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As a renewable biological macromolecule with aromatic structure, lignin can serve as matrix substance to maintain cell wall integrity and is regarded as the natural biomass recalcitrance. Substantial differences in the cell wall lignin topochemistry between opposite (Ow) and compression wood (Cw) trachieds in Pinus bungeana Zucc. were visualized during [Emim][OAc] pretreatment at room temperature. The ionic liqiuds treatment induced a more obvious wall swelling for highly lignified Cw tracheids than that of Ow, while dynamic Raman spectra analysis indicated the higher lignin and carbohydrates removal for Ow tracheids. Raman imaging further revealed that both lignin and carbohydrates were dissolved simultaneously within the middle lamella and secondary wall of Ow and pretreatment has little effects on Cw tracheids wall. Moreover, it was demonstrated that lignin composition was the key factor to affect the composition dissolution. In particular, lignin G-units were selectively removed from cell corner middle lamella (52.3 %) and secondary wall (62.0 %) of Ow tracheids. When cotton fiber, as a reference was treated under the same conditions, lattice conversion moving from cellulose I to II occurred. The findings confirmed the important role of lignin compostion in the dissolution behavior of carbohydrate dominant tracheids wall.

Sustainable biomass resources are favored by researchers on account of their biodegradability and biocompatibility, which is a replacement for non-renewable fossil fuels. The development of low-carbon, green, and high-value bio-based adhesives are the inevitable trend of the industry development. However, the main factors limiting their application are poor water resistance and low bonding performance. Herein, the crosslinking network was constructed based on the reaction between the epoxy groups of trimethylolpropane glycidyl ether (TMPEG) and the amino groups of the synthesized aminated cellulose (AC) to form an interlocking bond. Through the synergy of covalent bond, electrostatic interaction, and hydrogen bond, the bonding strength and water resistance of the proposed adhesive can be effectively improved. Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and solid-state nuclear magnetic resonance spectroscopy (

Biomass-based adhesives are considered to be the preferred alternative to formaldehyde-type wood adhesives due to their wide range of sources, low cost, and sustainability. Herein, an environmentally friendly Schiff base cross-linked compact three-dimensional network structure bio-adhesive (DAC-PEI-U) derived from polyethyleneimine (PEI), urea, and cellulose was successfully prepared, verifying by detailed FTIR, NMR, and XPS analysis. Schiff base bridging between aldehyde groups in dialdehyde cellulose (DAC) and amino groups in polyurea (PEIU) not only constructed crosslinking networks but also endowed adhesives with good adhesion property. The dry bond strength of DAC-PEI-U adhesive reached 2.71 MPa, and the wet shear strength was 1.51 MPa (hot water) and 1.34 MPa (boiling water), respectively. It not only improves the water resistance and bonding process, but also displays simple synthesis and low cost. The improved performance of DAC-PEI-U adhesive is attributed to the generation of hyperbranched cross-linking structure in the adhesive system, which results in increased cross-linking density and promotes the formation of dense cross-sections in the curing adhesive. This work paves a solid way for developing cellulose-based wood adhesives with wet bonding properties, thus holding great potential as an alternative to formaldehyde-type adhesives in wood-based panel and indoor panel bonding industries.

The current study investigates for the first time the physico-chemical performances of lignins from cactus waste seeds (CWS) and spent coffee (SC) in comparison to previously isolated lignins from sugar byproducts (bagasse (SCB) and beet pulp (SBP)). In this work, lignin-phenol formaldehyde (LPF) resins were formulated using various lignin loadings (5-30 wt%), characterized and applied in the manufacturing of plywood panels. Several characterization techniques were applied to identify the chemical and morphological properties, thermal stability, and phenolic content of the extracted lignins, as well as the bonding strength and wood failure of the formulated resins. Results showed that the CWS and SC could be considered as an important source for lignin recovery with a considerable yield of 15.46 % and 27.08 % and an important hydroxyl phenolic content of 1.26 mmol/g and 1.36 mmol/g for CWS and SC, respectively. Interestingly, 20 wt% of extracted lignins in PF adhesives were the optimal formulation showing an improved modulus of elasticity (MOE) of about 3505, 3536 and 3515 N/mm

The cellulose nanocrystals (CNCs) were produced from spruce wood using less hazardous and toxic reagents with understanding of influence of process parameters on CNCs properties. This study employed acetosolv pulping followed by alkaline-peroxide bleaching, eliminating highly reactive chemicals such as Na-chlorites and Na-sulfite for cellulose pulp extraction from spruce wood. Cellulose pulp yield of 41.5 ± 0.7 wt% of dry wood was obtained from pulping followed by bleaching treatment. Cellulose pulp was hydrolyzed with 59.0-65.0 wt% sulfuric acid followed by ultrasonic treatment to produce CNCs. CNCs yield of 8.0 ± 3.2 wt% of dry wood was obtained at 65 wt% acid concentration and yield of 25.1 ± 0.7 wt% at 62 wt% acid concentration. The optimization of acid hydrolysis and ultrasonic treatment resulted in CNCs with high aspect ratios (length/width) up to 48.1. It was demonstrated that higher acid concentration requires lower intensity of ultrasonic treatment for CNCs dispersion, and that higher intensity could enhance aspect ratio without impacting the crystallinity index. However, ultrasonic treatment for longer than 5 min led to destruction of the whisker morphology of CNCs. The extracted CNCs possess high crystallinity index of 80.8 ± 1.7 %, low residual hemicellulose (2.0 %) and lignin (0.7 %), and high-char content of 26.7 wt% from thermal degradation.

The high density and poor thermal insulation of traditional wood-plastic composites limited the application in the field of building materials. In this paper, wood fiber (WF) and PLA were used as raw materials and azodicarbonamide was used as the foaming agent. Lightweight WF/PLA composites were prepared by the hot-pressing foaming method, aiming to obtain renewable, low-density material with high strength-to-weight ratio and thermal insulation performance. The results showed that after adding 20 % WF into PLA, the cell morphology was excellent and the cell size was uniform. The magnification reached the minimum value of 0.36 g/cm

Exploring the reusability of wood-based panels is imperative in the wood industry for sustainable development and carbon balance. Non-reusable adhesives make wood-based panel recycling difficult. In this study, inspired by the adhesion and de-adhesion behavior of snail slime, we built dynamic covalent/hydrogen hybrid networks into adhesive system for achieving both high bonding performance and reusability. Specifically, the softwood lignin was purified and pretreated by ultrasonication to form a catechol structure (UAL) and then combined with soybean protein to develop a 100 % bio-based wood adhesive. The catechol structure of UAL formed dynamic covalent bonds (CN) with the amino groups of the protein to improve the water resistance and formed multiple hydrogen bonds as a sacrificial network to improve the toughness of the adhesive. Thus, the wet shear strength of plywood bonded by the resultant adhesive improved by 101.4 % to 1.37 MPa. The adhesive also exhibited flame retardancy (LOI = 37.7 %), mildew resistance (60 h), and antibacterial performance (inhibition zone = 8 mm). Notably, owing to the rearrangement of dynamic covalent/hydrogen hybrid networks and the thermoplastic property of UAL, the resultant adhesive was reusable (3 cycles) and degradable (2 months), which provides a potential method for the reuse of wood-based panels.

