During kraft pulping of wood, a considerable part of biomass is solubilized, forming a black liquor from which material can be taken out as by-products. Of these, extractive-derived fractions such as tall oil and raw turpentine has long seen technical utilization, and presently, lignin degradation products have garnered a large interest. The carbohydrate degradation products, however, have seen considerably less focus. In this work, we have investigated the structure of a high molecular-weight fraction of the carbohydrate degradation products using nuclear magnetic resonance spectroscopy, finding it to be a conjugated aromatic structure rich in methyl, methylidine, alcohol and carboxylic acid groups. Based on this information, we suggest a structure based on hydroxymethylfurfural as the repeating unit, with sugar acid substituents providing additional functionality. Additionally, UV-vis data of the polymer is compared with data from the kraft cooking of cotton linters and other model systems to corroborate the hypothesis that this polymer is indeed present in black liquor and potentially responsible for some of its characteristic colour. It also reacts in the kappa number analysis, exhibiting 40 % of the permanganate consumption predicted for pure lignin. Finally, the technical significance of these carbohydrate degradation products is discussed based on the structural findings.

Lignin nanoparticles (LNPs) are gaining increasing interest for applications in various fields, where the particle homogeneity, morphology, and surface properties are critical for performance. In this study, lignin obtained via kraft process from spruce and eucalyptus was employed as precursor for the fabrication of lignin nanoparticles with tunable physicochemical properties. Linear ester groups with varying chain lengths were introduced to systematically investigate the effects of the hydrophobic moiety distribution on lignin nanoparticle formation via solvent-shifting self-assembly. Results demonstrated that esterification-induced structural changes altered the balance of key noncovalent interactions (hydrogen bonding, π–π stacking, and hydrophobic interactions), which collectively governed the self-assembly process, with longer ester chains promoting compact particles with hydrophobic surfaces. By directly linking molecular-level modification of lignin to alterations in the inter- and intramolecular interactions driving the self-assembly of nanoparticles, this study provides a mechanistic framework for the rational design of lignin nanoparticles through controlled chemical modification, thereby expanding their application flexibility.

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.

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 °C for 3 h and a cooking step at 160 °C for 4 h. A nuclear magnetic resonance study on the dissolved lignin produced for said experiment showed characteristics typical of other kraft lignins.

Samples of Eucalyptus dunnii with high calcium content have less good pulping properties regarding delignification and polysaccharide degradation, as it was shown by us earlier. In this work, we tested the addition of black liquor and green liquor to the Eucalyptus dunnii chips before kraft pulping, Specific improvements were obtained with both liquors, but the most substantial effect was observed with the green liquor, where even wood with the highest calcium content was pulped with a good result. Delignification was faster, and viscosity losses (degree of polymerization of cellulose) were higher for samples treated with green liquor prior to kraft pulping. Bleaching experiments showed that the bleachability of the green liquor-treated pulp was virtually the same as for a control pulp and that the higher viscosity of the bleached pulp was maintained. Possible chemical explanations for the results obtained are discussed.

Studies have shown that the size of LNP depends on the molecular weight (M-w) 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 M-w 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 pi-pi 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.

Water electrolysis is a promising approach for the sustainable production of hydrogen, however, the unfavorable thermodynamics and sluggish kinetics of oxygen evolution reaction (OER) are associated with high anodic potentials. To lower the required potentials, an effective strategy is proposed to substitute OER with partial oxidation of degradation products of carbohydrate origin from the waste stream of a chemical pulping industry. In this work, two different catalytic materials - PdNi and NiO are investigated comparatively to understand their catalytic performance for the oxidation of carbohydrate alkaline degradation products (CHADs). PdNi can catalyze CHADs with low potential requirements (-0.11 V vs. Hg/HgO at 150 mA cm(-2)) but is limited to current densities <200 mA cm(-2). In contrast, NiO can operate at very high current densities but required relatively higher potentials (0.53 V vs. Hg/HgO at 500 mA cm(-2)). The performance of this non-noble metal catalyst compares favorably with that of Pd-based catalysts for hydrogen production from CHADs at high conversion rates. This work shows the potential to utilize waste streams from a large-scale process industry for sustainable hydrogen production, and also opens up opportunities to study earth-abundant electrocatalysts to efficiently oxidize biomass-derived substances.

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. 

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.