Cellulose crystallinity assessment is important for optimizing the yield of cellulose products, such as bioethanol. X-ray diffraction is often used for this purpose for its perceived robustness and availability. In this work, the five most common analysis methods (the Segal peak height method and those based on peak fitting and/or amorphous standards) are critically reviewed and compared to two-dimensional Rietveld refinement. A larger (n ¼ 16) and more varied collection of samples than previous studies have presented is used. In particular, samples (n ¼ 6) with low crystallinity and small crystallite sizes are included. A good linear correlation (r 2 ! 0:90) between the five most common methods suggests that they agree on large-scale crystallinity differences between samples. For small crystallinity differences, however, correlation was not seen for samples that were from distinct sample sets. The least-squares fitting using an amorphous standard shows the smallest crystallite size dependence and this method combined with perpendicular transmission geometry also yielded values closest to independently obtained cellulose crystallinity values. On the other hand, these values are too low according to the Rietveld refinement. All analysis methods have weaknesses that should be considered when assessing differences in sample crystallinity.
Composite fibres that contain cellulose and lignin were produced from ionic liquid solutions by dry-jet wet spinning. Eucalyptus dissolving pulp and organosolv/kraft lignin blends in different ratios were dissolved in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate to prepare a spinning dope from which composite fibres were spun successfully. The composite fibres had a high strength with slightly decreasing values for fibres with an increasing share of lignin, which is because of the reduction in crystallinity. The total orientation of composite fibres and SEM images show morphological changes caused by the presence of lignin. The hydrophobic contribution of lignin reduced the vapour adsorption in the fibre. Thermogravimetric analysis curves of the composite fibres reveal the positive effect of the lignin on the carbonisation yield. Finally, the composite fibre was found to be a potential raw material for textile manufacturing and as a precursor for carbon fibre production.
Balsa, with its low density and relatively high mechanical properties, is frequently used as the core in structural sandwich panels, in applications ranging from wind turbine blades to racing yachts. Here, we describe both the cellular and cell wall structure of balsa, to enable multi-scale modelling and an improved understanding of its mechanical properties. The cellular structure consists of fibers (66-76%), rays (20-25%) and vessels (3-9%). The density of balsa ranges from roughly 60 to 380 kg/m 3 ; the large density variation derives largely from the fibers, which decrease in edge length and increase in wall thickness as the density increases. The increase in cell wall thickness is predominantly due to a thicker secondary S2 layer. Cellulose microfibrils in the S2 layer are highly aligned with the fiber axis, with a mean microfibril angle (MFA) of about 1.4°.The cellulose crystallites are about 3 nm in width and 20-30 nm in length. The degree of cellulose crystallinity appears to be between 80-90%, considerably higher than previously reported for other woods. The outstanding mechanical properties of balsa wood in relation to its weight are likely explained by the low MFA and the high cellulose crystallinity.
BackgroundLignocellulose from fast growing hardwood species is a preferred source of polysaccharides for advanced biofuels and “green” chemicals. However, the extensive acetylation of hardwood xylan hinders lignocellulose saccharification by obstructing enzymatic xylan hydrolysis and causing inhibitory acetic acid concentrations during microbial sugar fermentation. To optimize lignocellulose for cost-effective saccharification and biofuel production, an acetyl xylan esterase AnAXE1 from Aspergillus niger was introduced into aspen and targeted to cell walls.Results
AnAXE1-expressing plants exhibited reduced xylan acetylation and grew normally. Without pretreatment, their lignocellulose yielded over 25% more glucose per unit mass of wood (dry weight) than wild-type plants. Glucose yields were less improved (+7%) after acid pretreatment, which hydrolyses xylan. The results indicate that AnAXE1 expression also reduced the molecular weight of xylan, and xylan–lignin complexes and/or lignin co-extracted with xylan, increased cellulose crystallinity, altered the lignin composition, reducing its syringyl to guaiacyl ratio, and increased lignin solubility in dioxane and hot water. Lignin-associated carbohydrates became enriched in xylose residues, indicating a higher content of xylo-oligosaccharides.ConclusionsThis work revealed several changes in plant cell walls caused by deacetylation of xylan. We propose that deacetylated xylan is partially hydrolyzed in the cell walls, liberating xylo-oligosaccharides and their associated lignin oligomers from the cell wall network. Deacetylating xylan thus not only increases its susceptibility to hydrolytic enzymes during saccharification but also changes the cell wall architecture, increasing the extractability of lignin and xylan and facilitating saccharification.Electronic supplementary materialThe online version of this article (doi:10.1186/s13068-017-0782-4) contains supplementary material, which is available to authorized users.
Bamboo is an underutilized resource widely available in countries with rapidly developing economies. Structural bamboo products, analogous to wood products, allow flexibility in the shape and dimensions of bamboo structural members. Here, the ultrastructure, microstructure, cell wall properties and flexural properties of three species of bamboo (Moso, Guadua and Tre Gai) are compared. At a given density, the axial modulus of elasticity of Guadua is higher than that of Moso or Tre Gai, which are similar; ultrastructural results suggest that Guadua has a higher solid cell wall stiffness. At a given density, their moduli of rupture are similar.
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