Irregular hemorrhagic traumas always threaten the health of patients due to uncontrollable bleeding and wound infections. The traditional hemostatic materials show dissatisfactory hemostatic efficiency and antibacterial activity in solving these potential bleeding dangers. Herein, we proposed a kind of composites based on flexible wood membrane (FWM) loaded with chitosan/alginate derivative for accelerating rapid hemostasis and preventing infection. FWM was removed part of hemicellulose and lignin by using NaOH/Na

Hemicellulose is an important component of the plant cell wall which vary in structure and composition between plant species. The research of hemicellulose structures is primarily focused on fast-growing plants during xylogenesis, with slow-growing and rare trees receiving the least attention. Here, hemicellulose structure of the rare species Castanopsis hystrix during xylogenesis was analyzed. Acetyl methyl glucuronide xylan was the most common type of hemicellulose in C. hystrix, with a unique tetrasaccharide structure at the reducing end. Hemicellulose type, structure, molecular weight, thermal stability, biosynthesis and acetyl substitution content and pattern remained stable during the xylogenesis in C. hystrix, which could be attributed to its slow growth. The stable polymer type, low side chain modification and high acetyl substitution of hemicellulose throughout the stems are among the reasons for the hardness and corrosion resistance properties of C. hystrix wood. Genetic modification can be used to improve these properties.

As a soybean oil extractive byproduct, high temperature defatted soy meal (HSM) presents great potential as a raw material for vegetable protein adhesives to replace aldehyde-based adhesives in the wood-based panel production. However, the application has been hindered by its poor cold-pressing adhesive performance. Herein, a novel HSM-based adhesive with excellent cold-pressing adhesion performance was developed based on mussel-inspired cation-π interactions. Highly reactive polyamidoamine-epichlorohydrin (PAE) and folic acid (FA) were added into an HSM-based adhesive to construct a dual-network system stabilized by strong cation-π interactions. The coacervate formed by PAE and FA served as an "internal adhesive" to bond HSM particles together, yielding high initial viscosity but easy sizing. As expected, the prepared adhesive exhibited an excellent cold-pressing bonding strength of 423 kPa, showing a 295% improvement compared to the soy protein (SP) adhesive. To improve the hot-pressing bonding strength of the adhesives, inorganic calcium carbonate (CaCO

To reveal the existence of p-hydroxyphenyl (H) units in compressed wood lignin, four different milled wood lignins were extracted using Pinus massoniana Lamb compressed wood, Pinus massoniana Lamb normal wood, and sugarcane bagasse as raw materials. Then, three dehydrogenation polymers (DHPs) were synthesized using coniferyl/p-coumaryl alcohol as raw materials to reveal the interunit linkages of H units. The lignin and DHP samples were systematically characterized by

Human health and environmental protection demand wood-based panel industry for innovative soy-based adhesives with high production efficiency, straightforward synthesis processes, non-toxicity, and high bonding performance. A simple and efficient microwave pretreatment process and low addition of bio-derived crosslinking agent was used in this study to prepare a non-toxic and high-bonding performance soybean protein-based adhesive. After 4 min of microwave pretreatment time, the complex quaternary structure of soybean protein molecule unfolds, the soybean protein disperses evenly and stably, and active groups of soybean protein molecules are exposed. After adding 3.85% crosslinking agent, the moisture absorption rate of the soybean protein-based adhesive decreases by 41.77%, the residual rate increases by 3.68%, and the wet shear strength of the resultant plywood increases to 1.12 MPa, which satisfies requirement of interior use plywood. Compared with previously reported soy-based adhesives, this adhesive is dependent on fewer chemical reagents, but has good bonding performance. The 204.41% of relative cell viability indicates the resultant adhesive was non-toxic. The proposed high-efficiency, high-performance, non-toxic biomass adhesive has great prospects for the industrial application.

Pure deep eutectic solvents (DESs) system of choline chloride (ChCl)/Lactic acid (Lac) were demonstrated to be an effective strategy for extraction of lignin. In this study, two kinds of different promising solid acid (SA) with DESs were designed to promote the pretreatment of lignocellulose. The SA of phosphotungstic acid (H3O40PW12) and iron bromide (FeBr3) were introduced into DESs to extract poplar wood lignin and evaluate the antioxidant activity. It was found that 82.2% and 80.9% of lignin were obtained from poplar wood under H3O40PW12-ChCl/Lac acid and FeBr3-choline ChCl/Lac system with 4 h and 8 h, respectively. The lignin fractions with a high purity (>89%), low molecular weight (Mw 1800–2000 g/mol). Besides, the antioxidant activities of lignin fractions were better than butyl hydroxyanisole (BHA). Therefore, DES lignin has prominent antioxidant activity and could developed a potential natural cosmetics and food packaging.

Wood from invasive tree species Acacia dealbata and Ailanthus altissima was used to produce high value-added nanocellulose. Firstly, bleached pulps were produced from the wood of these tree species after kraft cooking. Afterwards, the resultant pulps were pre-treated by TEMPO-mediated oxidation (Acacia dealbata) or enzymatic hydrolysis (Ailanthus altissima) followed by high-pressure homogenization. Hydrogels were obtained and characterized for their main physical and chemical properties, including rheology measurements. After freeze-drying, the surface properties of the materials were evaluated by inverse gas chromatography. Results showed that nano/micro fibrils could be obtained from the wood of these invasive species. Rheometry studies showed that Acacia-TEMPO cellulose nanofibrils form strong gels with high yield stress point and viscosities (reaching ca. 100,000 Pa·s). Additionally, the surfaces of the obtained nanocelluloses showed a dispersive component of the surface energy near 40 mJ/m2 and a prevalence of the Lewis acidic character over the basic one, as typical for cellulose-based materials. Finally, films with good mechanical and optical properties could be obtained from the cellulose hydrogels. Acacia-TEMPO film (produced by filtration/hot pressing) showed a tensile strength of 79 MPa, Young's modulus of 7.9 GPa, and a transparency of 88%. The water vapor barrier, however, was modest (permeability of 4.9 × 10−6 g/(Pa·day·m)).

