The autocatalyzed ethanolic organosolv process is gaining increasing attention for the sulfur-free isolation of lignin, which is subsequently used as a renewable substitute for various fossil-based applications. For the first time, the mechanochemical influence of seven different particle sizes of two different biomasses on the respective organosolv lignin structure is examined. Wine pruning (Pinot Noir) and wine pomace (Accent) are used for organosolv process with particle sizes ranging from 2.0-1.6 mm to less than 0.25 mm. As particle size decreases, the weight-average molecular weight increases, while the total phenol content decreases significantly. Additionally, the distribution of the lignin-typical monolignols and relevant substructures, as determined by two-dimensional heteronuclear nuclear magnetic resonance spectra single quantum coherence (HSQC), is observed. The degree of grinding of the biomass has a clear chemical-structural influence on the isolated HG and HGS organosolv lignins. Therefore, it is crucial to understand this influence to apply organosolv lignins in a targeted manner. In the future, particle size specifications in the context of the organosolv process should be expressed in terms of distribution densities rather than in terms of a smaller than specification.

The development of strategies allowing either the production of high value phenolics, or the isolation of properties-enhanced materials from technical lignins represents a fundamental step in the industrial upcycling of technical lignins. Both aims are met by the strategy presented in the present work, relying on the coupling of solvent-based fractionation with the oxidative action of a new type of alkaline-stable genetically modified bacterial laccase. The described approach succeeded in the tandem, high-yield and selective isolation of valuable lignin-monomeric compounds (MCs) and high molecular weight and hydrophobicity-tailored polymerised materials (PMs) from two technical lignins, namely softwood kraft lignin (SKL), and wheat straw organosolv lignin (WSL). With respect to MCs, higher yields as compared to similar studies (up to 17.2 mg/g) were achieved. PMs from SKL samples where characterised by an almost quadrupled Mw, while in the case of WSL the Mw was approximately doubled. Noteworthy, the reaction conditions were optimized in terms of reaction temperature, time, enzymatic loading, and alkalinity for the selective production of single MCs. Most interestingly, technical lignins as well as their fractions and the PMs deriving from their laccase-catalysed oxidation showed increased hydrophobicity.

Lignin has been overlooked and used as a waste for long due to its complex and partially hydrophobic structure. Many efforts have been carried out to overcome these deficiencies and apply it as a high-value product, which are insufficient to reach the full potential of lignin in various advanced applications, since they require with procedures for the obtaining of more specific and fine-tuned chemical structures. This work focuses on the obtaining of differently structured hydrophilic lignins derived both from Kraft and organosolv isolation processes. The chemical structures of the different lignin types were studied, and the effect of the structural differences in the modification processes and their subsequent properties analyzed, valorizing their potential application for diverse purposes. The carboxymethylation and sulfomethylation reactions were carried out with the aim of enhancing the polarity of the lignin samples, while the methylation reaction aimed to obtain lignins with higher stability. The physicochemical analyses of the samples, carried out by FTIR, GPC, 31P NMR, 13C NMR, and HSQC NMR, verified the effectiveness of the chemical reactions and conditions selected, obtaining lignins with lower hydroxyl content, due to their substitution and insertion of carboxymetyl, sulfomethyl and methyl groups, therefore obtaining more condensed, aromatic and oxygenated aromatic carbon structures. While the methylation reaction was the most efficient in substituting the OH groups, due to its non-selectivity, OL showed higher modification yields than KL. In terms of the thermal and morphological properties, analyzed by DLS and TGA respectively, it was observed that the modified samples showed lower Z potential values, along with higher conductivity, being the sulfomethylated organosolv lignin the one showing the best results, which was also the one with the smallest particle size and polydispersity index. Finally, all the modified samples showed higher T50% values, suggesting a better stability towards degradation.

