Glucuronoxylan is the main hemicellulose in the secondary cell wall of angiosperms. Elucidating its molecular structure provides a basis for more accurate plant cell wall models and the utilization of xylan in biorefinery processes. Here, we investigated the spacing of acetyl, glucuronopyranosyl and galactopyranosyl substitutions on Eucalyptus glucuronoxylan using sequential extraction combined with enzymatic hydrolysis and mass spectrometry. We found that the acetyl groups are preferentially spaced with an even pattern and that consecutive acetylation is present as a minor motif. Distinct odd and even patterns of glucuronidation with tight and sparse spacing were observed. Furthermore, the occurrence of consecutive glucuronidation is reported, which adds to the growing body of evidence that this motif is not only present in gymnosperms but also in angiosperms. In addition, the presence of terminal galactopyranosyl units, which can be released by β-galactosidase, altered the digestibility of the glucuronoxylan by GH30 and GH10 xylanase and appeared to be clustered within the polymeric backbone. These findings increase our understanding of the complex structure of glucuronoxylans and its effect on the extractability and biological degradation of Eucalyptus wood.

Brownstock washing, a critical process in cleansing kraft pulp, removes dissolved lignin residues from the pulp after it has passed through the cooking digester. It plays a significant role in kraft pulp mills by enhancing economic efficiency and environmental sustainability. Improved washing efficiency leads to better pulp quality and more effective recovery of cooking chemicals. Our study aimed to better understand the impact of different chemical compositions in washing liquors on washing performance. We tested a range of washing liquors, including neutral solutions (deionized water, 1M NaCl, 3M NaCl, 1M Na2SO4) and alkaline solutions (tap water, washing liquor composed of 0.35M NaOH and 1M Na2SO4, and white liquor with 50 g[OH]/l and 8.77 g[HS]/l). These liquors were evaluated for their efficacy in maximizing lignin extraction. Our findings suggest that salt solutions generally reduce washing efficiency. Deionized water and white liquor proved to be the most efficient washing agents, while high-concentration salts and those with high ionic strength negatively impacted washing efficiency. This suggests that brownstock washing may not be operating at its full potential.

In our previous study, we demonstrated that Eucalyptus dunnii samples containing high calcium content show inferior pulping properties concerning delignification and polysaccharide degradation. This led us to investigate alternative methods for improving the pulping process of these samples. In the present work, we evaluated the effects of incorporating black and green liquors into the Eucalyptus dunnii chips before kraft pulping, aiming to enhance the pulping process and overcome the negative impact of high calcium content. The addition of both black and green liquors resulted in specific enhancements, with the green liquor having a more significant impact on the pulping process. Even wood samples with the highest calcium content demonstrated satisfactory pulping results when treated with green liquor. Delignification occurred more rapidly, and selectivity was higher for samples pre-treated with green liquor before kraft pulping. Moreover, calcium tended to follow the fiber under these conditions rather than being released into the black liquor, which may contribute to the improved pulping performance. Subsequent bleaching tests revealed that the bleachability of green liquor-treated pulp was nearly identical to that of a control pulp, while maintaining a higher viscosity. This suggests that incorporating green liquor into the pre-treatment process not only improves the pulping performance of Eucalyptus dunnii samples with high calcium content but also maintains desirable bleachability characteristics. To better understand the underlying mechanisms of these findings, we discuss the potential chemical explanations behind the observed improvements.

This work has focused on oxygen's role in the delignification process within the context of pulp production. We have investigated the role of oxygen in a complex set of chemical reactions taking place during this process, including both oxidative and non-oxidative reactions. This study explores the impact of pH changes during the oxygen delignification process and the characteristics of the resulting pulps. Additionally, this research examines the effect of oxygen, by comparing conventional oxygen delignification with trials using air and nitrogen. Industrial softwood kraft pulps with a kappa number of 35 were subjected to delignification for 20-120 min under alkaline conditions. The resulting pulps were assessed for kappa number, intrinsic viscosity, fiber charge, and ISO brightness. An important observation from this research is the reduction in lignin molecular weight upon exposure to oxygen and air, suggesting depolymerization reactions facilitated by oxygen species, whereas nitrogen exposure results in less pronounced changes. This finding underscores the impact of oxygen in altering lignin structure, thus informing the selectivity and effectiveness of the delignification process.

