growth stress was quantified. Lignin distribution in the cell wall was investigated using ultraviolet (UV) microspectrophotometry to examine its relation to the intensity of growth stress. The UV absorption at cell corner middle lamella and in the compound middle lamella remained virtually constant, irrespective of the contractive released strain (i.e., tensile growth stress). The gelatinous (G)-layer began to differentiate, and the UV absorption decreased there in accordance with increases in the contractive released strain. The absorption maximum (max) remained virtually constant at the cell corner middle lamella and in the compound middle lamella at 277–280nm, irrespective of the released strain. The max for the secondary wall of normal wood was 272nm and shifted to 268nm in the G-layer of tension wood as the contractive released strain increased. The percentage of the cross-sectional area, consisting of the G-layer, with respect to the whole cross-sectional area increased with the contractive released strain.     

Comparative study of anatomy and lignin distribution in normal and tension wood of Salix gordejecii

Fibre morphology, anatomy and ultrastructure in cell wall of Salix gordejecii normal wood were examined by transmission electron microscopy (TEM). S. gordejecii tension wood can be recognized anatomically by the presence of gelatinous (G) fibres, which contain a conspicuously thickened inner cell wall layer. TEM images showed that cell wall of S. gordejecii normal wood was typically divided into three layers including the primary wall (P), the middle lamellar (ML) and the secondary wall (S₁, S₂ and S₃). Lignin distribution was determined by using confocal laser scanning microscopy (CLSM) and transmission electron microscopy with energy dispersive X-ray analysis (TEM-EDXA). Confocal images (530 nm) of S. gordejecii normal wood showed strongly lignified CCML, and weakly lignified ML and S2 layer. Weakly lignified fibres (F) and strongly lignified vessels (V) were also detected by using CLSM. Results obtained from confocal microscopy were further confirmed by using TEM-EDXA, indicating that the ratio of lignin concentration in CCML, ML and S2 is 1.72 (1321):1.31 (1006):1 (768). Lignin distribution in tension wood is similar to that in normal wood, except for the non-lignified G layer.     

Compressive deformation of phenol formaldehyde (PF) resin-impregnated wood related to the molecular weight of resin

The effects of molecular weight of PF resin on the deformation behaviour of NaClO₂ treated resin-impregnated wood during compression were investigated. Blocks of Japanese cedar were subjected to 2% NaClO₂ aqueous solution. This was repeated up to four times resulting in a weight loss of 28%. Treated and untreated samples were impregnated with PF resin having different molecular weight. With increasing molecular weight, weight gain and volume gain decreased for untreated PF resin-impregnated wood, while NaClO₂ treated wood impregnated with high molecular weight PF resin showed almost double the weight gain compared to untreated condition. NaClO₂ treatment has shown considerable potential for high compression of PF resin-impregnated wood at lower pressing pressure regardless of the molecular weight of the resin. Low to high molecular weight resin was shown to penetrate into NaClO₂ treated wood as estimated by weight gain contributing to the plasticization of cell wall considerably and thus resulting in cell wall collapse at low pressing pressure. The density of NaClO₂ treated wood impregnated with high molecular weight resin attained a value of over 0.8 g/cm³ which is close to the density of untreated wood impregnated with low molecular weight resin. Such compressed wood exhibited high dimensional stability after boiling for 3 h. Thus, the penetration of resin into wood contributes to highly compressed dimensional stable resin-impregnated wood at low pressing pressure.     

Effects of chemical treatments on ultra-high-yield pulping 1. Fiber separation

Summary Specially designed wood blocks from Norway spruce were used to study the nature of the fracture surfaces developed in shear using a tensile tester. In the case of the control (water-soaked blocks), the fracture in the latewood takes place mainly in the S₁ layer while in the earlywood the fracture occurs across the double cell wall. After dilute alkali treatment, some earlywood cells also fracture in the S₁ layer. For sulfite-treated samples, on the other hand, both earlywood and latewood fracture in the middle lamella.Financial support from the Empire State Paper Research Associates (ESPRA) is greatly appreciated     

