Structure Of Wood Cell Walls Research Articles

An Oxidative Enzyme Boosting Mechanical and Optical Performance of Densified Wood Films.

Nature has evolved elegant ways to alter the wood cell wall structure through carbohydrate-active enzymes, offering environmentally friendly solutions to tailor the microstructure of wood for high-performance materials. In this work, the cell wall structure of delignified wood is modified under mild reaction conditions using an oxidative enzyme, lytic polysaccharide monooxygenase (LPMO). LPMO oxidation results in nanofibrillation of cellulose microfibril bundles inside the wood cell wall, allowing densification of delignified wood under ambient conditions and low pressure into transparentanisotropic films. The enzymatic nanofibrillation facilitates microfibril fusion and enhances the adhesion between the adjacent wood fiber cells during densification process, thereby significantly improving the mechanical performance of the films in both longitudinal and transverse directions. These results improve the understanding of LPMO-induced microstructural changes in wood and offer an environmentally friendly alternative for harsh chemical treatments and energy-intensive densification processes thusrepresenting a significant advance in sustainable production of high-performance wood-derived materials.

Delignified Wood from Understanding the Hierarchically Aligned Cellulosic Structures to Creating Novel Functional Materials: A Review

AbstractUtilization of hierarchically aligned natural cellulosic structures has become a leading natural template scaffold for a diverse range of functional applications. This natural scaffold derived from wood by partial or full removal of lignin without altering or disturbing the hierarchically aligned cellulosic structure is known as delignified wood (DW). Over the past five years, various types of functional materials for diverse applications have been fabricated using DW. This review aims to highlight the significance of DW in functional material development by discussing the delignification impacts on the wood cell wall properties and review the different strategies used in functional materials fabrication. The first part of this review discusses the fundamental aspects of wood cell wall structure in relation to wood chemistry and lignin biosynthesis. The second part focuses on the different delignification methods used in partial and full lignin removal from wood cell walls and the fundamental properties (i.e., physical, mechanical, and chemical) of DW. The third part of this review discusses the strategies and the detailed current literature regarding the development of diverse functional materials based on DW. A greater understanding of DW provides the potential for further development of DW‐based functional materials for a diverse range of future applications.

Correlation between bacterial decay and chemical changes in waterlogged archaeological wood analysed by light microscopy and Py-GC/MS

AbstractErosion bacteria are the main degraders of archaeological wood excavated from waterlogged environments. Light microscopy and analytical pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) were exploited to study waterlogged archaeological wood (Pinus sylvestrisL.) at different stages of bacterial decay. The research explored the biochemical changes related to erosion bacteria degradation of the secondary cell wall in the wood cells and the chemical changes related to abiotic processes induced by the long-term waterlogged burial environment. Erosion bacteria were demonstrated by chemical analysis to cause significant holocellulose depletion. Detailed analysis of the holocellulose and lignin pyrolysis products revealed only minor chemical changes in the residual structure even after heavy erosion bacteria decay. Chemical changes in the lignin polymer is associated to enzymatic unlocking of the lignocellulose to gain access to the holocellulose fraction of the cell wall. Chemical changes in the holocellulose fraction are suggested to stem from depolymerisation and from alterations in the polymer matrix of the residual wood cell wall structure. Interestingly, a difference was observed between the sound reference wood and the waterlogged archaeological wood without erosion bacteria decay, indicating that long-term exposure in waterlogged environments results in partial decay of the holocellulose even in absence of bacterial activity.

Self-Densification of Highly Mesoporous Wood Structure into a Strong and Transparent Film.

In the native wood cell wall, cellulose microfibrils are highly aligned and organized in the secondary cell wall. A new preparation strategy is developed to achieve individualization of cellulose microfibrils within the wood cell wall structure without introducing mechanical disintegration. The resulting mesoporous wood structure has a high specific surface area of 197 m2 g-1 when prepared by freeze-drying using liquid nitrogen, and 249 m2 g-1 by supercritical drying. These values are 5 to 7 times higher than conventional delignified wood (36 m2 g-1 ) dried by supercritical drying. Such highly mesoporous structure with individualized cellulose microfibrils maintaining their natural alignment and organization can be processed into aerogels with high porosity and high compressive strength. In addition, a strong film with a tensile strength of 449.1 ± 21.8 MPa and a Young's modulus of 51.1 ± 5.2 GPa along the fiber direction is obtained simply by air drying owing to the self-densification of cellulose microfibrils driven by the elastocapillary forces upon water evaporation. The self-densified film also shows high optical transmittance (80%) and high optical haze (70%) with interesting biaxial light scattering behavior owing to the natural alignment of cellulose microfibrils.

