Polyphenolic Lignin Research Articles

Plant cell wall inspired lignin-based membrane with configurable radical scavenging activity

Natural antioxidants have received considerable attention due to their inherent biocompatibility and biodegradability, yet inferior antioxidant, storage instability, and structural heterogeneity limit applications. Drawing inspiration from plant structures, we develop antioxidant membranes that are entirely biomass-derived, metal-free, and customizable, using the layer-by-layer (LBL) assembly technique. The natural polyphenolic lignin co-assembles with lauryl alcohol derived from cassia bark into macroporous spherical particles in a γ-valerolactone (GVL)/water mixture, in which the pore size can be facilely adjusted by modulating feed ratio. Furthermore, the lignin nanospheres’ free radical scavenging ability is greatly enhanced by enlarging the pore size, offering an alternative way to improve the antioxidant performance. As the hydrophilic shells of lignin spherical assemblies display a strong affinity towards holocellulose nanofibrils (HCNF), multilayered antioxidant membranes with stable mechanical strength are constructed. The entirely biomass-derived antioxidant membrane has proven effective in recycled antioxidative microfiltration applications, demonstrating more than 90 % scavenging activity over seven cycles. Moreover, it exhibits biodegradability even in harsh conditions, with temperatures below 280 K and relative humidity less than 30 RH%. This work illuminates new possibilities for applying natural antioxidants in precise control materials.

Custom-designed polyphenol lignin for the enhancement of poly(vinyl alcohol)-based wood adhesive

Adhesives are used extensively in the wood industry. As resource and environmental issues become increasingly severe, the development of green and sustainable biomass-based adhesives has attracted increasing attention. In this work, a green wood adhesive is developed from poly(vinyl alcohol) and lignin with molecular designs of lignin extending beyond those in nature. The lignin undergoes extraction from corncob residue, aldehydration, and phenolisation (phenol, resorcinol, and catechol) to significantly increase the phenolic hydroxyl groups (over 7.92 mmol/g), which has the effect of enhancing the hydrogen bonding force between the adhesive and the wood, thereby greatly improving adhesive performance. Compared with pure PVA, polyphenol lignin-containing PVA showed improved adhesion strength and hydrophobicity. PVA/resorcinol-lignin has the significantly improved wood lap shear strength (6.27 MPa, 77.6 % improvement) and hydrophobicity (almost 100 % increase in wet shear strength). This research not only provides a green and high-performance alternative raw material for wood adhesives but also broadens the path for large-scale application of biomass.

Green and ultrastrong polyphenol lignin-based vitrimer adhesive with photothermal conversion property, wide temperature adaptability, and solvent resistance

Lignin, a natural adhesive in plants, has received extensive attention from both academia and industry. However, limited by the reactivity and heterogeneity of industrial lignin raw materials, lignin-based adhesives are not competitive in terms of adhesive performance and reusability. Here, a green and facile method is reported for a polyphenol lignin (Phenol-lignin)-based, ultrastrong, reusable, wide temperature adaptability, and solvent-resistant vitrimer adhesive with molecular designs of lignin extending beyond those in nature. The fabricated Phenol-lignin-based vitrimer exhibits the world’s highest wood lap shear strength of 12.87 MPa among the vitrimer adhesives. Even in extreme environments, such as boiling water (100 °C), liquid nitrogen (-196 °C), and organic solvents, the Phenol-lignin-based vitrimer-bonded wood sheets can still maintain a high level of strength. In addition, due to the good light-to-heat conversion performance of lignin, Phenol-lignin-based vitrimer can be repaired by infrared laser irradiation. The recycled adhesive retained 93.1 % of its strength. This new lignin material will be incorporated into not only industrial adhesives but also various green material systems in the future.

Strong and flexible lignocellulosic film fabricated via a feasible molecular remodeling strategy

Biomass-derived sustainable film is a promising alternative to synthetic plastic, but hampered by strength, toughness and flexibility trade-off predicament. Here, a feasible and scalable strategy was proposed to fabricate strong and flexible lignocellulosic film through molecular reconstruction of cellulose and lignin. In this strategy, polyphenol lignin was absorbed and wrapped on the surface of cellulose fiber, forming strong interfacial adhesion and cohesion via intramolecular and intermolecular hydrogen bonding. Further, covalent ether bond was generated between the hydroxyl groups of lignocellulose to form chemical cross-linking network induced by epichlorohydrin (ECH). The synergistic effect of hydrogen bonding and stable chemical cross-linking enabled the resultant lignocellulosic film (ELCF) with outstanding mechanical strength of 132.48 MPa, the elongation at break of 9.77 %, and toughness of 9.77 MJ·m−3. Notably, the integration of polyphenol lignin synergistically improved the thermal stability, water resistance, UV-blocking performances of ELCF. Importantly, after immersion for 30 d, ELCF still possessed high wet strength of 70.38 MPa, and elongation at break of 7.70 %, suggesting excellent and durable mechanical performances. Moreover, ELCF could be biodegraded in the natural soil. Therefore, this study provides a new and versatile approach to reconstruct highly-performance lignocellulosic films coupling strength, toughness with flexibility for promising plastic replacement.

