Beech sawdust was treated with a ternary solvent system based on binary aqueous ethanol with partial substitution of ethanol by acetone at four different water contents (60, 50, 40, and 30%v/v). In addition to standard, i.e., noncatalyzed treatments, the application of inorganic acid in the form of 20 mm H2SO4 was evaluated. The various solvent systems were applied at 180 °C for 60 min. The obtained biomass fractions were characterized by standard biomass compositional methods, i.e., sugar monomer and oligomer contents, dehydration product contents of the aqueous product, and lignin, cellulose, and hemicellulose contents in isolated solid fractions. More advanced analyses were performed on the lignin fractions, including quantitative 13C NMR analyses, 1H–13C HSQC analysis, size exclusion chromatography, and pyrolysis-GC/MS, and the aqueous product, in the form of size exclusion chromatography and determination of total phenol contents. The picture emerging from the thorough analytical investigation performed on the lignin fractions is consistent with that resulting from the characterization of the other fractions: results point toward greater deconstruction of the lignocellulosic recalcitrance upon higher organic solvent content, replacing ethanol with acetone during the extraction, and upon addition of mineral acid. A pulp with cellulose content of 94.23 wt % and 95% delignification was obtained for the treatment employing a 55/30/15 EtOH/water/acetone mixture alongside 20 mm H2SO4. Furthermore, the results indicate the formation of two types of organosolv furan families during treatment, which differ in the substitution of their C1 and C5. While the traditional lignin aryl–ether linkages present themselves as indicators for process severity for the nonacid catalyzed systems, the distribution of these furan types can be applied as a severity indicator upon employment of H2SO4, including their presence in the isolated lignin fractions.

Marine fouling poses significant challenges to the efficiency and longevity of marine engineering equipment. To address this issue, developing effective marine antifouling coatings is critical to ensure the economic viability, environmental sustainability, and safety of offshore operations. In this study, we developed an innovative green antifouling and wear-resistant coating based on lignin, a renewable and sustainable resource. Lignin is considered environmentally friendly because it is abundant, biodegradable, and reduces reliance on petroleum-based materials. The coating was formulated with a controlled hydrophilic-to-hydrophobic ratio of 2:8, leveraging lignin's unique properties. Applying lignin increased the water contact angle by 14.5 %, improving surface hydrophobicity and contributing to the coating's antifouling efficacy. Moreover, the mechanical strength of the coating was enhanced by approximately 200 %, significantly boosting its durability in harsh marine environments. Additionally, the friction coefficient was reduced by about 85 %, further preventing organism adhesion. These results demonstrate that lignin-based coatings offer a greener alternative to traditional antifouling solutions. The results of this study not only help advance antifouling coating technology but are also consistent with the broader goal of promoting environmental responsibility in marine engineering practice.

The rise in global temperature and accumulation of petroleum-based wastes in the environment forces the scientific focus towards renewable alternatives. In the present work, an under-exploited resource – spruce bark – is investigated as a raw material for production of bio-oil as a liquid energy carrier. To enhance the energy-content of the produced bio-crude, ultimately being produced through hydrothermal liquefaction, the polysaccharides were extracted through organosolv fractionation and converted to lipids by oleaginous microorganisms. The effect originating from tannins was also investigated by performing a pre-extraction before the organosolv fractionation. It was found that performing the organosolv fractionation and upgrading the isolated organosolv lignin to bio-oil greatly reduced the oxygen content of the oil fraction thereby improving its energy content, and introducing upgraded polysaccharides in the form of lipids, as well as pre-extracted tannins, caused clear changes in the product distribution of the final bio-oil and kept a final product with low oxygen content. The other factor largely influencing the product distribution originated from the various heating rates tested by altering operational mode of the HTL process between batch and semi-continuous. Ultimately, performing the organosolv fractionation and individual upgrading of the polysaccharides had a beneficial effect on reducing the final solids content and enhancing the liquid oil yield.