Lignocellulose including cellulose, lignin, and hemicellulose could be extracted from wood, and has been used to prepare carbon electrode. However, complicated extraction greatly increases preparation cost. To achieve maximum utilization of lignocellulose and avoid complicated extraction, wood with porous structure and good mechanical strength is used as carbon precursor. Additionally, chemical activation is commonly used to create micropores to provide high capacitance, but it brings in natural structure destruction, and generation of wastewater during pickling. Moreover, to achieve desirable energy density, multi-step strategy with long duration is required for loading active materials on carbonized lignocellulose (CL). Herein, a one-step method is developed to prepare a free-standing hybrid CL electrode (CLE) by using Lewis acid in three aspects: (1) as structure protection agent, (2) as activating agent, (3) as active materials donor, which bypasses pickling and further avoids the generation of wastewater. Additionally, natural vessels in wood can not only provide large space for active materials loading, but also act as rapid ions diffusion way, simultaneously confining active materials detachment. Benefiting from the synergistic effect of porous structure and Lewis acid, this work not only makes full utilization of lignocellulose, but also makes CLE exhibit excellent performance in hybrid oxide supercapacitor.

In this study, two kinds of form-stable multifunctional materials with thermal and electrical response (FPCMs: DP-E7U3-CNT, DP-E7T3-CNT) are composed of wood-based honeycomb-like celluloses micro-framework (DP), carbon nanotubes (CNT), erythritol-urea (E7U3) or erythritol-thiourea (E7T3). In FPCMs, DP acts as a skeleton structure to seal E7U3 and E7T3 and provide more pathways for heat conduction. The CNT acts as an extended surface to further improve thermal conductivity. FE-SEM showed that the honeycomb-like pore structure of DP was completely filled with E7U3, E7T3 and CNT. FTIR and XRD analysis show that there is only a combination of physical interactions between the components of FPCMs. DSC curves and thermal conductivity analysis results show that DP-E7U3-1.5CNT and DP-E7T3-1.5CNT with the mass fraction of carbon nanotubes (1.5 wt%) have the highest latent heat values (230.3 J/g, 272.2 J/g) and thermal conductivity (0.9832 W/(m·K), 0.9363 W/(m·K)). Both DP-E7U3-1.5CNT and DP-E7T3-1.5CNT exhibit high latent heat retention and thermal stability after 100 heating-cooling cycles. In addition, DP-E7U3-1.5CNT and DP-E7T3-1.5CNT show excellent performance in light-heat energy conversion-storage, actual latent heat storage and release, thermal and electrical response performance, which make it has great potential to be multifunctional materials with thermal storage sand electrical response.

Polymeric wood hemicelluloses are depicted to join cellulose, starch and chitosan as key polysaccharides for sustainable materials engineering. However, the approaches to incorporate hemicelluloses in emerging bio-based products are challenged by lack of specific benefit, other than the biomass-origin, although their utilization would contribute to sustainable material use since they currently are a side stream that is not valorized. Here we demonstrate wood-xylans as swelling modifiers for neutral and charged nanocellulose films that have already entered the sustainable packaging applications, however, suffer from humidity sensitivity. The oxidative modification is used to modulate the water-solubility of xylan and hence enable adsorption in an aqueous environment. A high molecular weight grade, hence less water-soluble, adsorbed preferentially on the neutral surface while the adsorbed amount on a negatively charged surface was independent of the molecular weight, and hence, solubility. The adsorption of the oxidized xylans on a neutral cellulose surface resulted in an increase in the amount of water in the film while on the negatively charged cellulose the total amount of water decreased. The finding of synergy of two hygroscopic materials to decrease swelling in hydrophilic bio-polymer films demonstrates the oxidized macromolecule xylan as structurally functional component in emerging cellulose products.

The present work aims at assessing the main characteristics of lignocellulosic micro/nanofibers (LCMNF) from bleached thermomechanical pulp (BTMP) from spruce while glimpsing the suitability of cationic demand (CD) as effective monitoring parameter of the fibrillation process. For this, BTMP was mechanically refined at different times in a Valley beater, aiming at determining the required refining time and fiber length to be later fibrillated in a high-pressure homogenizer. It was found that 150 min treatment is required to avoid clogging in the pressure chambers of the homogenizer. The mechanically treated BTMP was gradually passed through a high-pressure homogenizer, leading to four LCMNF with different fibrillation degree. The main characteristics of the LCMNF were determined, as well as the effect that high-pressure homogenization may generate onto the LCMNF structure. It was observed that CD is a robust parameter to monitor the fibrillation process, as it is a good indicator of the LCMNF characteristics. In addition, it was found that WRV may not be a good indicator of the extent of fibrillation for LCMNF, as the lignin content varies with the homogenization intensity. Finally, the limitations of CD as monitoring parameter and perspectives on this regard are provided to the reader.

Cellulose nanocrystals (CNCs) have been recognized as one of the most promising nanofillers in modern science and technology owing to their outstanding characteristics of renewability, biodegradability, excellent mechanical strength, and liquid crystalline behavior. Interestingly, these properties are dependent on their genetic and also on the isolation process. Therefore, this research aimed to unveil how the biological variations of cellulose can influence on the physical properties of the extracted CNCs. A standard optimized extraction process was adopted to isolate the CNCs from different sources. Extracted CNCs were compared through characterization tools, including Fourier Transformation Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Thermogravimetry Analysis (TGA), Dynamic Light Scattering (DLS), Field Emission Scanning Electron Microscopy (FE-SEM), Atomic Force Microscopy (AFM), and Polarized Optical Microscopy (POM). Different self-assembly patterns were observed for different CNCs, owing to their biological variations. The resultant nanocrystals displayed variable morphologies such as spherical, rod, and needle shape. The hydrodynamic diameter, crystallinity index, decomposition temperature, liquid crystallinity, and storage modulus were varied. Nanocrystals isolated from non-wood feedstock have shown a higher degree of polymerization of 108.2 and a high Crystllinity Index (C·I.) of 55.1%. The rod-like morphology with the liquid crystalline pattern was obtained at 3 wt% concentration for SCNC.