Improvement of Mechanical, Hydrophobicity and Thermal Properties of Chinese Fir Wood by Impregnation of Nano Silica Sol.

In this paper, a wood-SiO2 composite material was prepared via in-situ polymerization using vacuum/pressure impregnation technology using commercial scale nano silica sol and Chinese Fir (Cunninghamia lanceolate (Lamb.) Hook.). Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TG), and water contact angle were used to study the changes in the microstructure and physical and mechanical properties of this composite. The results showed that silica sol can penetrate and distribute into the wood cell cavities and surface of cell walls and hence combine with the substances of wood materials. FTIR results indicated that the –OH groups of wood can polycondense in-situ with silica sol to form Si–O–C covalent bonds, and amorphous SiO2 formed from Si–O–Si bonds between the –OH groups of silica sol did not change the crystalline structure of wood cell walls. This in-situ formulating composite significantly improved the compact microstructure, thermal and mechanical properties, and hydrophobicity of the composites.

Nanostructural Analysis of Enzymatic and Non-enzymatic Brown Rot Fungal Deconstruction of the Lignocellulose Cell Wall†.

Brown rot (BR) decay mechanisms employ carbohydrate-active enzymes (CAZymes) as well as a unique non-enzymatic chelator-mediated Fenton (CMF) chemistry to deconstruct lignocellulosic materials. Unlike white rot fungi, BR fungi lack peroxidases for lignin deconstruction, and also lack some endoglucanase/cellobiohydrolase activities. The role that the CMF mechanism plays in “opening up” the wood cell wall structure in advance of enzymatic action, and any interaction between CMF constituents and the selective CAZyme suite that BRs possess, is still unclear. Expression patterns for CMF redox metabolites and lytic polysaccharide monooxygenase (LPMO–AA9 family) genes showed that some LPMO isozymes were upregulated with genes associated with CMF at early stages of brown rot by Gloeophyllum trabeum. In the structural studies, wood decayed by the G. trabeum was compared to CMF-treated wood, or CMF-treated wood followed by treatment with either the early-upregulated LPMO or a commercial CAZyme cocktail. Structural modification of decayed/treated wood was characterized using small angle neutron scattering. CMF treatment produced neutron scattering patterns similar to that of the BR decay indicating that both systems enlarged the nanopore structure of wood cell walls to permit enzyme access. Enzymatic deconstruction of cellulose or lignin in raw wood samples was not achieved via CAZyme cocktail or LPMO enzyme action alone. CMF treatment resulted in depolymerization of crystalline cellulose as attack progressed from the outer regions of individual crystallites. Multiple pulses of CMF treatment on raw wood showed a progressive increase in the spacing between the cellulose elementary fibrils (EFs), indicating the CMF eroded the matrix outside the EF bundles, leading to less tightly packed EFs. Peracetic acid delignification treatment enhanced subsequent CMF treatment effects, and allowed both enzyme systems to further increase spacing of the EFs. Moreover, even after a single pulse of CMF treatment, both enzymes were apparently able to penetrate the cell wall to further increase EF spacing. The data suggest the potential for the early-upregulated LPMO enzyme to work in association with CMF chemistry, suggesting that G. trabeum may have adopted mechanisms to integrate non-enzymatic and enzymatic chemistries together during early stages of brown rot decay.

On the use of vibrational spectroscopy and scanning electron microscopy to study phenolic extractability of cooperage byproducts in wine

Wood is an important source of phenolic compounds, which can be transferred to wine during aging process, improving its properties, from an organoleptic point of view. Therefore, understanding and optimizing the extractability of phenolic compounds from wood are crucial in the oenological field. The structural composition of oak wood samples has been evaluated using Raman and attenuated total reflectance Fourier transform infrared (ATR–FTIR) spectroscopies, and their main spectral features have been linked to phenolic compound extractabilities, as measured by classic chemical analyses. To support the analysis, microscopic images of the samples were also recorded using scanning electron microscopy (SEM). The applied methodology is shown to be useful to relate the wood cell wall structure to phenolic extractability levels of wood samples. It could assist in selecting oak wood suited for improving wine quality with regard to its color or/and stability through the addiction of external copigments to wine.