Silver nanoparticles (AgNPs) are excellent antimicrobial agents and promising candidates for preventing or treating bacterial infections caused by antibiotic resistant strains. However, their increasing use in commercial products raises concerns about their environmental impact. In addition, traditional physicochemical approaches often involve harmful agents and excessive energy consumption, resulting in AgNPs with short-term colloidal stability and silver ion leaching. To address these issues, we designed stable hybrid lignin–silver nanoparticles (AgLigNPs) intended to effectively hit bacterial envelopes as a main antimicrobial target. The lignin nanoparticles (LigNPs), serving as a reducing and stabilizing agent for AgNPs, have a median size of 256 nm and a circularity of 0.985. These LigNPs were prepared using the dialysis solvent exchange method, producing spherical particles stable under alkaline conditions and featuring reducing groups oriented toward a wrinkled surface, facilitating AgNPs synthesis and attachment. Maximum accumulation of silver on the LigNP surface was observed at a mass reaction ratio mAg:mLig of 0.25, at pH 11. The AgLigNPs completely inhibited suspension growth and reduced biofilm development by 50% in three tested strains of Pseudomonas aeruginosa at a concentration of 80/9.5 (lignin/silver) mg L–1. Compared to unattached AgNPs, AgLigNPs required two to eight times lower silver concentrations to achieve complete inhibition. Additionally, our silver-containing nanosystems were effective against bacteria at safe concentrations in HEK-293 and HaCaT tissue cultures. Stability experiments revealed that the nanosystems tend to aggregate in media used for bacterial cell cultures but remain stable in media used for tissue cultures. In all tested media, the nanoparticles retained their integrity, and the presence of lignin facilitated the prevention of silver ions from leaching. Overall, our data demonstrate the suitability of AgLigNPs for further valorization in the biomedical sector. 

In this Thesis, organosolv fractionation of softwood (spruce), hardwood (birch and beech), and herbaceous crops (wheat straw) was performed by applying various organosolv process conditions. Among these were a novel steam-explosion/organosolv hybrid mode, and two ternary solvent systems utilizing water/ethanol/acetone, and water/acetone/acetic acid. In addition, the effect of using inorganic acidic catalyst (H2SO4) was investigated for all raw material classes. Also, alkaline catalyst (NaOH) was investigated for wheat straw due to its reported high content of inorganics which presence adds additional structural complexity to the lignocellulosic recalcitrance. Following the organosolv fractionation, structural characterization was performed (content of cellulose, hemicellulose, lignin) in the isolated product fractions. Additionally, in-depth characterization of the isolated lignins was performed by combining Pyrolysis-Gas Chromatography Mass Spectroscopy (Pyr-GC/MS), Gel Permeation Chromatography (GPC), and different modes of Nuclear Magnetic Resonance (NMR; 13C, 1H-13C, 31P). Complementary analytics, such as content of monomeric/oligomeric sugars, dehydration products, total phenolics, and Size-Exclusion Chromatography (SEC) of the isolated product liquor, were performed to provide a comprehensive understanding of the process. Special attention was given the lignin structural changes occurring throughout the organosolv process. This was done as the use of lignin for higher-value application is considered crucial for the economic viability and development of a modern biorefinery. For this reason, significant focus was given to study how the lignin characteristics translate into physical properties such as solubility. The latter property was measured through solubility trials in binary aqueous acetone solutions, as well as solvent-based fractionation (acetone-water system). A coherent picture was aimed for, where structural motifs and lignin characteristics were correlated to reductions/enhancements in solubility at various water contents. To finally bridge this with a potential down-stream application, DPPH radical scavenging was performed in DMSO with and without intercalating Lithium Bromide (LiBr) for a selection of organosolv lignins, as well as their acetone/water fractionated lignins. This was complemented with a UV absorption study of the lignin solutions.The results provide a descriptive span of chemical characteristics related to organosolv lignins, where they range between highly native, to non-native. Whereas the former lignins are largely comprised of inter-unit motifs such as β-O-4’, β-β’ and β-5’, the non-native lignins are instead better characterized by a high content of oxidized sidechains, biaryls and bifurans, as well as showing strong indications of having quaternary cross-linkers originating from ketone functionalities. The ketones are also found to undergo aldol condensation with aldehydes formed throughout the process. Interestingly, these two extremes in lignin characteristics yield highly varying physical properties, where the predominantly native and non-native lignins for example display low and high solubility in pure acetone, respectively. Simultaneously, the latter is more prone towards water-induced precipitation, whereas the former instead require water to display complete (~100%) solubility at specific concentrations. These properties and findings are eventually consistent with recent literature where lignin aggregates also dominate their dissolved state, and the interunit motifs dictate the affinity on forming such aggregates which are important for both their dissolution, precipitation, but also their display of functionality such as antioxidant activity.                    