Kraft lignin, so far useful for energy generation, has been gathering considerable attention as an alternative material to replace fossil-based resources mainly due to its high phenolic content. However, the wide molecular weight distribution and chemical composition heterogeneity led to the development of fractionation methods. Herein, to narrow such characteristics we used eucalypt kraft lignin fractionated at pH's 9, 7, 5 and 3 by sequential acid precipitation. These lignin fractions were first characterised by simultaneous pyrolysis and trimethylsilylation (SPyT) with N-Methyl-N-(trimethylsilyl) trifluoroacetamide with posterior tests of antioxidant, antibacterial, and antitumour activities. We observed higher ratio of syringyl/guaiacyl groups and increase in antioxidant activity in those fractions with lower molecular weight (precipitated at lower pH's). Fractions precipitated at pH's 9 and 7 have shown an outstanding antibacterial activity against five bacteria. Moreover, fractions 7 and 5 presented at cytotoxicity tests higher ability to inhibit the growth of U87MG and T98G glioma cells, while only a slight inhibition of adult human fibroblasts (non-tumour cells) was detected.

In this work, twenty-five kinds of choline chloride (ChCl)-based deep eutectic solvents (DESs) containing acid, hydroxyl, amide, and binary hydrogen bond donors (HBDs) were prepared and successfully used to pretreat pine wood powder. As a result of the pretreatment, the glucan content in the pretreated biomass was increased, whereas the contents of hemicellulose and lignin were significantly decreased. The biomass pretreatment efficiency of the DESs had improved with increasing the polarity and hydrogen bond acidity (α) of the DESs. Among the studied DESs, ChCl:lactic acid:formic acid (1:1:1) with the highest α value was the most efficient DES in extracting lignin from biomass. The pretreated biomass also showed an enhanced enzymatic saccharification yield owing to the decreased particle size of the biomass and reduced content of hemicellulose and lignin. During the pretreatment process of biomass using DESs, the extracted lignin could be recovered successfully, with a yield of up to 60% and purity of over 90%. The molecular weight of the extracted lignin was much lower than that of the native cellulolytic enzyme lignin. The DES used for pretreatment process could be also successfully reused with high recovery yield of DES and high retention of delignification capacity.

Ginkgo shells as by-products from Ginkgo biloba L. industries with a remarkable annual output up to now are not fully analyzed and exploited. For the application of ginkgo shells beyond their current roles, structure and antioxidant activity of milled wood lignins successively extracted from two ginkgo shell species were investigated. Results showed lignin in ginkgo shells is abundant in guaiacyl units with the presence of ferulates and p-coumarates and demonstrates a high yield of vanillin (1.47–1.65 mmol/g-lignin) by nitrobenzene oxidation, much higher than general softwoods and hardwoods (0.6–0.9 mmol/g-lignin), which makes ginkgo shells good feedstocks for the production of food and beverage flavoring agent. By increasing the extent of ball-milling (4–8 h), the polydispersity of lignin molecular weight exhibits negligible change, but condensation and aldol interconversion occur to its Cβ/C5 structure and end-groups, respectively. Lignin in ginkgo shells also features outstanding antioxidant activity with the optimal radical scavenging index of 6.9, much higher than commercial butyl hydroxyanisole (3.85) and butylated hydroxytoluene (0.29), and the phenolic hydroxyl is demonstrated to dominate this contribution by the analysis of statistical product and service solutions. These results reveal lignin in ginkgo shells shows many unique structural and biological properties for materials.

Nature has given several unique features to one of the most abundant and inexhaustible biopolymers on the earth, i.e., cellulose. Besides, biodegradability, and cost-effectiveness, cellulose possesses attractive properties such as the ability to undergo chemical and structural modification, plus its light weight and thermal and mechanical stability. Cellulose originates from natural sources, including being significant components of plants (ca. 33%), wood (ca. 50%), and cotton (ca. 90%). It can also be synthesized and modified further into a variety of functionalized nanomaterials for diversified sectors, such as bio-medical, food, customer care, and environmental services. Considering the significant growth in product development and interdisciplinary cellulose-based research, the proposed chapter will let the reader gain knowledge about in-vitro extraction, synthesis of nanomaterials, and applications to resolve ongoing environmental challenges.

Here, firstly lignin sulfonate was produced from sulfite liquor provided by Mazandaran wood & paper industries (Chookam). Then, the role of effective parameters including reaction temperature, duration time, and amounts of pyridine and acetic anhydride respectively as the catalyst and the esterification agent on the acetylation rate of lignin sulfonate were studied and the process parameters were optimized through multiple experiments. In this investigation, using 1 g lignin sulfonate, the effect of various levels of temperature (ranged from room temperature to 140 °C), reaction time (12–72 h), pyridine volume (0–30 mL), and acetic anhydride volume (5–30 mL) were evaluated. Based on the results of several esterification processes, the optimal values of temperature and reaction time were obtained to be 100 °C and 48 h, respectively, and the optimal volumes of acetic anhydride and pyridine were 20 mL (with equal amounts). Besides, the characterization tests of lignin sulfonate and acetylated lignin sulfonate were performed using FT-IR and NMR techniques. Also in this paper, the morphology and crystallinity/amorphicity of lignin sulfonate and acetylated lignin sulfonate were examined using SEM images and XRD patterns.

Xylan extracted from neem sawdust gave 22.5%, (w/w) yield. The extracted xylan was composed of xylose and glucuronic acid at a molar ratio of 8:1 and with a molecular mass, ~66 kDa. FTIR and NMR analyses indicated a backbone of xylan substituted with 4-O-methyl glucuronic acid at the O-2 position. FESEM analysis showed a highly porous and granular surface structure of xylan. A thermogravimetric study of xylan showed thermal denaturation at 271 °C. The hydrolysis of xylan by recombinant endo-β-1,4-xylanase produced a mixture of xylooligosaccharides ranging from degree of polymerization 2–7. Xylooligosaccharides inhibited cell growth of human colorectal cancer (HT-29) cells but did not affect the mouse fibroblast cells confirming its biocompatibility. Western blotting, DNA laddering and flow cytometric analysis displayed inhibition of HT-29 cells by xylooligosaccharides. FLICA staining and mitochondrial membrane potential analyses confirmed the activation of the intrinsic pathway of apoptosis. The study amply indicated that the xylooligosaccharides produced from neem xylan could be potentially used as an antiproliferative agent.