Assessing multi-scale deconstruction of wood cell wall subjected to mechanical milling for enhancing enzymatic hydrolysis

The hierarchical structure of wood cell walls resulting from complex arrangement and distribution of the heterogeneous components is considered to impact significant impediment to enzymatic hydrolysis of cellulose for biofuels. In this work, micronized wood with significant cell wall ultrastructural deconstruction were effectively produced from ring and puck milling within 12min. In a subsequent enzymatic hydrolysis, micronized wood resulted in increase of cellulose hydrolysability by 4–14 folds over that of starting material. The underlying mechanism towards facilitating enzymatic hydrolysis was studied through delineating the ultrastructural changes and alternation of cellulose chemistry in micronized wood cell wall using SEM, TEM, CLSM, GPC, XRD, HPLC and Simon’s staining techniques. Electronic microscopy revealed distinct stages of wood cell wall deconstruction that was coincident with particle size reduction, including cell fracture and delamination, cell wall disintegration, and amorphization of cell wall fragments. Simons’ staining results also indicated increasing substrate accessibility and porosity of micronized wood, likely due to the ultrastructure alternation of cell walls. GPC and XRD revealed significant decrease of cellulose degree of polymerization (DP) and crystallinity. The correlation of these factors with cellulose hydrolysability was studied and further arranged in order through principal component analysis. The major positive factors affecting hydrolysability were surface accessibility and porosity, while cellulose crystallinity and DP were the major negative factors accompanied by particle size. The established weighed order of factors behind hydrolysability provides insights of lowering cell wall structural recalcitrance by mechanical manner.

The COST action FP1105 – a research network to understand wood cell wall structure, biopolymer interaction and composition

The COST action FP1105 : a research network to understand wood cell wall structure, biopolymer interaction and composition

Effect of compression combined with steam treatment on the porosity, chemical compositon and cellulose crystalline structure of wood cell walls

The changes of porosity, chemical composition and cellulose crystalline structure of Spruce (Picea abies Karst.) wood cell walls due to compression combined with steam treatment (CS-treatment) were investigated by nitrogen adsorption, confocal Raman microscopy (CRM) and X-ray diffraction (XRD), respectively. A number of slit-shaped mesopores with a diameter of 3.7nm was formed for the CS-treated wood, and more mesopores were found in the steam-treated wood. CRM results revealed cellulose structure was affected by treatment and β-aryl-ether links associated to guaiacyl units of lignin was depolymerized followed by re-condensation reactions. The crystallinity index (CrI) and crystallite thickness (D200) of cellulose for CS-treated wood were largely increased due to crystallization in the semicrystalline region. Higher degree of increase in both CrI and D200 was observed in both the earlywood and latewood of steam-treated wood, ascribing to the greater amount of mesopores in steam-treated wood than CS-treated wood.

Fully biodegradable modification of wood for improvement of dimensional stability and water absorption properties by poly(ε-caprolactone) grafting into the cell walls

Materials derived from renewable resources are highly desirable in view of more sustainable manufacturing. Among the available natural materials, wood is one of the key candidates, because of its excellent mechanical properties. However, wood and wood-based materials in engineering applications suffer from various restraints, such as dimensional instability upon humidity changes. Several wood modification treatments increase water repellence, but the insertion of hydrophobic polymers can result in a composite material which cannot be considered as renewable anymore. In this study, we report on the grafting of the fully biodegradable poly(e-caprolactone) (PCL) inside the wood cell walls by Sn(Oct)2 catalysed ring-opening polymerization (ROP). The presence of polyester chains within the wood cell wall structure is monitored by confocal Raman imaging and spectroscopy as well as scanning electron microscopy. Physical tests reveal that the modified wood is more hydrophobic due to the bulking of the cell wall structure with the polyester chains, which results in a novel fully biodegradable wood material with improved dimensional stability.