Metal nanoparticle synthesis via environmentally friendly methods is gaining interest for their potential advantages over conventional physico-chemical approaches. Herein, we propose a robust green synthesis route for lignin-modified silver nanoparticles, utilizing the recovery of lignin as a renewable raw material and exploring its application in valuable areas. Through a systematic approach combining UV-Vis spectroscopy with AAS and DLS, we identified repeatable and scalable reaction conditions in an aqueous solution at pH 11 for homogeneous silver nanoparticles with high uniformity. The TEM median sizes ranged from 12 to 15 nm with circularity between 0.985 and 0.993. The silver nanoparticles yield exceeded 0.010 mol L−1, comparable with traditional physico-chemical methods, with a minimal loss of silver precursor ranging between 0.5 and 3.9%. Characterization by XRD and XPS revealed the presence of Ag-O bonding involving lignin functional groups on the pure face-centered cubic structure of metallic silver. Moreover, the lignin-modified silver nanoparticles generated a localized thermal effect upon near-infrared laser irradiation (808 nm), potentially allowing for targeted applications in the biomedical field. Our study showcases the potential of lignin as a renewable reducing and capping agent for silver nanoparticle synthesis, addressing some shortcomings of green synthesis approaches and contributing to the development of suitable nanomaterials.

Halophytes have major potential in biorefinery as these salt tolerant crops have prospects as an alternative biomass to meet energy demands and provide value-added products with reduced effects in terms of food security and environmental damage when compared to other crops. In this study, we investigated the effects of organosolv pretreatment process parameters on the fractionation of residual fibers from pressed Salicornia ramosissima and how it affects the fractions of cellulose, lignin, and hemicelluloses. Pretreated pulps contained as high as 48.95% w/w cellulose, a 2.9-fold increase from the untreated fibers. The delignification of pulp was as high as 75.01% and hemicellulose removal reached 96.38%. The hemicellulose fractions contained as high as 78.49% oligomers and we identified up to 30.4% linear xylooligosaccharides in the composition. The majority of the fragments of hemicelluloses had molecular weights lower than 1000 Da. Isolated lignin samples had in most cases very low sugar and ash contamination with a reduced molecular weight. The typical G-, S-, and H-type aromatic units were detected in the lignin, together with & beta;-O-4 & PRIME;, & beta;-5 & PRIME;, & beta;-& beta;& PRIME;, and dibenzodioxocine links. The results suggest a novel applicability of S. ramosissima in a biorefinery context with fractionation deriving building blocks for value added products.

Organosolv lignins (OSLs) are important byproducts of the cellulose-centred biorefinery that need to be converted in high value-added products for economic viability. Yet, OSLs occasionally display characteristics that are unexpected looking at the lignin motifs present. Applying advanced NMR, GPC, and thermal analyses, isolated spruce lignins were analysed to correlate organosolv process severity to the structural details for delineating potential valorisations. Very mild conditions were found to not fractionate the biomass, causing a mix of sugars, lignin-carbohydrate complexes (LCCs), and corresponding dehydration/degradation products and including pseudo-lignins. Employing only slightly harsher conditions promote fractionation, but also formation of sugar degradation structures that covalently incorporate into the oligomeric and polymeric lignin structures, causing the isolated organosolv lignins to contain lignin-humin hybrid (HLH) structures not yet evidenced as such in organosolv lignins. These structures effortlessly explain observed unexpected solubility issues and unusual thermal responses, and their presence might have to be acknowledged in downstream lignin valorisation.

In this study, a facile synthesis method was employed to create lignin-castor oil-based oleogels by modifying organic lignin with two silane coupling agents. The resulting oleogels demonstrated outstanding lubricating and antioxidation properties, establishing them as promising green lubricating greases. Compared with the pure castor oil, the oxidation induction time (OIT) value of the synthesized oleogels was significantly increased from 20 s (pure castor oil) to 1959 s (oleogel with 20 wt % lignin), indicating an effective improvement of the oxidation resistance. The steel contacts lubricated by the synthesized oleogel also had lower wear than those lubricated by pure castor oil, signifying the better lubricating properties of oleogels. The oleogel with 20 wt % lignin showed the lowest wear, which was around 64% lower than that of pure castor oil. The exceptional performance and environmentally sustainable composition of these oleogels, with the biomass content exceeding 80%, allow them to be used as green lubricating greases for industrial applications. Overall, this study provides valuable insights into the development of high-performance, eco-friendly lubricants.

Conversion of organosolv lignins isolated with and without an inorganic acid catalyst (H2SO4) from hard- and softwood (birch and spruce) into bio-oil through hydrothermal liquefaction has been investigated. Furthermore, fractions of the isolated bio-oils were catalytically deoxygenated to improve the bio-oil properties. As elucidated through NMR, both biomass source and extraction mode influence the bio-oil product distribution. Depending on whether the lignins carry a high content of native structures, or are depolymerized and subsequently condensed in the presence of sugar dehydration products, will dictate heavy oil (HO) and light oil (LO) distribution, and skew the HO product composition, which again will influence the requirements upon catalytical deoxygenation.