Alkaline soda lignin (AL) was sequentially fractionated into six fractions of different molecular size by means of solvent extraction and their phenolic hydroxyl groups were chemoselectively methylated to determine their effect on nanoparticle formation of lignin polymers. The effect of the lignin structure on the physical properties of nanoparticles was also clarified in this study. Nanoparticles were obtained from neat alkaline soda lignin (ALNP), solvent-extracted fractions (FALNPs, i.d. 414–1214 nm), and methylated lignins (MALNPs, i.d. 516–721 nm) via the nanoprecipitation method. Specifically, the size properties of MALNPs showed a high negative correlation (R² = 0.95) with the phenolic hydroxyl group amount. This indicates that the phenolic hydroxyl groups in lignin could be influenced on the nucleation or condensation during the nanoprecipitation process. Lignin nanoparticles exhibited high colloidal stability, and most of them also showed good in vitro cell viability. This study presents a possible way to control nanoparticle size by blocking specific functional groups and decreasing the interaction between hydroxyl groups of lignin.

In recent years, several studies focused on the synthesis of lignin-based nanoparticle in aqueous solution and its potential applications of the drug carrier were investigated. In this study, soda lignin (SL) nanoparticles (i.d. 128–560 nm) were synthesized by the nanoprecipitation process at three different concentrations (1, 2, and 4 mg/mL THF) with various molecular sizes of soda lignin (NP-F1, NP-F2, and NP-F3) obtained from sequential solvent extraction. The average molecular weights of SL, F1, F2, F3, F4, and F5 were 3130, 1190, 2550, 3680, 5310, and 14,650, respectively. The average size of the spherical lignin nanoparticle was a minimum of 128 nm for NP-C1 and the size increased up to 560 nm with increasing concentration. Particle surface charge increased with increasing concentration from −26 mV for NP-C1 to −38 mV for NP-C4. Contrary to expected general trends in polymeric nanoparticles, there was no remarkable change or trend with increasing lignin molecular weight since chemical structures of each lignin fraction are also remarkably different. Further studies to learn correlation between properties of lignin nanoparticle and its additional details regarding the chemical structures is needed.

Gamma-valerolactone (GVL) was found to be an effective, sustainable alternative in the lignocellulose defragmentation for carbohydrate isolation and, more specifically, for lignin dissolution. In this study, it was adapted as a green pretreatment reagent for milled pinewood biomass. The pretreatment evaluation was performed for temperature (140–180 °C) and reaction time (2–4 h) using 80% aqueous GVL to obtain the highest enzymatic digestibility of 92% and highest lignin yield of 33%. Moreover, the results revealed a positive correlation (R² = 0.82) between the lignin removal rate and the crystallinity index of the treated biomass. Moreover, under the aforementioned conditions, lignin with varying molecular weights (150–300) was obtained by derivatization followed by reductive cleavage (DFRC). 2D heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC-NMR) spectrum analysis and gel permeation chromatography (GPC) also revealed versatile lignin properties with relatively high β-O-4 linkages (23.8%–31.1%) as well as average molecular weights of 2847–4164 with a corresponding polydispersity of 2.54–2.96, indicating this lignin to be a heterogeneous feedstock for value-added applications of biomass. All this suggested that this gamma-valerolactone based pretreatment method, which is distinctively advantageous in terms of its effectiveness and sustainability, can indeed be a competitive option for lignocellulosic biorefineries.

In this study an empty fruit bunch (EFB) was subjected to a two-step pretreatment to defragment cellulose-rich fractions as well as lignin polymers from its cell walls. First pretreatment: acid-catalyzed steam explosion (ACSE) pretreatment of EFB was conducted under the temperature range of 180–220 °C and residence time of 5–20 min. The ACSE-treated EFB was further placed into the reactor containing 50% aq. ethanol and NaOH as a catalyst and heated at a temperature of 160 °C for 120 min for the second pretreatment: alkali-catalyzed organosolv treatment (ACO). The mass balance and properties of treated EFB were affected by the residence time. The lowest yield of a solid fraction was obtained when the residence time was kept at 15 min. Xylose drastically decreased, especially under the ACSE pretreatment. However, the crystallinity of cellulose increased by increasing the severity factor of the pretreatment and was 47.8% and 57% udner the most severe conditions. The organosolv lignin fractions also showed the presence of 14 major peaks via their pyrolysis-GC analysis. From here, it can be suggested that this kind of pretreatment can indeed be one potential option for lignocellulosic pretreatment.

A synergistic combination of dioxane, acetic acid, and HCl was investigated for lignin extraction from pine wood biomass. After initial screening of reagent combination, response surface methodology (RSM) was used to optimize the lignin yield with respect to the variables of time 24–72 h, solids loading 5–15%, and catalyst dose 5–15 mL. A quadratic model predicted 8.33% of the lignin yield, and it was further confirmed experimentally and through the analysis of variance (ANOVA). Lignin at optimum combination exhibited features in terms of derivatization followed by reductive cleavage (DFRC) with a value of (305 µmol/gm), average molecular weights of 4358 and polydispersity of 1.65, and 2D heteronuclear single quantum coherence nuclear magnetic resonance spectrum (2D-HSQC NMR) analysis showing relative β-O-4 linkages (37.80%). From here it can be suggested that this fractionation can be one option for high quality lignin extraction from lignocellulosic biomass.