The intricate structure of lignin, characterized by a mix of hydrophilic components and hydrophobic structures from its aliphatic and aromatic constituents, poses challenges in creating monodisperse particles. This is due to the need for precise modulation of self-assembly kinetics. Herein, we explore a correlation between the substructure of lignin and its capacity for self-assembly. We have conducted an in-depth investigation into the interactions between hydrophilic groups, such as phenolic and aromatic-OH, and monolignols with interunit linkages that are involved in the formation of lignin particles (LPs). A high degree of hydrophilicity with a condensed structure is crucial for high supersaturation levels, which in turn determines the growth phase and leads to small LPs. An approach based on tailoring the supersaturation level which is contingent on the structural characteristics of extracted organosolv lignin was used to obtain remarkably uniform LPs with mean diameters of approximately 230 and 480 nm. The results of this study have the potential to serve as a foundation for the preparation of monodisperse LPs derived from various lignin sources as well as for the development of methods to extract lignin containing a specific chemical substructure.

Laccase-like multicopper oxidases are recognized for their potential to alter the reactivity of lignins for application in value-added products. Typically, model compounds are employed to discover such enzymes; however, they do not represent the complexity of industrial lignin substrates. In this work, a screening pipeline was developed to test enzymes simultaneously on model compounds and industrial lignins. A total of 12 lignin-active fungal multicopper oxidases were discovered, including 9 enzymes active under alkaline conditions (pH 11.0). Principal component analysis revealed the poor ability of model compounds to predict enzyme performance on industrial lignins. Additionally, sequence similarity analyses grouped these enzymes with Auxiliary Activity-1 sub-families with few previously characterized members, underscoring their taxonomic novelty. Correlation between the lignin-activity of these enzymes and their taxonomic origin, however, was not observed. These are critical insights to bridge the gap between enzyme discovery and application for industrial lignin valorization.

Lignin, the second most abundant biopolymer on earth and with a predominantly aromatic structure, has the potential to be a raw material for valuable chemicals and other bio-based chemicals. In industry, lignin is underutilized by being used mostly as a fuel for producing thermal energy. Valorization of lignin requires knowledge of the structure and different linkages in the isolated lignin, making the study of structure of lignin important. In this article, lignin samples isolated from two types of reactors (autoclave reactor and displacement reactor) were analyzed by FT-IR, size exclusion chromatography, thermogravimetric analysis (TGA), and Py-GC-MS. The average molecular mass of the organosolv lignins isolated from the autoclave reactor decreased at higher severities, and FT-IR showed an increase in free phenolic content with increasing severity. Except for molecular mass and molecular mass dispersity, there were only minor differences between lignins isolated from the autoclave reactor and lignins isolated from the displacement reactor. Carbohydrate analysis, Py-GC-MS and TGA showed that the lignin isolated using either of the reactor systems is of high purity, suggesting that organosolv lignin is a good candidate for valorization.

This article provides UV-spectrophotometry data of technical lignin samples in solutions, which were acquired after ambient aging for up to 110 days or looped measurements on fresh solutions. UV-spectrophotometry of lignin is a useful technique, as it can a) quantify the concentration and purity of lignin in a given sample, b) determine the abundance of phenolic hydroxyl groups, and c) yield qualitative information about chemical modification of the lignin macromolecule. In addition, the technique is rapid and easy to use. Still, solutions of lignin are known to be unstable; in particular at high pH or in presence of UV-light. The data in this article may hence serve as guide in the experimental conduct and design, as it shows the reproducibility of UV-spectrophotometry measurements of lignin. Stock solutions of technical lignin were made according to previously published procedure [1]. The solutions in dimethyl sulfoxide (DMSO) were aged in 100 mL volumetric flasks with glass stopper, taking periodic samples for measurements in a Shimadzu UV-1900 UV-vis spectrophotometer. The instrument recorded the spectrum from 500 to 200 nm at 1.0 nm intervals and medium speed, using quartz cuvettes with a pathlength of 1 cm. In addition, looped measurements were conducted on fresh solutions, where the instrument repeated the spectral range of 500 to 200 nm for in total sixteen times. The latter examined solutions of technical lignin in DMSO solvent as well as in 0.2 N NaOH in water.

