Influence of Lignin On Plastic Flow Deformation of Wood

In this study, we clarified the influence of lignin in wood on its plastic flow deformation due to shear sliding of wood cells. Wood samples were subjected to delignification, where the lignin structure gradually changed, and characterized for their chemical and physicochemical properties, and deformability by free compression testing. The delignified wood deformed by efficient stretching and maintained its cell structures at a lower pressure compared to the untreated wood. The deformability was evaluated from two viewpoints: the initial resistance to plastic flow and final stretchability. The deformability of the delignified and untreated wood increased with increasing compressive temperature, even though the changes in molecular motility associated with the glass transition of lignin contributed minimally to the improvement in deformability. In the early stages of delignification, the molecular mass of lignin in the compound middle lamella decreased, which reduced the initial resistance to plastic flow. However, during the early stages of delignification, the stretchability of delignified wood was scarcely affected by changes in lignin. As the amount of lignin was further reduced and delignification proceeded in the vicinity of the polysaccharides, the stretchability significantly improved. The correlation between chemical and physicochemical properties and plastic flow deformability presented in this paper will be helpful for low-energy and highly productive forming of solid-state wood.

Histochemical Structure and Tensile Properties of Birch Cork Cell Walls

Tensile tests of birch cork were performed in the tangential direction. Birch cork in the wet state showed significantly higher extensibility and toughness than those in the oven-dried state. The histochemical structure of birch cork was investigated by microscopic observation and spectroscopic analysis. Birch cork cell walls showed a three-layered structure. In transmission electron micrographs, osmium tetroxide stained the outer and inner layers, whereas potassium permanganate stained the middle and inner layers. After chemical treatment to remove suberin and lignin, the outer and inner layers disappeared and Fourier-transformed infrared spectra showed the cellulose I pattern. Polarizing light micrographs indicated that molecular chains in the outer and inner layers were oriented perpendicular to suberin lamination, whereas those in the inner layer showed longitudinal orientation. These results suggested that the outer and inner layers mainly consist of suberin, whereas the middle layer and compound middle lamella consist of lignin, cellulose, and other polysaccharides. We hypothesized a hierarchical model of the birch cork cell wall. The lignified cell wall with helical arrangement of cellulose microfibrils is sandwiched between two suberized walls. Cellulose microfibrils in the middle layer act like a spring and bear tensile loads. In the wet state, water and cellulose in the compound middle lamella transfer tensile stress between cells. In the dried state, this stress-transferal system functions poorly and fewer cells bear stress. Suberin in the outer and inner layers prevents absolute drying to maintain mechanical properties of the bark and to bear tensile stress caused by trunk diameter growth.

Characterisation of compound middle lamella isolated by a combination of wet-beating, sedimentation, and methanol dialysis

A simple method was developed to isolate the compound middle lamella (CML) in its natural state using wet-beating, sedimentation, and methanol dialysis. The isolated CML fraction was characterised. The CML was isolated in 2.0% yield from the mature wood of Ginkgo biloba. Scanning electron microscopy (SEM) images of the isolated CML fraction showed the presence of flake-like structures. However, some small amounts of secondary wall substance was observed. The lignin content of the CML fraction was approximately 45%. Thioacidolysis reactions with the isolated CML fraction revealed that the lignin β-O-4 structure was scarce in the isolated fraction and that numerous structures with two or more consecutive condensed-type bonds were present. Results from the solid-state carbon-13 nuclear magnetic resonance (13C NMR) experiments indicated that the CML fraction had low crystallinity, indicating low cellulose content. Liquid-state NMR analysis of the lignin from the CML fraction revealed the absence of p-hydroxyphenyl (H) units.

Xylan deposition and lignification in differentiating tension wood fibers in Mallotus japonicus (Euphorbiaceae) with multi-layered structure

Xylan deposition and lignification processes were examined in tension wood fibers with gelatinous layers (G-layers) in Mallotus japonicus (Euphorbiaceae). The cell walls consisted of a multi-layered structure of S1 + S2 + G + n(L + G), where n indicates the number of repetitions (n = 0–3) and L indicates very thin lignified layers. The formation and lignification processes of the multi-layered structure of tension wood fibers were examined by light microscopy, ultraviolet microscopy, and transmission electron microscopy (TEM) following KMnO4 staining. The deposition of xylan was examined by immunoelectron microscopy with a monoclonal antibody (LM11). Immunolabelling of xylan appeared in lignified cell wall layers, except in the compound middle lamella (CML), i.e., the S1, S2, and L layers but not the G-layers. The density of LM11 xylan immunogold labeling in S2 layers increased during the formation of G-layers. This increase was due to the shrinkage of S2 layers during development rather than intrusive deposition of xylan through G-layers. Lignification of the CML, S1, and S2 layers proceeded during G-layer formation. The shrinkage of S2 layers occurred almost simultaneously with the lignification of the S2 layers during G-layer formation, suggesting that the S2 layers shrank with lignification.