Kraft pulping of wood is based on efficient depolymerization and solubilization of lignin, while cellulose is relatively undamaged. Non-cellulose cell wall polysaccharides are however in some cases heavily degraded, especially pectin and to a lesser degree also glucomannan while, xylan is relatively stable. In this mini-review, the most important reactions in lignin and polysaccharide degradation in kraft pulping are described, both the technically favorable and the problematic reactions, and the chemical background to discuss the advantages and drawbacks of the process. An attempt to put the different reactions in the perspective of the goals of the pulping process is made and a special focus is on the development of color in the pulp fiber during the kraft pulping.

Studies have shown that the size of LNP depends on the molecular weight (Mw) of lignin. There is however need for deeper understanding on the role of molecular structure on LNP formation and its properties, in order to build a solid foundation on structure–property relationships. In this study, we show, for similar Mw lignins, that the size and morphology of LNPs depends on the molecular structure of the lignin macromolecule. More specifically, the molecular structure determined the molecular conformations, which in turn affects the inter-molecular assembly to yield size- and morphological-differences between LNPs. This was supported by density functional theory (DFT) modelling of representative structural motifs of three lignins sourced from Kraft and Organosolv processes. The obtained conformational differences are clearly explained by intra-molecular sandwich and/or T-shaped π–π stacking, the stacking type determined by the precise lignin structure. Moreover, the experimentally identified structures were detected in the superficial layer of LNPs in aqueous solution, confirming the theoretically predicted self-assembly patterns. The present work demonstrates that LNP properties can be molecularly tailored, consequently creating an avenue for tailored applications.

Although organosolv processes using high-boiling solvents have been investigated in recent decades for developing novel industrial processes, there are potential benefits of using high-boiling point solvents for traditional sulphate-based cooking processes, both from an industrial perspective and from a laboratory perspective. Using high-boiling solvents, experiments can be done under atmospheric conditions, thus making it easier to continually monitor laboratory experiments and extracting aliquots at desired intervals. Using such a system, alkaline consumption was monitored during impregnation of spruce chips in glycerol media using chemical charges of 1 M NaOH and 0.1 M NaHS, i. e., kraft pulping conditions, and compared to a similar investigation of alkaline consumption in water media using steel autoclaves. The resulting data was fitted to a first order kinetic model, with an apparent activation energy of 22 kJ mol(-1) in glycerol media. Finally, a "normal quality pulp" of kappa number 28 and a viscosity of 1113 ml g(-1) was successful produced using a cooking process with an impregnation step at 140 degrees C for 3 h and a cooking step at 160 degrees C for 4 h. A nuclear magnetic resonance study on the dissolved lignin produced for said experiment showed characteristics typical of other kraft lignins.

Eucalyptus dunnii is cultivated in Uruguay for kraft pulping purposes. However, depending on the growth site, the kraft pulping properties of the wood vary highly, and in some cases, pulping is difficult. Different batches of wood were chemically characterized and the only significant difference related to the pulping properties was the calcium content. The calcium appears to at least partly be present in the form of crystals in the lumen. Kraft pulping experiments on wood with different calcium contents indicated that high calcium led to slower delignification, and higher yield losses. Hexeneuronic acid formation was not significantly affected. Possible mechanistic explanations for these effects are discussed.