Rust powder collected from an archeological iron was evaluated by complementary analyses such as FTIR, XRD, XRF, and SEM/EDX. The analyses revealed that lepidocrocite (L) was the major component in the archeological iron. Coconut husk (CH) can be classified as a type of lignocellulosic biomass of renewable resources that are widely available, especially in coastal areas. In this research, the isolated lignin extracted from CH is being studied as a potential alternative for environmentally friendly applications. The isolated lignin from soda and organosolv pulping went through several analyses such as FTIR, NMR (13C and 2D-HSQC), and TGA analyses. The analyses showed that lignin isolated via soda pulping has superior antioxidant capabilities due to its greater phenolic-OH content compared to lignin isolated from organosolv pulping. The effects of lignin concentrations, pH, and reaction time were utilized in rust conversion studies of an archeological iron. 5 wt% of soda lignin (SL) was revealed as the ideal condition in this rust conversion study with a value of 84.21 %. The treated rust powder with 5 wt% of SL was then further gone through several complementary analyses, which revealed that the treated rust had nearly transformed into an amorphous state.

Despite lignin\'s global abundance and its use in biomedical studies, our understanding of how lignin regulates disease through modulation of cell morphology and associated phenotype of human cells is unknown. We combined an automated high-throughput image cell segmentation technique for quantitatively measuring a panel of cell shape descriptors, droplet digital Polymerase Chain Reaction for absolute quantification of gene expression and multivariate data analyses to determine whether lignin could therapeutically modulate the cell morphology and phenotype of inflamed, degenerating diseased human cells (osteoarthritic (OA) chondrocytes) towards a healthier cell morphology and phenotype. Lignin dose-dependently modified all aspects of cell morphology and ameliorated the diseased shape of OA chondrocytes by inducing a less fibroblastic healthier cell shape, which correlated with the downregulation of collagen 1A2 (COL1A2, a major fibrosis-inducing gene), upregulation of collagen 2A1 (COL2A1, a healthy extracellular matrix-inducing gene) and downregulation of interleukin-6 (IL-6, a chronic inflammatory cytokine). This is the first study to show that lignin can therapeutically target cell morphology and change a diseased cells\' function towards a healthier cell shape and phenotype. This opens up novel opportunities for exploiting lignin in modulation of disease, tissue degeneration, fibrosis, inflammation and regenerative medical implants for therapeutically targeting cell function and outcome.

Bio-polyols, produced by liquefying lignin with polyhydric alcohols, offer a promising alternative to conventional polyols for polyurethane production. To enhance the sustainability on the production of these bio-polyols, this study proposes the use of crude glycerol and microwave-assisted liquefaction as substitutes for conventional methods and commercial glycerol. This approach reduces the energy requirements of the reaction while also adding value to this by-product. The synthesis of bio-polyols with suitable properties to produce elastic and rigid polyurethane was carried out using previously optimised reaction conditions. Organosolv lignins obtained from Eucalyptus globulus and Pinus radiata were employed, using polyethylene glycol and crude glycerol as solvents and sulphuric acid as a catalyst. Several parameters of the bio-polyols were analysed, including hydroxyl number (IOH), acid number (An), and functionality (f), suggesting that the bio-polyols were suitable for polyurethane synthesis. Bio-polyols formulated to produce rigid polyurethanes exhibited IOH values of 554 and 383 (mg KOH/g), An values of 1.91 and 4.21 (mg KOH/g), and functionalities of 4.16 and 3.14 for Eucalyptus globulus and Pinus radiata lignin. In the case of bio-polyols for elastic polyurethanes, the values were 228 and 173 (mg KOH/g) (IOH), 20.94 and 25.09 (mg KOH/g) (An), and functionalities of 3.51 and 2.08.