Comparative study of the topochemistry on delignification of Japanese beech (Fagus crenata) in subcritical phenol and subcritical water

The delignification of Japanese beech (Fagus crenata) has been evaluated under conditions of subcritical phenol (230°C/1.2 MPa) and subcritical water (230°C/2.9 MPa). In the former, more than 90% of the original lignin was decomposed and removed, while in subcritical water, around half of the original lignin was left as insoluble residue. Ultraviolet (UV) microscopic images of the insoluble residues showed that the lignin in the secondary walls is decomposed and removed under both conditions. These images also revealed that the lignin in the compound middle lamella (CML) is resistant to subcritical water, but not to subcritical phenol. Results of alkaline nitrobenzene oxidation of the residual lignin confirmed these observations. Lignin in Japanese beech wood was phenolated by subcritical phenol, which was efficiently removed due to its high solubility in the reactant. It is obvious that CML is rich in condensed-type linkages facilitating rapid solvolysis by phenol. The topochemistry of the plant has a pronounced impact on its delignification behavior.

Chemical and ultrastructural changes of ash wood thermally modified (TMW) using the thermo-vacuum process: II. Immunocytochemical study of the distribution of noncellulosic polysaccharides

Following structural and cytochemical studies (Part I) on thermally modified ash wood (TMW) by the thermo-vacuum (Termovuoto) process, changes in the distribution of noncellulosic polysaccharides have been investigated in TMW treated for 3 h at 220°C (TMW3 h, 220°C) by means of immunogold localization methods. Pectins (homogalacturonan, rhamnogalacturonan-I) and xyloglucan were significantly degraded in compound middle lamella (CML), including the middle lamella cell corner regions (CMLcc), of all xylem cells after thermal modification. Xylan and mannan degradation were also visible in fiber cell walls. In particular, degradation of mannan was very significant and showed variation between cell wall regions even within the same cell wall. The degradation of pectins was more significant than that of hemicelluloses. In summary, results suggest that each noncellulosic polysaccharide may have a different degradation process in ash TMWs.

Chemical and ultrastructural changes in compound middle lamella (CML) regions of softwoods thermally modified by the Termovuoto process

Silver fir and Norway spruce wood have been thermally modified (TMW) for 3–4 h at 160°C, 180°C, 200°C, and 220°C by means of the thermovacuum process (Termovuoto), and the ultrastructural and chemical changes in the compound middle lamella (CML), including the middle lamella cell corner (MLcc) regions (CMLcc), were investigated. Severe anatomical and histochemical changes were prominent above treatment temperatures of 200°C; thus, woods treated at 220°C for 4 h were in focus. Immunocytochemical studies showed that noncellulosic polysaccharides, such as pectin, xyloglucan, xylan, and mannan, were significantly degraded in CMLcc regions of TMWs. After treatment, the CMLcc regions were composed almost entirely of modified lignin with increased amounts of acidic groups. With cytochemical staining for lignin, many electron dense particulates were detected in the CMLcc regions of TMWs, indicating early degradation/alteration by the Termovuoto treatment.

Proposed supramolecular structure of lignin in softwood tracheid compound middle lamella regions

The structure of lignin in the compound middle lamella (CML) of softwood tracheids differs from that in the secondary wall (SW) in regard to the content of condensed structures (5-5′-biphenyl, dibenzodioxocin and 4-O-5′-diphenyl ether). In an early stage of cell wall formation, random coarse networks composed of thin cellulose microfibrils (CMFs), hemicelluloses, and pectin are formed in the CML, then globular p-hydroxyphenyl/guaiacyl lignin (HG-lignin) is deposited quickly into the network. The globular lignin is assumed to be a micellar aggregate of oligolignols folded at the β-O-4 bond with their phenolic ends on the outer part of the aggregate. When 3D clusters of the globules are deposited on the preformed network of polysaccharides, further growth of the oligolignols by endwise addition of new monolignols is spatially limited, so frequent condensation occurs between growing aromatic ends of adjacent HG-oligolignols within the globule and between the wide contact boundaries of the 3D clustered globules to produce a highly condensed supramolecule in CML. In SW, the folded G-oligolignols are deposited slowly in the narrow tubular space surrounding thick CMFs coated with hemicelluloses. Condensation occurs mostly between adjacent growing ends of the oligolignols within the tubular aggregates. Spatial regulation of condensation of folded polylignols is one of the factors producing a different supramolecular structure for CML lignin than for SW lignin.

Within-process and seasonal changes during industrial production of high-density fibreboard. Part 1: Influence of wood species composition on polyoses in the products

Industrially produced high-density fibreboard fibres are inhomogeneous in structure and chemical composition. Changes in polysaccharide chemistry during processing have an impact on strength loss, fibre separation and structural alterations. In the present study, carbohydrate composition of extracted wood chips and refiner fibres was monitored for a year at an industrial HDF plant. The polysaccharides were analysed via methanolysis and quantification of the monomeric sugars released. Significant reductions of arabinose, xylose, rhamnose and galacturonic acid were observed. The amount of glucose and extractable substances increased. The depletion of galacturonic acid and rhamnose indicates a degradation of pectin located in the compound middle lamella. The diminishing amounts of the other sugars and elevated extractive contents are a result of hemicellulose degradation. A pronounced seasonal variability of the data was observed depending on the processed wood species and degree of chemical degradation.