The natural polymer, lignin, possesses unique biodegradable and biocompatible properties, making it highly attractive for the generation of nanoparticles for targeted cancer therapy. In this study, we investigated spruce and eucalyptus lignin nanoparticles (designated as S-and E-LNPs, respectively). Both LNP types were generated from high-molecular-weight (M-w) kraft lignin obtained as insoluble residues after a five-step solvent fractionation approach, which included ethyl acetate, ethanol, methanol, and acetone. The resulting S-and E-LNPs ranged in size from 16 to 60 nm with uniform spherical shape regardless of the type of lignin. The preparation of LNPs from an acetone-insoluble lignin fraction is attractive because of the use of high-M-w lignin that is otherwise not suitable for most polymeric applications, its potential scalability, and the consistent size of the LNPs, which was independent of increased lignin concentrations. Due to the potential of LNPs to serve as delivery platforms in liver cancer treatment, we tested, for the first time, the efficacy of newly generated E-LNPs and S-LNPs in two types of primary liver cancer, hepatocellular carcinoma (HCC) and cholangiocarcinoma (CCA), in vitro. Both S-LNPs and E-LNPs inhibited the proliferation of HCC cells in a dose-dependent manner and did not affect CCA cell line growth. The inhibitory effect toward HCC was more pronounced in the E-LNP-treated group and was comparable to the standard therapy, sorafenib. Also, E-LNPs induced late apoptosis and necroptosis while inhibiting the HCC cell line. This study demonstrated that an elevated number of carbohydrates on the surface of the LNPs, as shown by NMR, seem to play an important role in mediating the interaction between LNPs and eukaryotic cells. The latter effect was most pronounced in E-LNPs. The novel S- and E-LNPs generated in this work are promising materials for biomedicine with advantageous properties such as small particle size and tailored surface functionality, making them an attractive and potentially biodegradable delivery tool for combination therapy in liver cancer, which still has to be verified in vivo using HCC and CCA models.

Interaction between xylan and cellulose microfibrils is required to maintain the integrity of secondary cell walls. However, the mechanisms governing their assembly and the effects on cellulose surface polymers are not fully clear. Here, molecular dynamics simulations are used to study xylan adsorption onto hydrated cellulose fibrils. Based on multiple spontaneous adsorption simulations it is shown that an antiparallel orientation is thermodynamically preferred over a parallel one, and that adsorption is accompanied by the formation of regular but orientation-dependent hydrogen bond patterns. Furthermore, xylan adsorption restricts the local dynamics of the adjacent glucose residues in the surface layer to a level of the crystalline core, which is manifested as a three-fold increase in their 13C NMR T1 relaxation time. These results suggest that xylan forms a rigid and ordered layer around the cellulose fibril that functions as a transition phase to more flexible and disordered polysaccharide and lignin domains.

Abstract Bleachability is evaluated as how easily a pulp sample is bleached and it depends on the structure of residual lignin and carbohydrates. Also, the bleachability varies depending on the bleaching sequence. ECF light sequences have been improved significantly in the recent years. However, we still don’t fully understand how ECF light bleach plants are optimally run. This work studies the bleachability of softwood kraft pulp in an ECF light bleaching sequence, (OO)Q(OP)D(PO). Three pulp samples with brown stock kappa number 27, 32 and 35 were bleached and studied for residual lignin, hexenuronic acid and carbohydrate content. It was found that in the bleaching stages that are highly delignifying, it is beneficial with a higher kappa number for the delignifying bleachability. However, in the bleaching stages where the objective is brightness increase, the brightness gain bleachability is improved by a lower kappa number. We also intended to determine which of the three samples had the best suited kappa number for this particular bleaching sequence. According to our results, the bleaching was most effective with kappa number around 32. Although an even higher kappa number resulted in higher yield after cooking, it seemed that this bleaching sequence cannot preserve the yield gain.

A method for the polymerization modification of nanoscale fumed silica by crosslinking a lignin layer adsorbed on a nanosilica surface under a gas dispersion medium is described. A mixture of phenol and formaldehyde in the presence of HCl proved to be the most effective crosslinking agent. It has been suggested that the crosslinking of lignin molecules occurs by a mechanism similar to the production of phenol formaldehyde resins.