Protic ionic liquids have been proposed as effective solvents for the selective extraction of lignin from wood. In this work, the protic ionic liquid 1-methylimidazolium chloride has been used to extract lignin at different biomass loadings, temperatures, and times to understand the influence of treatment severity on the lignin dissolution mechanism. The maximum lignin recovery (82.35 g lignin/100 g biomass lignin) was achieved at 10% (w/w) biomass loading, 135 °C, and 6 h. An increase in treatment severity leads to an acid cleavage of ether linkages, which increases the average molecular weight and thermal stability of lignins due to C-C repolymerization. HSQC-NMR analysis showed the effect of operating conditions on the predominant mechanism of lignin depolymerization. At mild conditions, there is a preferential degradation of G units (the typical depolymerization mechanism of ionic liquid treatments); but at the most severe conditions, S units are predominantly removed, as usually occurs in acidic treatments. This work contributes to better understanding the different lignin extraction mechanisms occurring with a protic ionic liquid depending on different operating conditions.

Agricultural wastes are an alternative to the use of wood in plastic composites, thanks to their abundance, easy availability and other environmental and economic advantages. Agricultural wastes can be processed to obtain lignocellulosic fibers of different compositions that will allow better performance of their composites and the final desired residues' valorization. In this context, the current investigation aims at the management of corn stover wastes to be applied as reinforcement of polypropylene (PP). Four types of lignocellulosic fibers were obtained by submitting the wastes to mechanical, thermomechanical, semi-chemical or chemical processes. Corn fibers were characterized in terms of chemical composition, morphology and mechanical properties. In addition, PP was reinforced with corn fibers and the composites' stiffness evaluated. An assessment of the influence of the fiber composition on the mechanical performance of the composites is conducted. It is observed the key role of lignin content on the intrinsic modulus of the reinforcing fibers, which directly affected the final stiffness of composites. The best performance was achieved for an optimal kappa number between 40 and 50, corresponding to the semi-chemical fibers. The intrinsic modulus of the fibers, as well as the efficiency factor, length and orientation factors in composites were determined via micromechanical models.

Soda process is one of the most important pulping processes in paper industry producing large quantities of alkali lignins that can afford plenty of biofuels, aromatic chemicals and materials. However, the structural and size-related heterogeneities and complexities hinder the development in these directions. Herein, we report new insights into the structure of alkali lignin, through investigating the formation and transformation of enol ether and arylglycerol structures that are significant responsible for the structural transformation from native lignin to alkali lignin. Four-type enol ethers composed of G/S units in hardwood alkali lignin were identified by 2D HSQC NMR. A series of alkali lignins prepared by alkali treatment of eucalyptus cellulolytic enzyme lignin under various temperatures were analyzed by 2D HSQC NMR, 31P NMR and gel permeation chromatography (GPC). Upon these analyses and related model compound studies, it was found that the arylglycerols formed from native β-O-4 linkages tends to be oxidized with the further degradation of aryl ether bonds, and that the enol ether linkages are facile to be hydrolyzed or oxidized in the air. These insights improve the mechanistic understanding for the structural evolution and the diversity of alkali lignins and will aid the development of further lignin valorization strategies.

The aim of this work was to synthesize pinus residue/pectin-based composite hydrogels for the immobilization of β-D-galactosidase. These hydrogels were synthesized via chemical crosslinking, and characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, thermal analysis, mechanical assays, X-ray diffraction, and swelling kinetics. The water absorption mechanism in the hydrogel networks occurs by non-Fickian transport. The β-D-galactosidase immobilization capacities of the hydrogels containing 0, 5 and 10% of pinus residue were respectively 242.08 ± 0.36, 181.27 ± 0.50 and 182.71 ± 0.36 mg enzyme per g dried hydrogel, at pH 4.0 and after 600 min. These values were 182.99 ± 0.41, 219.99 ± 0.47 and 218.56 ± 0.39 mg g−1, respectively, at pH 5.6. Pectin-based hydrogels demonstrated to be excellent solid supports for the immobilization of enzymes. β-D-Galactosidase immobilized in pectin-based hydrogels could be applied in the hydrolysis of lactose contained in either dairy foods or lactose-intolerant individuals.

The inter-particle interference of lignocellulosic materials describes the order of the macromolecules at a larger size scale, which can give information about the pore structure, and interface of cellulose and lignin. The pore structure and interface influence the rate of enzymatic hydrolysis and thermal decomposition in cellulosic ethanol manufacturing. In this study, the inter-particle interference of cellulose and lignin of three major categories of lignocellulosic materials: wood-based (cedar and oak), energy crop (bamboo), and agricultural or forestry waste (palm) were evaluated. Scanning electron microscopy (SEM) reveals morphological irregularities in the case of bamboo and palm, which may form nucleation sites for faster accessibility to enzyme molecules. Small-angle X-ray scattering (SAXS) shows increased power-law exponent for palm, suggesting a less clustered structure, which was consistent with the rough surface morphology as detected by the SEM. Differential Scanning Calorimetry (DSC) showed a higher temperature maximum for cedar and oak, which is indicative of higher intermolecular forces within their organic compounds, and could result in slower disintegration of the macromolecules during biochemical processing. This study will help to estimate the activity of the macromolecules and absorption capacity of lignocellulosic materials during biochemical processing.

The production of cellulose nanofibers (CNF) usually consist of two different phases. First of all, lignocellulosic fibers need to be treated by means of either chemical, enzymatic or mechanical treatments. Then, in the second phase, the treated lignocellulosic fibers need to be submitted to mechanical fibrillation. This last treatment is usually critical in terms of energy consumption, as well as for providing the appropriate characteristics to the resulting CNF. In the present work, we have investigated the effect of fibrillating lignocellulosic nanofibers (LCNF) made from eucalyptus sawdust by means of high-pressure homogenization and grinding. The obtained results showed that, to achieve the same property level of LCNF, the grinder consumed 12.86 kWh/kg, while the homogenizer, 19.07 kWh/kg, bringing to the light the suitability of grinding for LCNF production. Overall, the present work shows the feasibility of using eucalyptus sawdust, which is a residue from the pulp and paper industry, as raw material for LCNF production, at the same time that brings to the light the relevance of the fibrillation equipment in terms of energy efficiency, approaching the production of LCNF to the industry.