Improvement of wood properties by urea-formaldehyde resin and nano-SiO2

In order to improve wood properties of triploid clones of Populus tomentosa, urea-formaldehyde (UF) resin was compounded with nano-SiO₂, coupling agents and flame retardants in different ways to prepare five kinds of modifiers. The poplar wood samples were impregnated with the modifiers and heated to prepare UF-SiO₂-wood composites. The antiswelling efficiency, resistance of water absorption, oxygen index and hardness of the composites were measured. Results show that all of the modifiers reduced water absorption of poplar wood and enhanced flame resistance and hardness. Nano-SiO₂ showed a marked effect in improving the hardness of wood. In addition, all of the modifiers, except UF-C-SiO₂-polymer, improved the dimensional stability of poplar wood. The UF resin and nano-SiO₂ compound improved general properties of poplar wood. __________ Translated from Journal of Beijing Forestry University, 2006, 28(2): 123–128 [译自: 北京林业大学学报]     

Effects of UV light irradiation on colour stability of thermally modified, copper ethanolamine treated and non-modified wood: EPR and DRIFT spectroscopic studies

A series of experiments were carried out to investigate the colour stability of chemically treated and thermally modified wood compared to non-modified wood during long term artificial UV light irradiation. One set of wood samples was vacuum-pressure impregnated with alkaline (pH 9.8) copper (II) ethanolamine aqueous solution, while another set of samples from the same wood block was thermally modified at 210°C and −0.90 bar for 2 h. The treated and modified wood samples along with the non-modified ones were exposed to artificial UV light with the wave length in the region of UVA (315–400 nm) and UVB (280–315 nm) intermittently for 500 h. Colour measurements were carried out throughout the irradiation period at an interval of 100 h according to CIEL*a*b* system, where the results are presented in terms of ΔE, ΔL*, Δa* and Δb* values. Better photo-stability in terms of colour changes was recorded for both treated and modified woods compared to the non-modified one. By means of EPR and DRIFT spectroscopic study it was shown that some degree of colour stability of treated and modified woods, achieved during artificial UV light irradiation, resulted from lignin modifications and monomers of phenolic compounds.     

Recent progress in the chemistry and topochemistry of compression wood

Summary A review of the chemistry and topochemistry of compression wood with 200 references. Compression wood contains on the average 30% cellulose, 35–40% lignin, 10% galactan, 9% galactoglucomannan, 8% xylan, and 2% of a 1,3-glucan (laricinan). The cellulose is less crystalline, and the xylan has fewer arabinose side chains than in normal wood. The lignin is composed of guaiacylpropane and p-hydroxyphenylpropane units. It is more condensed, has a higher proportion of carbon-carbon bonds, and contains fewer arylglycerol--aryl ether structures than a normal conifer lignin. The ray cells and the primary wall of the tracheids have the same chemical composition in normal and compression woods. The galactan is largely located in the outer region of the secondary wall. Only 5–10% of the lignin in compression wood tracheids is extracellular. The middle lamella is less lignified than in normal wood, while the S₁ and inner S₂ layers have a lignin concentration of 30–40% which is twice as high as in normal wood. The lignin content of the S₂ (L) layer is equal to or higher than that of the intercellular region along the wall. The review is concluded with a brief reference to areas where present information is incomplete or lacking.A portion of an Academy Lecture of the International Academy of Wood Science, presented at the International Symposium on Wood and Pulping Chemistry (Ekmandagarna 1981), held in Stockholm, Sweden, June 9–12, 1981. Reprints of the unabridged review, published under the title Recent Progress in the Chemistry, Ultrastructure, and Formation of Compression Wood in the preprints of the symposium (SPCI Report 38, Vol. 1, p. 99–147) are available from the author. I wish to express my gratitude to my colleague Professor Robert A. Zabel for generous travel assistance     

Nanostructural assembly of cellulose,hemicellulose, and lignin in the middle layer of secondary wall of ginkgo tracheid

Physical, chemical, and biological properties of wood depend largely on the properties of cellulose, noncellulosic polysaccharides, and lignin, and their assembly mode in the cell wall. Information on the assembly mode in the main part of the ginkgo tracheid wall (middle layer of secondary wall, S2) was drawn from the combined results obtained by physical and chemical analyses of the mechanically isolated S2 and by observation under scanning electron microscopy. A schematic model was tentatively proposed as a basic assembly mode of cell wall polymers in the softwood tracheid as follows: a bundle of cellulose microfibrils (CMFs) consisting of about 430 cellulose chains is surrounded by bead-like tubular hemicellulose-lignin modules (HLM), which keep the CMF bundles equidistant from each other. The length of one tubular module along the CMF bundle is about 16 ± 2 nm, and the thickness at its side is about 3–4 nm. In S2, hemicelluloses are distributed in a longitudinal direction along the CMF bundle and in tangential and radial directions perpendicular to the CMF bundle so that they are aligned in the lamellae of tangential and radial directions with regard to the cell wall. One HLM contains about 7000 C₆-C₃ units of lignin, and 4000 hexose and 2000 pentose units of hemicellulose.     