Multi-scale finite element model for a new material inspired by the mechanics and structure of wood cell-walls

This paper proposes a fully coupled multi-scale finite element model for the constitutive description of an alumina/magnesium alloy/epoxy composite inspired in the mechanics and structure of the wall of wood cells. The mechanical response of the composite (the large scale continuum) is described by means of a representative volume element (RVE, corresponding to the intermediate scale) in which the fibre is represented as a periodic alternation of alumina and magnesium alloy fractions. Furthermore, at a lower scale the overall constitutive behavior of the alumina/magnesium alloy fibre is modelled as a single material defined by a large number of RVEs (the smallest material scale) at the Gauss point (intermediate) level. Numerical material tests show that this new composite maximises its toughness when the hierarchical design of wood cellulose fibres is replicated. The above results provide for the first time new clues into the understanding of how trees and plants optimise their microstructures at the cellulose level in order to absorb a large amount of strain energy before failure. These findings are likely to shed more light into natural materials and bio-inspired design strategies, which are still not well-understood at present.

REORIENTATION OF FIBRES AND LOCAL MECHANISMS OF DEFORMATION IN A WOOD-INSPIRED COMPOSITE

This paper investigates the reorientation of fibres and local mechanisms of deformation in a composite material inspired by the mechanics and structure of wood cell-walls. The mechanical response of the material is calculated under tensile loading conditions by means of the computational homogenisation of a two-dimensional representative volume element (RVE) of material. Here, the fibres are represented by a periodic alternation of alumina and magnesium alloy fractions, embedded in a soft epoxy matrix. In order to validate the present multi-scale framework, we compare our numerical prediction for the reorientation of fibres in the wood cell-wall composite with experimental data, finding a good agreement for a wide range of strains. Numerical simulations show that the model is able to describe the reorientation of fibres and the different stages of local deformation and failure in the proposed wood-inspired material. Furthermore, we assess a simple expression to calculate the reorientation of fibres and the in-plane Poisson's ratio of the present composite.

Cell wall features with regard to mechanical performance. A review COST Action E35 2004–2008: Wood machining – micromechanics and fracture

Abstract The mechanical performance of wood and wood products is highly dependent on the structural arrangement and properties of the polymers within the fibre cell wall. To improve utilisation and manufacture of wood materials, there is an increasing need for a more detailed knowledge regarding structure/property relations at the micro- or nanostructural level. In this article, recent developments regarding our understanding of the wood cell wall structure and its mechanical performance are summarised. The new results are interpreted in relation to property performances of wood fibres and wood tissues. Suggestions are made for future requirements for research in this field.

Synchrotron Radiation X-Ray Scattering Techniques for Studying the Micro- and Nanostructure of Wood and their Relation to the Mechanical Properties

X-ray scattering techniques have been a very useful tool for the non-destructive analysis of the wood structure. X-rays are sensitive to structural parameters such as the composite structure of wood cell walls, the crystal structure of cellulose microfibrils and their helical arrangement in the cell wall, which is usually described by the microfibril angle (MFA). With the availability of synchrotron radiation sources novel experiments on wood have become possible. The increased flux of X-rays makes the in situ and time-resolved investigation of structural changes upon mechanical stress possible. The low-divergence synchrotron radiation X-rays can be focused down to sub-micrometer size, enabling scanning studies of the wood nanostructure with (sub-)microscopic position resolution. This chapter highlights very recent advances in the understanding of wood micro- and nanostructure, which were only possible using synchrotron radiation. Examples include the MFA determination in the individual layers of the secondary cell wall, the imaging of the helical structure of the cellulose microfibrils in the cell wall, lattice strain as induced by applied mechanical stress and the structural changes of different wood types under external tensile stress.