Nanocellulose membranes based on tunicate-derived cellulose nanofibers, starch, and ~5% wood-derived lignin were investigated using three different types of lignin. The addition of lignin into cellulose membranes increased the specific surface area (from 5 to ~50 m2/g), however the fine porous geometry of the nanocellulose with characteristic pores below 10 nm in diameter remained similar for all membranes. The permeation of H2, CO2, N2, and O2 through the membranes was investigated and a characteristic Knudsen diffusion through the membranes was observed at a rate proportional to the inverse of their molecular sizes. Permeability values, however, varied significantly between samples containing different lignins, ranging from several to thousands of barrers (10−10 cm3 (STP) cm cm−2 s−1 cmHg−1cm), and were related to the observed morphology and lignin distribution inside the membranes. Additionally, the addition of ~5% lignin resulted in a significant increase in tensile strength from 3 GPa to ~6–7 GPa, but did not change thermal properties (glass transition or thermal stability). Overall, the combination of plant-derived lignin as a filler or binder in cellulose–starch composites with a sea-animal derived nanocellulose presents an interesting new approach for the fabrication of membranes from abundant bio-derived materials. Future studies should focus on the optimization of these types of membranes for the selective and fast transport of gases needed for a variety of industrial separation processes.

Valorization of lignin is still an open question and lignin has therefore remained an underutilized biomaterial. This situation is even more pronounced for hydrolysis lignin, which is characterized by a highly condensed and excessively cross-linked structure. We demonstrate the synthesis of photoactive lignin/Bi4O5Br2/BiOBr bio-inorganic composites consisting of a lignin substrate that is coated by semiconducting nanosheets. The XPS analysis reveals that growing these nanosheets on lignin instead on cellulose prevents the formation of Bi5+ ions at the surface region, yielding thus a modified hetero-junction Bi4O5Br2/BiOBr. The material contains 18.9% of Bi4O5Br2/BiOBr and is effective for the photocatalytic degradation of cationic methylene blue (MB) and zwitterionic rhodamine B (RhB) dyes under light irradiation. Lignin/Bi4O5Br2/BiOBr decreases the dye concentration from 80 mg L-1 to 12.3 mg L-1 for RhB (85%) and from 80 mg L-1 to 4.4 mg L-1 for MB (95%). Complementary to the dye degradation, the lignin as a main component of the composite, was found to be efficient and rapid biosorbent for nickel, lead, and cobalt ions. The low cost, stability and ability to simultaneously photo-oxidize organic dyes and adsorb metal ions, make the photoactive lignin/Bi4O5Br2/BiOBr composite a prospective material for textile wastewaters remediation and metal ions recycling. (C) 2021 The Author(s). Published by Elsevier Ltd.

Valorization of lignin is still an open question and lignin has therefore remained an underutilized biomaterial. This situation is even more pronounced for hydrolysis lignin, which is characterized by a highly condensed and excessively cross-linked structure. We report on photoactive lignin/Bi4O5Br2/BiOBr bio-inorganic composites consisting of a lignin substrate that is coated by Bi4O5Br2/BiOBr nanosheet photocatalysts. The structure of the hybrid material was investigated by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy including energy dispersive X-ray (EDX) spectroscopy, and solid state 1H−13C nuclear magnetic resonance spectroscopy (1H−13C NMR). The material contains 18.9% of Bi4O5Br2/BiOBr and was found to be effective for the photocatalytic degradation of cationic methylene blue (MB) and zwitterionic rhodamine B (RhB) dyes under irradiation with 405 nm light. Lignin/Bi4O5Br2/BiOBr was able to decrease the dye concentration from 80 mg·L–1 to 12.3 mg·L–1 for RhB (85%) and from 80 mg·L–1 to 4.4 mg·L–1 for MB (95%). Complementary to the dye degradation, the lignin as a main component of the composite, was found to be efficient and rapid biosorbent for metal ions in aqueous solutions. The highest adsorption capacity was found after 2 hours of phases contact and reached 0.45 mmol·g–1 for Ni(II) ions (neutral media). The low cost, simplicity of the synthesis, good stability and ability to simultaneously photooxidize organic dyes and to adsorb metal ions, make the developed photoactive lignin/Bi4O5Br2/BiOBr composite a prospective material for textile wastewaters remediation

The diagram showing how the size, shape, and dispersity of the LNPs is depending on the structural properties of initial lignin and how they can be tailored by changing lignin concentration and by applying lignins with different molecular weights.