TGA modeling of the thermal decomposition of CCA treated lumber waste

 To guide the development of thermal decomposition methods for disposal of CCA treated wood, reactions during the thermal decomposition of CCA treated wood were modeled using thermogravimetric analysis (TGA), with special focus placed on arsenic volatilization. Simple inorganic compounds, such as As₂O₅, CuO, and Cr₂O₃, were used to model the thermal behavior of the inorganics in CCA treated wood. In air and nitrogen, arsenic (V) oxide began to volatilize at 600 °C during temperature ramps at 5 °C/min. During a 5 °C/min ramp in a hydrogen mix, arsenic (V) oxide began decomposition at 425 °C. Arsenic volatile loss from CCA treated wood can depend strongly on the gases produced by wood thermal decomposition. In the presence of As₂O₅, chromium (III) oxide and copper (II) oxide formed arsenates in air and nitrogen. Chromium arsenates began decomposition as low as 790 °C. This suggested that chromium arsenates in CCA treated wood formed during original preservative fixation may decompose as low as 790 °C. Copper arsenates were stable up to 900 °C in air, but showed only a limited range of stability in nitrogen. Depending on process conditions, the formation of copper arsenates may limit arsenic loss during thermal decomposition of CCA treated wood up to 900 °C. The thermal decomposition of inorganic oxides was influenced by interactions with wood and wood decomposition products. In a dry YP sawdust/As₂O₅ mix, arsenic (V) oxide volatilized at 370 °C during inert pyrolysis at 5 °C/min and at 320 °C during smoldering combustion at 5 °C/min. Thermal dwells of a dry YP/As₂O₅ mix showed no arsenic loss at 250 °C, but significant loss occurred during higher temperature dwells. During inert pyrolysis at 5 °C/min, the formation of complexes and hydrates were shown to prevent arsenic loss up to 400 °C. Received 14 July 1999     

Dielectric relaxation due to heterogeneous structure in moist wood

Dielectric properties in three main directions for hinoki wood (Chamaecyparis obtusa) specimens conditioned at various levels of relative humidity were measured in the frequency range from 20 Hz to 10 MHz over the temperature range from −150°C to 20°C. Three relaxations were observed in the specimens conditioned at high levels of relative humidity. The relaxation in the highest frequency range was ascribed to the motions of adsorbed water molecules. The relaxation in the middle frequency range remained unchanged by the ethanol–benzene extraction of specimens. The relaxation location was independent of measuring directions. The relaxation in the lowest frequency range was not detected in the specimens impregnated with methyl methacrylate (MMA). This result suggested that the relaxation was due to electrode polarization. The Cole-Cole circular arc law applied well to two relaxations recognized in the specimens impregnated with MMA. The relaxation magnitude in the middle frequency range was extremely large, and the distribution of relaxation times was very narrow. These characteristics suggested relaxation of the Maxwell-Wagner type resulting from the interfacial polarization in the heterogeneous structure, which included adsorbed water with large electrical conductivity within the insulating cell walls.     

Interaction of lignin and polysaccharides in beech wood (Fagus sylvatica) during drying processes

Summary ¹³C CP MAS NMR spectroscopy was used to characterize the structural changes of cell wall polymers in beech wood Fagus sylvatica during drying processes. The analysis of five wood samples, namely, untreated, untreated dried, pre-treated by steam and/or NaOH subjected to drying showed partial depolymerization of lignin component as well as the change of the ratio of the crystalline and of the amorphous parts of cellulose as the consequence of wood pre-treatment. In addition, T_1ρ(¹H) relaxation times were determined in beech wood sample pre-treated with steam at 135 °C and the lignin isolated from this sample. The magnitudes of the relaxation times were found comparable in both samples as well as in the lignin-cellulose model compound. These unique T_1ρ (¹H) values indicate that spin diffusion is complete and homogeneous due to spatial proximity of spins and confirmed the formation of lignin-cellulose complex during thermal treatment of wood. Received 30 June 1997