Modelling polymer interactions of the ‘molecular Velcro’ type in wood under mechanical stress

Trees withstand wind and snow loads by synthesising wood that varies greatly in mechanical properties: flexible in twigs and in the stem of the sapling, and rigid in the outer part of the mature stem. The ‘molecular Velcro’ model of Keckes et al. [2003. Cell-wall recovery after irreversible deformation of wood. Nat. Mater. 2, 810–814] permits the simulation of the tensile properties of water-saturated wood as found in living trees. A basic feature of this model is the presence of non-covalent interactions between hemicellulose chains attached to adjacent cellulose microfibrils, which are disrupted above a threshold level of interfibrillar shear. However, other evidence does not confirm the importance of hemicellulose–hemicellulose association in the cohesion of the interfibrillar matrix. Here, we present an alternative model in which hemicellulose chains bridging continuously from one microfibril aggregate (macrofibril) to the next provide most of the cohesion. We show that such hemicellulose bridges exist and that the stripping of the bridging chains from the cellulose surfaces under the tensile stress component normal to the macrofibrils can provide an alternative triggering mechanism for shear deformation between one macrofibril and the next. When one macrofibril then slides past another, a domain of the wood cell wall can extend but simultaneously it twists until the spacing between macrofibrils is reduced again and contact through hemicelluloses bridges is restored. Overall deformation therefore takes place through a series of local stick–slip events involving temporary twisting of small domains within the wood cell wall. Modelled load–deformation curves for this modified ‘molecular Velcro’ model are similar, although not identical, to those for the original model. However, the mechanism is different and more consistent with current views of the structure of wood cell walls, providing a framework within which the developmental control of rigidity in wood synthesised in different parts of a tree may be considered.

Properties of piezoelectric voltage considering the microscopic structure of wood cell walls

Abstract The combined effects of the grain-angle (θ) and the microfibril angle (MFA) on the piezoelectric voltage (P) are discussed for a wood specimen subjected to unidirectional stress. The fiber axis of the specimen investigated was not parallel to the loading direction. A theoretical discussion is provided concerning fundamental elastic equations that predict the elastic strain field in the crystalline cellulose microfibril (CMF). It was assumed that an ideal wood specimen could be represented by a multi-tracheid model consisting mainly of the middle layer of the secondary wall. Experimental results revealed that plots of the piezoelectric voltage (P) versus the grain angle (θ) show concave curves with a maximum at θ=45°, regardless of MFA in the specimen. A similar tendency was obtained for the relationship predicted between the average shear strain along the CMF and θ. The results indicate that generation of a shear strain in the CMF positively contributes to the piezoelectric effect in wood.

The importance of seasonal differences in the cellulose microfibril angle in softwoods in determining acoustic properties

The influence of the micro- and mesoscopic structure of wood cell walls on the acoustic properties of softwood was investigated in a synchrotron X-ray microbeam diffraction experiment with particular attention to the seasonal differences in crystallographic features. A multiple regression analysis was performed for data from 12 different softwood species in order to determine the dependence of longitudinal relative Young's modulus (E/ρ) and loss tangent (tanδ) on seasonal cellulose microfibril angles (MFAs), crystal width of cellulose microfibrils etc. We conclude that a low MFA in both latewood and earlywood yields high E/ρ and low tanδ, which is an attribute of wood used as violin or piano soundboards. Among the softwood species we characterized Sitka spruce best fits this criterion.

Dielectric behavior of wood–polystyrene composite

AbstractThe dielectric phenomena for alder wood natural and modified with polystyrene were studied. Temperature dependences of the complex permittivity components of these materials were obtained for the temperature interval from 100 to 450 K at the frequencies of measuring electric field of 420 Hz, 2 kHz, and 10 kHz. The changes in structure of wood cell walls were found, detected as an increase in number of polar functional groups taking part in the relaxation processes and as a partial freezing of conformational degrees of freedom of macromolecule fragments carrying these groups. The origin of the structural changes can be the efect of wood substance swelling caused by polystyrene, which penetrates the composite cell walls.

Ultramicrotomy, its application in wood research

Forced by the progressive perfectionation of the ultramicrotomes and by the improvement of preparation methods, the ultrathin sectioning technique has gained high importance for the electron-microscopical studies of the fine structure of wood cell walls. Wood has its own problems for ultramicrotomy. During cutting, the inhomogeneity of the cell wall and its chemical nature result in the formation of wrinkles and holes in the ultrathin sections. These artefacts are not completely avoidable but can be reduced by suitable embedding and by choosing the most suitable knife to a minimum. It is pointed out that for the best and most reliable statement on the object the cutting of serial sections is indispensable.