Lignin is a renewable biopolymer, and its chemical functionalization renders it a prospective material for a plethora of applications. Within this respect, we present a method for lignin immobilization on the surface of mesoporous silica. Two types of lignins were used to prove the feasibility of the fabrication of either hydrophilic or hydrophobic biocoatings on silica. The procedure permits to immobilize 17 mg of lignosulfonate (LS) or 37 mg of kraft lignin (KL) per gram of silica. The bioinorganic composites display a synergistic effect in the adsorption of cobalt(II) ions from aqueous solutions because the adsorption efficiency outperforms the individual constituents. These results demonstrate that thin lignin overlayers, exhibiting polymer concentrations of 0.07 mg.m(-2) for LS-SiO2, and 0.14 mg.m(-2) for KL-SiO2, provide new functionality in comparison to bulk lignin and metal oxides. According to the Langmuir isotherm model, the adsorption capacity toward aqua complexes of Co(II) was found to be 75 and 59 mg.g(-1) for the LS- or KL-coated silica, respectively. The kinetic study revealed that lignin-SiO2 composites gained the features of inorganic sorbents because 1-1.5 h was sufficient for effective cobalt extraction. The adsorption on the bioinorganic composites proceeds with the pseudo-second-order kinetics model. The adsorption of Co(II) ions was confirmed by means of solid-state H-1 magic-angle spinning (MAS) NMR spectroscopy. The simplicity of the synthesis, low-cost and abundancy of substrates, high capacity, and fast kinetics make such lignin-coated silica a promising material for cobalt recovery.

Abstract Commercial birch xylan (CX) and alkali-soluble birch xylan (ASX) were subjected to controlled acetylation and used for film formation in the presence (20% and 40%) or absence of plasticizers (i.e. glycerol, sorbitol and xylitol). Although the content of Klason lignin was similar (1.2–1.4%), the acetylation process was favored by the high-purity CX (97% xylan) over the ASX (89% xylan). On the other hand, the presence of residual pectin heteropolysaccharides rather than xylan in the ASX sample was beneficial for film formation. These heteropolysaccharides seemed to act as natural plasticizers during film formation, allowing the formation of coherent films from ASX, even in the absence of an external plasticizer. The use of plasticizers favored the mechanical properties of films, especially in a dosage of 40%, when plastic behavior was created. Acetylation favored the film formation and slightly improved the mechanical properties of the films, and this improvement was in the same range as that achieved when using 20% plasticizer in non-acetylated ASX.

H-1 liquid-state nuclear magnetic resonance (NMR) spectroscopy was applied for the first time to lignin nanoparticles (LNPs) in an aqueous suspension to study the surface composition of LNPs and to acquire a better understanding of the mechanism of their formation. A series of LNPs were prepared from spruce and eucalyptus kraft lignin fractions with narrow molecular weight distributions and functionalities. An NMR pulse program combining presaturation with excitation sculpting increased the signal resolution, making it possible to observe a superficial layer of LNPs directly in the aqueous suspension, "as prepared". The particle size, charge, and surface morphology were characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). According to liquid-state NMR, methoxy groups from syringyl and guaiacyl units of lignin are the main groups present on the surface of LNPs. The presence of aliphatic moieties, mainly from side chains of lignin molecules, has also been confirmed. Taking into consideration the chemical composition of the lignin fractions, the structure of lignin NPs as shown by NMR spectroscopy and their size and surface charge, a pattern of lignin self-assembly into LNPs has been suggested.