Lignin with controlled structural properties by N-heterocycle-based deep eutectic solvent extraction.

The complex and heterogeneous nature of the lignin macromolecule has presented a lasting barrier to its utilization. To achieve high lignin yield, the technical lignin extraction process usually severely modifies and condenses the native structure of lignin, which is a critical drawback for its utilization in conversion processes. In addition, there is no method capable of separating lignin from plant biomass with controlled structural properties. Here, we developed an N-heterocycle-based deep eutectic solvent formed between lactic acid and pyrazole (La-Py DES) with a binary hydrogen bonding functionality resulting in a high affinity toward lignin. Up to 93.7% of lignin was extracted from wheat straw biomass at varying conditions from 90 °C to 145 °C. Through careful selection of treatment conditions as well as lactic acid to pyrazole ratios, lignin with controlled levels of ether linkage content, hydroxyl group content, and average molecular weight can be generated. Under mild extraction conditions (90 °C to 120 °C), light-colored native-like lignin can be produced with up to 80% yield, whereas ether linkage-free lignin with low polydispersity can be obtained at 145 °C. Overall, this study offers a new strategy for native lignin extraction and generating lignin with controlled structural properties.

Unveiling the Structural Characteristics of Lignin and Lignin-Carbohydrate Complexes in Fibers and Parenchyma Cells of Moso Bamboo during Different Growing Years.

Understanding and recognizing the structural characteristics of lignin-carbohydrate complexes (LCCs) and lignin in different growth stages and tissue types of bamboo will facilitate industrial processes and practical applications of bamboo biomass. Herein, the LCC and lignin samples were sequentially isolated from fibers and parenchyma cells of bamboo with different growth ages. The diverse yields of sequential fractions not only reflect the different biomass recalcitrance between bamboo fibers and parenchyma cells but also uncover the structural heterogeneity of these tissues at different growth stages. The molecular structures and structural inhomogeneities of the isolated lignin and LCC samples were comprehensively investigated. The results showed that the structural features of lignin and LCC linkages in parenchyma cells were abundant in ß-O-4 linkages but less with carbon-carbon linkages, suggesting that lignin and cross-linked LCC in parenchyma cells are simple in nature and easily to be tamed and tractable in the current biorefinery. Parallelly, the different ball-milled samples were directly characterized by high-resolution (800 M) solution-state 2D-HSQC NMR to analyze the whole lignocellulosic material. Overall, the scheme presented in this study will provide a comprehensive understanding of lignin and LCC linkages in fibers and parenchyma cells of bamboo and enable the utilization of bamboo biomass.

Innovative flow-through reaction system for the sustainable production of phenolic monomers from lignocellulose catalyzed by supported Mo2C.

Molybdenum carbide supported on activated carbon (ß-Mo2C/AC) has been tested as catalyst in the reductive catalytic fractionation (RCF) of lignocellulosic biomass both in batch and in Flow-Through (FT) reaction systems. High phenolic monomer yields (34 wt.%) and selectivity to monomers with reduced side alkyl chains (up to 80 wt.%) could be achieved in batch in the presence of hydrogen. FT-RCF were made with no hydrogen feed, thus via transfer hydrogenation from ethanol. Similar selectivity could be attained in FT-RCF using high catalyst/biomass ratios (0.6) and high molybdenum loading (35 wt.%) in the catalyst, although selectivity decreased with lower catalyst/biomass ratios or molybdenum contents. Regardless of these parameters, high delignification of the lignocellulosic biomass and similar monomer yields were observed in the FT mode (13-15 wt.%) while preserving the holocellulose fractions in the delignified pulp. FT-RCF system outperforms the batch reaction mode in the absence of hydrogen, both in terms of activity and selectivity to reduced monomers that is attributed to the two-step non-equilibrium processes and the removal of diffusional limitations that occur in the FT mode. Even though some molybdenum leaching was detected, the catalytic performance could be maintained with negligible loss of activity or selectivity for 15 consecutive runs.

Selecting Suitable Near-Native Lignins for Research.

There are several methods to isolate near-native lignins, including milled-wood lignin, enzymatic lignin, cellulolytic enzyme lignin, and enzymatic mild-acidolysis lignin. Which one is the most representative of the native lignin? Herein, near-native lignins were isolated from different plant groups and structurally analyzed to determine how well these lignins represented their native lignin counterparts. Analytical methods were applied to understand the molecular weight, monomer composition, and distribution of interunit linkages in the structure of the lignins. The results indicated that either enzymatic lignin or cellulolytic enzyme lignin may be used to represent native lignin in softwoods and hardwoods. None of the lignins, however, appeared to represent native lignins in grasses (monocot plants) because of substantial syringyl/guaiacyl differences. Complicating the understanding of grass lignin structure, large amounts of hydroxycinnamates acylate their polysaccharides and, when released, are often conflated with actual lignin monomers.

Sequential aqueous acetone fractionation and characterization of Brauns native lignin separated from Chinese quince fruit.

Lignin, especially Brauns native lignin (BNL), from Chinese quince (Chaenomeles sinensis) fruit represents a potential source of natural antioxidants. However, the highly inhomogeneous structure and the carbohydrate impurity reduce the antioxidant properties of BNL. Accordingly, a sequential aqueous acetone fractionation was used to prepare pure lignin fractions with homogeneous molecular structures; these fractions showed strong antioxidant properties. Analytical results showed that the yields of F50% and F60% exceeded 20% (i.e., 20.6% and 24.1%, respectively). The sugar impurities in BNL were mainly retained in the F30% and F40% fractions. For all fractions, molecular weight increased as the acetone concentration increased. The results from 2D HSQC NMR and 31P NMR indicated that the number of lignin linkages (ß-O-4', ß-ß' and ß-5') and functional groups (S-OH, G-OH, H-OH, and COOH) of these fractions varied with their molecular weights. Antioxidant assays showed that F40%, F50% and F60% had higher antioxidant properties than BNL. Overall, the study provides a simple, environmentally friendly fractionation method to prepare lignin with various structural features and strong antioxidant properties from Chinese quince fruit. These lignin fractions have promising application in some fields with high value, such as antioxidants production, biomaterials, packaging materials, and drug delivery and so on.