The Effect of Ball Milling Time on the Isolation of Lignin in the Cell Wall of Different Biomass

Ball milling technology is the classical technology to isolate representative lignin in the cell wall of biomass for further investigation. In this work, different ball milling times were carried out on hardwood (poplar sawdust), softwood (larch sawdust), and gramineous material (bamboo residues) to understand the optimum condition to isolate the representative milled wood lignin (MWL) in these different biomass species. Results showed that prolonging ball milling time from 3 to 7 h obviously increased the isolation yields of MWL in bamboo residues (from 39.2% to 53.9%) and poplar sawdust (from 15.5% to 35.6%), while only a slight increase was found for the MWL yield of larch sawdust (from 23.4% to 25.8%). Importantly, the lignin substructure of ß-O-4 in the MWL samples from different biomasses can be a little degraded with the increasing ball milling time, resulting in the prepared MWL with lower molecular weight and higher content of hydroxyl groups. Based on the isolation yield and structure features, milling time with 3 and 7 h were sufficient to isolate the representative lignin (with yield over 30%) in the cell wall of bamboo residues and poplar sawdust, respectively, while more than 7 h should be carried out to isolate the representative lignin in larch sawdust.

Understanding the effects of different residual lignin fractions in acid-pretreated bamboo residues on its enzymatic digestibility

Background During the dilute acid pretreatment process, the resulting pseudo-lignin and lignin droplets deposited on the surface of lignocellulose and inhibit the enzymatic digestibility of cellulose in lignocellulose. However, how these lignins interact with cellulase enzymes and then affect enzymatic hydrolysis is still unknown. In this work, different fractions of surface lignin (SL) obtained from dilute acid-pretreated bamboo residues (DAP-BR) were extracted by various organic reagents and the residual lignin in extracted DAP-BR was obtained by the milled wood lignin (MWL) method. All of the lignin fractions obtained from DAP-BR were used to investigate the mechanism for interaction between lignin and cellulase using surface plasmon resonance (SPR) technology to understand how they affect enzymatic hydrolysis Results The results showed that removing surface lignin significantly decreased the yield for enzymatic hydrolysis DAP-BR from 36.5% to 18.6%. The addition of MWL samples to Avicel inhibited its enzymatic hydrolysis, while different SL samples showed slight increases in enzymatic digestibility. Due to the higher molecular weight and hydrophobicity of MWL samples versus SL samples, a stronger affinity for MWL (KD = 6.8–24.7 nM) was found versus that of SL (KD = 39.4–52.6 nM) by SPR analysis. The affinity constants of all tested lignins exhibited good correlations (r > 0.6) with the effects on enzymatic digestibility of extracted DAP-BR and Avicel. Conclusions This work revealed that the surface lignin on DAP-BR is necessary for maintaining enzyme digestibility levels, and its removal has a negative impact on substrate digestibility.

SUGARCANE BAGASSE LIGNIN OBTAINED BY DIFFERENT EXTRACTION METHODS

Sugarcane bagasse (SB) is a by-product of ethanol production obtained in large quantities worldwide, including Brazil. Lignin is one of SB components, and its extraction is of great interest due to its vast potential for use. In this study, sugarcane bagasse was subjected to two methods of lignin extraction to obtain: Klason lignin (LKL) and milled wood lignin (MWL). The syringil/guaiacyl ratio of the lignin obtained from sugarcane bagasse was 1.67. Thermogravimetric analysis showed that LKL is more resistant to thermal degradation than MWL. According to the FTIR spectra, LKL yields a more oxidized lignin, presenting greater changes in its structure than MWL. Thus, this study provides information on the changes caused by different extractions and strengthens future studies on the transformation of lignin into products of high added value.

Structural Changes in Milled Wood Lignin (MWL) of Chinese Quince (Chaenomeles sinensis) Fruit Subjected to Subcritical Water Treatment

Subcritical water treatment has received considerable attention due to its cost effectiveness and environmentally friendly properties. In this investigation, Chinese quince fruits were submitted to subcritical water treatment (130, 150, and 170 °C), and the influence of treatments on the structure of milled wood lignin (MWL) was evaluated. Structural properties of these lignin samples (UL, L130, L150, and L170) were investigated by high-performance anion exchange chromatography (HPAEC), FT-IR, gel permeation chromatography (GPC), TGA, pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), 2D-Heteronculear Single Quantum Coherence (HSQC) -NMR, and 31P-NMR. The carbohydrate analysis showed that xylose in the samples increased significantly with higher temperature, and according to molecular weight and thermal analysis, the MWLs of the pretreated residues have higher thermal stability with increased molecular weight. The spectra of 2D-NMR and 31P-NMR demonstrated that the chemical linkages in the MWLs were mainly β-O-4′ ether bonds, β-5′ and β-β′, and the units were principally G- S- H- type with small amounts of ferulic acids; these results are consistent with the results of Py-GC/MS analysis. It is believed that understanding the structural changes in MWL caused by subcritical water treatment will contribute to understanding the mechanism of subcritical water extraction, which in turn will provide a theoretical basis for developing the technology of subcritical water extraction.

Correction: Spruce milled wood lignin: linear, branched or cross-linked?

Correction for ‘Spruce milled wood lignin: linear, branched or cross-linked?’ by Mikhail Balakshin et al., Green Chem., 2020, 22, 3985–4001, DOI: 10.1039/D0GC00926A.

Spruce milled wood lignin: linear, branched or cross-linked?

Plausible up-to-date structural model of spruce MWL in agreement with the current structural and molecular weight data.

Structural Characterization and Antioxidant Activity of Milled Wood Lignin from Xylose Residue and Corncob

Xylose residue (XR), after diluted acid treatment of corncob, consists of cellulose and lignin. However, structural changes of XR lignin have not been investigated comprehensively, and this has seriously hindered the efficient utilization of lignin. In this study, corncob milled wood lignin (CC MWL), and xylose residue milled wood lignin (XR MWL) were isolated according to the modified milled wood lignin (MWL) method. The structural features of two lignin fractions were thoroughly investigated via fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and two dimensional nuclear magnetic resonance (2D NMR) spectroscopy techniques. XR MWL with higher yield and lower bound carbohydrate contents presented more phenolic OH contents than CC MWL due to partial cleavage of β-O-4. Furthermore, the molecular weights of XR MWL were increased, possibly because of condensation of the lignin during the xylose production. A study on antioxidant activity showed that XR lignin had better radical scavenging ability than that of 2,6-Di-tert-butyl-4-methyl-phenol (BHT) and CC MWL. The results suggested that the lignin in xylose residue, showing great antioxidant properties, has potential applications in food additives.