Enhancing the performance of starch-based wood adhesive is vitally important for its practical applications. Accordingly, we designed the use of micronized starch (MS) to prepare micronized starch-based wood adhesive (MSWA) by incorporating 0, 2, 4 and 6% (w/w, dry basis starch) sodium dodecyl sulfate (SDS). The results showed that 2% SDS exhibited remarkable improvement in shear strength and viscosity of MSWA. The grafted reaction was demonstrated by 1H NMR and the steady shear results indicated that the adhesive possessed a pseudoplastic behavior under yield stress conditions. Besides, dynamic rheological measurements were applied to evaluate the structure of MSWA under varying frequencies, temperatures and constant stain. The transmission electron microscopy (TEM), Zeta potential and surface tension indicated that SDS could improve the surficial properties. Meanwhile, the microstructure of adhesive films and fracture surfaces of glued wood veneers by scanning electron microscopy (SEM) demonstrated that the migration of SDS led to the formation of surfactant layer. Furthermore, element analysis revealed the distribution of S/N in latex slices. The results of this study provide the detailed information about the influence of SDS on the rheological properties and microstructures of MSWA, which may facilitate the preparation of high performance bio-based adhesive for wood applications.

Ceriporiopsis subvermispora (C. subvermispora) is a selective degrader of lignin in the woody biomass. Glutathione S-transferases (GSTs) are multifunctional enzymes that play important roles in cellular detoxification and metabolism. The crystal structures of a GST of C. subvermispora, CsGST83044, in GSH-free and -bound forms were solved at 1.95 and 2.19 A resolution, respectively. The structure of the GSH-bound form revealed that CsGST83044 can be categorized as an atypical-type of GST. In the GSH-bound form of CsGST83044, Asn22, Asn24, and Tyr46 are located closest to the sulfur atom and form hydrogen bonds with the thiol group. The functional mutagenesis indicated that they are critical for the enzymatic activities of CsGST83044. The critical residues of an atypical-type GST belonging to the GSTFuA class were revealed for the first time. A previous study indicated that CsGST83044 and another GST, CsGST63524, differ in substrate preference; CsGST83044 prefers smaller substrates than CsGST63524 for its esterase activity. The GSH-bound pocket of CsGST83044 turns out to be small, which may explain the preference for smaller substrates. Protein engineering of GSTs of C. subvermispora in the light of the obtained insight may pave a path in the future for utilization of the woody biomass.

Chelator-mediated Fenton chemistry is capable of reducing non-stochiometric amounts of iron via hydroquinone oxidation. These types of reactions have previously been demonstrated to be promoted by some lignocellulose degrading fungi in generating hydroxyl radicals to permit lignified plant cell wall deconstruction. Here we demonstrate that lignocellulose surfaces, when exposed by chemical treatment or fragmentation, can promote a similar multi-oxidative mechanism in the presence of iron. Iron reduction by lignin surfaces permits the generation of hydroxyl radicals in the cell wall to help explain fungal non-enzymatic cell wall deconstruction, and it also provides an explanation for certain phenomenon such as the anthropogenic generation of formaldehyde by wood. The mechanism also provides a basis for the generation of electrons by lignin that are required by certain fungal redox enzymes active in plant cell wall degrading systems. Overall, the data demonstrate that iron found naturally in lignocellulose materials will promote the oxidation of phenolic lignin compounds in the naturally low pH environments occurring within lignified plant cell walls, and that this activity is promoted by cell wall fragmentation.

The Symphyta has long been recognized as a paraphyletic grade forming the base of the remaining Hymenopteran, and the superfamily relationships within Symphyta remain controversial. Here, the first two representative mitochondrial genomes from the superfamily Siricoidea and Xiphydrioidea (Hymenoptera: Symphyta) are obtained using next-generation sequencing. The complete mitochondrial genome of Xiphydria sp. is 16,482 bp long with an A + T content of 84.18% while the incomplete one of Tremex columba is 16,847 bp long and A + T content is 81.69%. All 37 typical mitochondrial genes are possessed in both species. The secondary structure of tRNAs and rRNAs for both species are successfully predicted. Compared with the ancestral organization, seven and five tRNA genes are rearranged in mitochondrial genomes of Tremex and Xiphydria, respectively, which are the most rearrangement events within Symphyta. The rearrangement patterns in Tremex and Xiphydria present in this study are all novel to the Symphyta. Phylogenetic relationships among the major lineages of Symphyta are reconstructed using mitochondrial genomes. Both maximum likelihood and Bayesian inference analyses highly support Symphyta is a paraphyletic grade, Xyeloidea + (Tenthredinoidea + (Pamphilioidea + (Xiphydrioidea + (Cephoidea + (Orussoidea + Apocrita))))).

Brown-rot fungi are the wood-decay basidiomycetes and have ability to break down plant cell wall carbohydrates. It has been suggested that degradation of pectin is important for the initial stages of brown rot. We purified an endo-polygalacturonase (FpPG28A) from the brown-rot fungus Fomitopsis palustris, analysis of the predicted amino acid sequence indicated that FpPG28A belongs to GH family 28. The highest activity of purified FpPG28A was observed at 60 °C in 50 mM sodium acetate buffer (pH 5.0); this activity was highly specific for polygalacturonic acid chains. However, calcium polygalacturonate gel was not degraded by FpPG28A under those optimal conditions. We observed that calcium polygalacturonate gel was readily degraded by the enzyme in the oxalate buffer. Furthermore, the thermostability of FpPG28A was elevated in oxalate buffer at pH 3.0. These results indicated that oxalate has an important role in the degradation of woody pectin by FpPG28A.

Alkali‑oxygen cooking of lignocellulose offers lignin many structural properties and bioactivities for biorefinery. In this work, milled wood lignin (MWL) and alkali‑oxygen lignin (AOL) were isolated from rice straw and alkali‑oxygen black liquor, respectively. The lignin structure was characterized by spectroscopy and wet chemistry. Antioxidant activity of lignins was assessed by DPPH·and ABTS scavenging ability assay. Results showed the oxidization and condensation of lignin occurred during alkali‑oxygen cooking. The p-hydroxyphenyl was more easily removed from rice straw than guaiacyl and syringyl units. The ester or ether linkages derived from hydroxycynnamic acids, and the main interunit linkages, i.e. β–O–4′ bonds, were mostly cleaved. Lignin-xylan complex had high reactivity under alkali‑oxygen condition. Tricin, incorporated into lignin, was detected in MWL but was absent in AOL. Nitrobenzene oxidation showed MWL can well represent the protolignin of rice straw, and the products yield decreased dramatically after alkali‑oxygen cooking. AOL had higher radical scavenging ability than MWL indicating alkali‑oxygen cooking was an effective pathway for the enhancement of antioxidant activity of lignin.

Activated carbon (AC) prepared from Jatropha curcas and graphene oxide (GO) were employed in the preparation of natural polymer based wood starch composites (WSC) through the solution blending technique using water as a solvent. In this study, methyl methacrylate (MMA) was grafted onto the starch polymer and this MMA grafted starch (MMA-g-starch) was cross-linked with the cheap soft wood flour using the citric acid as cross-linker and water as a solvent in the whole process. The prepared GO and AC were characterized through Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), thermogravimetric analysis (TGA) and Raman study. The interaction of GO and AC, with MMA-g-starch, citric acid and wood were studied by FTIR, XRD and SEM analysis. The GO and AC treated composites exhibited outstanding mechanical properties, thermal stability and fire resistance properties. The tensile strength of the composites increased by 178% and 200% with addition of 2 phr AC and GO respectively compared to untreated composites. A significant enhancement in water resistance properties of GO and AC treated composites was also attained. The study showed that the properties of the composites containing AC prepared from the seeds of Jatropha curcas was quite comparable with the composites reinforced with GO.

Nanotechnology-inspired biocatalytic systems attracted attention for many applications since nanosized supports for enzyme immobilization can improve efficiency-determining factors e.g. enhancing the surface area and loading capacity and reducing the mass transfer resistance. Among the nanomaterials, nanobiochar has unique features as a support for enzyme immobilization i.e. high surface to volume ratio, porous structure, and presence of functional groups on its surface. However, the performance of the immobilization is highly dependent on the immobilization conditions and the properties of the enzyme and the support material. In this research, crude laccase was covalently immobilized onto functionalized nanobiochar using a two-step method of diimide-activated amidation. The effect of different parameters was investigated. The optimal conditions were found to be 14 mg/mL of laccase concentration, 5 mg/mL of nanobiochar, 8.2 mM of cross-linker and 3 h of contact time. For investigating the pH, thermal, storage, and operational stability, the sample obtained from the optimized conditions was used. The results showed the higher stability of immobilized laccase against temperature and pH variation compared to free laccase. In addition, immobilized laccase maintained its catalytic performance up to seven cycles of utilization and showed more than 50% of initial activity after two months of room temperature storage.

Near infrared (NIR) spectroscopy coupled with partial least squares (PLS-1) regression was used to predict the lignin contents and monosaccharide compositions of milled wood of Pinus radiata. The effects of particle size and moisture content were investigated by collecting NIR spectra of four sample types: large (

Enhancing the performance of wood adhesive is important for its industrial applications. Accordingly, we designed and demonstrated the use of two co-monomers vinyl acetate (VAc) and butyl acrylate (BA) for promoting the graft copolymerization while improving the bonding performance of wood adhesive. The results showed that the addition of co-monomers in the ratio of VAc/BA 6:4 (v/v, volume basis of VAc) could improve the shear strength to 6.68MPa and 3.32MPa in dry and wet states, respectively. 1H-nuclear magnetic resonance (1H NMR) and fourier transform infrared spectroscopy (FT-IR) analysis revealed successful graft copolymerization reaction while the morphologies were observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Furthermore, the grafting reaction and thermal stabilities of wood adhesive were analyzed by X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The results showed that the properties of wood adhesive could improve dramatically by using two co-monomers VAc and BA during the graft copolymerization reaction.

Glutathione S-transferases (GSTs) of wood-degrading fungi play essential roles in cellular detoxification processes and endogenous metabolism. Fungal GSTs of GSTFuA class are suggested to be involved in lignin degradation. Ceriporiopsis subvermispora is one of the important model fungi of the selective lignin degraders, we found it interesting to study its GSTs. Here, we characterized the activities of two GSTs of the GSTFuA class of C. subvermispora (CsGST63524 and CsGST83044). A high-yield expression systems involving Escherichia coli was developed for each of these enzymes. Both enzymes were found to exhibit GSH-conjugation activity toward 1-chloro-2,4-dinitrobenzene, and GSH-peroxidase activity toward cumene hydroperoxide. Both enzymes showed high GSH-conjugation activity under basic conditions (pH8.0 to 9.0), and the optimum temperature for their activity was 40°C. In addition, three fluorescent compounds were used i.e., methylumbelliferyl acetovanillone was used to monitor etherase activity, and 5-chloromethylfluorescein diacetate and 4-methylumbelliferyl acetate to monitor esterase activity. CsGST83044 exhibited both etherase and esterase activities, while CsGST63524 displayed only esterase activity, which was much higher than that of CsGST83044. These findings imply the functional diversity of the GSTFuA class GSTs of C. subvermispora, suggesting that each protein plays distinctive roles in both the fungal detoxification system and wood compound metabolism.

A large number of archaeological wooden building poles have been excavated from the Hai Menkou site (Yunnan province, China). Lignin can be transformed and altered accompanied with significant loss of carbohydrates during this process. Elucidation of chemical and structural transformations of lignin is of primary importance for understanding both the nature of degradation processes and the structure of waterlogged archaeological wood, and crucial for developing proper consolidation technology and restoring artifacts of historical and cultural value. In this study, state-of-the-art analytical techniques, including SEM, FT-IR, XRD, CP-MAS 13C NMR, 2D-HSQC NMR, 31P-NMR, CRM, GPC and TG analysis, were all employed to elucidate the structural characteristics of lignin in waterlogged and reference Pinus wood. The results interpreted by NMR analysis demonstrated the depolymerization of lignin via cleavage of β-O-4, β-5, −OCH3 and some LCC linkages, leading to a higher amount of free phenol OH groups in the lignin from the ancient waterlogged wood as compared to that of the reference wood. Microscopically, it was found that extensive degradation of carbohydrates in cell walls was mainly occurred in secondary cell walls, while the lignin concentrations were relatively increased in CCML and S regions in the plant cell wall of the ancient wood.

Chemical and structure properties of Ethanol lignin (EL), alkali lignin (AL), milled wood lignin (MWL) and cellulase enzymatic lignin (CEL) extracted from acorn shell of Quercus variabilis Bl. was studied by GPC, TG, SEM, FT-IR, 13C NMR, DEPT-135 NMR, 2D-HSQC and functional groups measurement. Results indicated that AL had a lower quantity of ArOH (2.19mmol/g) in four lignin samples. TG results proved the existence of a less thermally stable domain within the lignin polymer. SEM, FT-IR, 13C NMR, DEPT-135 NMR and 2D-HSQC confirmed the lignin structural characters of the extracted samples, it was found that the relative content of β-O-4' linkage in MWL (51.15%) was lower than that of in EL(55.83%), AL (57.93%) and CEL (64.81%), suggesting that β-O-4' linkage was cleaved greatly during the milled wood lignin isolation process. AL had a higher S/G ratio than EL, MWL and CEL. The indentified substructures are plotted depended on the spectrogams. The differences in the composition of the lignin samples further supported that the deposition of lignin in the shell of Q. variabilis is inhomogeneous. In short, these findings will enhance our understanding of native lignin in acorn shell and theoretical foundation is laid for the further study of degradation.

Lignin solvent fractionation is one of the promising methods for homogenizing and utilizing lignin commercially. In this work, fractionation characteristics of two lignin fractions were compared to investigate the potential of utilization of fractionated lignin. Two lignins [milled wood lignin(MWL) and organosolv lignin(OL) from yellow poplar] were sequentially fractionated with ethyl acetate(F1), 2-butanone(F2), methanol(F3), acetone(F4), and dioxane/water(F5). Yields of five MWL fractions F1 to F5 were 11.7%, 11.7%, 15.3%, 11.8%, and 49.6%, respectively, and yields of OL fractions were 26.2%, 26.1%, 18.7%, 3.7% and 25.4%. Average molecular weight of F1 (lowest molecular weight fraction) ranged from 1000 to 2400Da, whereas that of F5 (highest molecular weight fraction) was above 10000Da. According to functional group analysis, contents of phenolic hydroxyl groups and methoxyl groups decreased gradually with increasing molecular weight. DFRC analysis was performed to investigate the frequency of β-O-4 linkages and it revealed that the higher molecular weight fractions yielded larger amounts of DFRC monomers, indicating that those fractions more frequently contain aryl ether linkages. TG/DTG showed that the low molecular weight fractions generally have lower initial thermal stability. Tg of the fractions ranged from 126°C to 156°C, increasing as the molecular weight of the lignin fraction increased.

In the present work, lignocellulosic micro/nanofibers (LCMNF) were produced from pine sawdust. For that, pine sawdust was submitted to alkali treatment and subsequent bleaching stages, tailoring its chemical composition with the purpose of obtaining effective LCMNF. The obtained LCMNF were characterized and incorporated to recycled cardboard boxes with the purpose of producing recycled paper. The obtained results showed that it was possible to obtain LCMNF with the same reinforcing potential than those cellulose nanofibers (CNF) prepared by oxidative or other chemical methods In fact, the obtained papers increased the breaking length of recycled cardboard from 3338 m to 5347 m, being a value significantly higher than the requirements to produce paper bags. Overall, the studied strategies could allow a significant reduction of paper basis weight, with the consequent material saving and, thus, contribution to the environment.

A facile approach was developed to dramatically boost the performance of high amylose starch-based wood adhesive (HASWA) by addition of sucrose fatty acid esters (SEs). The results showed that the addition of 6% (w/w, dry starch basis) SEs significantly improved the bonding strength in both dry and wet states as well as the mobility and storage stability of the adhesive. The formation of amylose-SEs complexes were proved by blue value or differential scanning calorimetry (DSC) analysis. The results also indicated that the incorporation of SEs into the HASWA hindered the aggregation of latex particles and enhanced the thermal stability of starch molecules. Furthermore, SEs addition in the adhesive system resulted in the inhibition of starch retrogradation as observed by time sweep and pulsed nuclear magnetic resonance (PNMR) analysis. These findings provide important information to prepare bio-based high performance wood adhesive by adding SEs to replace the traditional petro-chemical based stocks adhesives.

Composite materials mimicking the plant cell wall structure were made by culturing cellulose-producing bacteria together with secondary-wall hemicelluloses from wood. The effects of spruce galactoglucomannan (GGM) and beech xylan on the nanoscale morphology of bacterial cellulose were studied in the original, hydrated state with small-angle X-ray scattering (SAXS). The SAXS intensities were fitted with a model covering multiple levels of the hierarchical structure. Additional information on the structure of dried samples was obtained using scanning and transmission electron microscopy and infra-red spectroscopy. Both hemicelluloses induced a partial conversion of the cellulose crystal structure from Iα to Iβ and a reduction of the cross-sectional dimensions of the cellulose microfibrils, thereby affecting also their packing into bundles. The differences were more pronounced in samples with xylan instead of GGM, and they became more significant with higher hemicellulose concentrations.

In this study, effects of starch heat pretreatment at 70, 80 and 90°C on graft copolymerization reaction with vinyl acetate (VAc) and the performance of the resulting starch-based wood adhesive (SWA) were investigated. It was shown that SWA pretreated at 90°C achieved the best performance. At this temperature, the bonding capacity improved by 17.84% compared to the adhesive synthesized without heat pretreatment and the viscosity increased by 18.16% after 7 free-thaw cycles, much better than other samples. Scanning electron microscopy (SEM) and polarizing microscopy demonstrated that structures of starch granules were fully damaged after heat pretreatment at 90°C. The reaction took place not only on the surface of starch granules, but also internally, leading to improvement in the grafting amounts and grafting efficiency by 42.86% and 39.03%, respectively. This was further confirmed by Fourier transform infrared spectroscopy (FT-IR), Confocal Raman microscopy (CRM) and X-ray photoelectron spectroscopy (XPS), which also showed better reaction homogeneity both between different starch granules and from granule surface to its internal structure.

Wood rotting basidiomycetes produce extracellular mucilaginous sheaths interfacing fungal hyphae and plant biomass. While the versatility of these fungal sheaths has been addressed, sheaths generated by selective white-rot fungi remain poorly understood. To fill this gap, the sheath produced by the basidiomycete Ceriporiopsis subvermispora, which degrades lignin while inflicting limited cellulose damage, was analyzed in this study. Fluorescence and transmission electron microscopy revealed that the sheath formed three days after inoculation into a beech wood slice on an agar plate and was embedded at the interface between fungal hyphae and wood cell walls. The sheath's chemical structure was evaluated from fungus cultures in a liquid medium containing [U-13C6]-d-glucose and beech wood slices. Compositional analysis, methylation analysis, and 13C NMR demonstrated that the sheath mainly consisted of a comb-like β-1,6-glucopyranose residue-branched β-1,3-glucan, which is advantageous to retain water and extracellular secondary metabolites.