Integrated Approach for Bioethanol and Paper Production using Populus deltoides Wood Biomass: An Experimental Study

Lignocellulosic materials contain two major sugar macromolecules, cellulose and hemicellulose, and polyphenolic lignin. During pulping, lignin and hemicellulose are broken down into smaller molecules such as organic acids, and removed in the black liquor, leaving cellulose fibers for papermaking. Lignocellulose consists of approximately 28–35% hemicelluloses, which are lost during the pulping process in black liquor and are an important source of sugars that can be used to produce bioethanol as a liquid fuel. The hemicellulosic sugars from the Populus deltoides (poplar) lignocellulosic biomass were partially extracted keeping in mind that it does not affect the properties of paper beyond acceptable limits, further converting these extracted sugars by fermentation to bioethanol, followed by pulping the residual biomass and papermaking and determining pulping and papermaking properties. With the increasing demand for lignocellulosic biomass by various industries, an integrated biorefinery approach for maximum utilization of its chemical components with minimum degradation is necessary in the future. The maximum bioethanol yield was found to be 3.58 g/L. On manufactured paper sheets, the mechanical properties tensile index and tear index of pre-extracted biomass were observed as 19.23 Nm/g and 3.5 mNm2/g and slightly lower against the control 21.34 Nm/g and 4.0 mNm2/g. The main objective of the present study is to recover reducing sugars before the pulping process for bioethanol production and to further utilize the remaining residue for papermaking without disturbing its fiber integrity.

Combined Catalysis: A Powerful Strategy for Engineering Multifunctional Sustainable Lignin-Based Materials

The production and engineering of sustainable materials through green chemistry will have a major role in our mission of transitioning to a more sustainable society. Here, combined catalysis, which is the integration of two or more catalytic cycles or activation modes, provides innovative chemical reactions and material properties efficiently, whereas the single catalytic cycle or activation mode alone fails in promoting a successful reaction. Polyphenolic lignin with its distinctive structural functions acts as an important template to create materials with versatile properties, such as being tough, antimicrobial, self-healing, adhesive, and environmentally adaptable. Sustainable lignin-based materials are generated by merging the catalytic cycle of the quinone-catechol redox reaction with free radical polymerization or oxidative decarboxylation reaction, which explores a wide range of metallic nanoparticles and metal ions as the catalysts. In this review, we present the recent work on engineering lignin-based multifunctional materials devised through combined catalysis. Despite the fruitful employment of this concept to material design and the fact that engineering has provided multifaceted materials able to solve a broad spectrum of challenges, we envision further exploration and expansion of this important concept in material science beyond the catalytic processes mentioned above. This could be accomplished by taking inspiration from organic synthesis where this concept has been successfully developed and implemented.

Fascinating polyphenol lignin extracted from sawdust via a green and recyclable solvent route

Due to the complexity, heterogeneity and recalcitrant structure of lignin, the extraction of multifunctional lignin directly from lignocellulose is still a challenge. Here, a green and recyclable route was proposed to separate high-quality lignin and tailor its functionalities. Through tuning the components of deep eutectic solvent (DES) and separation procedures, DES extracted lignin (DESL) exhibited high purity of 99.6 %, yield of 83.2 % and phenolic hydroxyl content of 8.33 wt%. The results of FTIR and 13C NMR demonstrated that DESL possessed more oxygen-containing reactive groups compared with commercial lignin (CL), enabling DESL with more superior functional activities. DESL exhibited higher antioxidant activity with the DPPH capture rate of 73.2 %. Meanwhile, DESL showed strong bactericidal effects against E. coli (100 %) and S. aureus (100 %) due to higher phenolic hydroxyl content, which could destroy bacterial cell membranes and inhibit bacterial metabolism by interacting with phospholipid layer and protein. Additionally, DESL displayed strong UV absorption and could be blended with polyurethane to enhance UV shielding property of polyurethane composite film with >50 of UPF value. In summary, DES treatment is a suitable strategy for high-quality lignin separation, which opens a broad spectrum of possibilities for lignin valorization.

Antiflammatory activity and potential dermatological applications of characterized humic acids from a lignite and a green compost

Long-term exposure to air pollution has been associated with the development of some inflammatory processes related to skin. The goal of modern medicine is the development of new products with antiflammatory action deriving from natural sources to improve environmental and economic sustainability. In this study, two different humic acids (HA) were isolated from from lignite (HA-LIG) and composted artichoke wastes (HA-CYN) and characterized by infrared spectrometry, NMR spectroscopy, thermochemolysis-GC/MS, and high-performance size-exclusion chromatography (HPSEC), while their antiflammatory activity was evaluated on HaCaT cells. Spectroscopic results showing the predominance of apolar aliphatic and aromatic components in HA-LIG, whereas HA-CYN revealed a presence of polysaccharides and polyphenolic lignin residues. The HA application on human keratinocyte pre-treated with Urban Dust revealed a general increase of viability suggesting a protective effect of humic matter due to the content of aromatic, phenolic and lignin components. Conversely, the gene expression of IL-6 and IL-1β cytokines indicated a significant decrease after application of HA-LIG, thus exhibiting a greater antiflammatory power than HA-CYN. The specific combination of HA protective hydrophobic components, viable conformational arrangements, and content of bioactive molecules, suggests an innovative applicability of humic matter in dermatology as skin protectors from environmental irritants and as antiflammatory agents.

Direct Construction of Catechol Lignin for Engineering Long-Acting Conductive, Adhesive, and UV-Blocking Hydrogel Bioelectronics.

Long-active conductivity, adhesiveness, and environmental stability are essential in the applications of hydrogel electronics. Integrating different functional materials into one system suffers from compatibility and cost problems. Inspired by the unique o-methoxyl structure in polyphenol lignin and its binding role in plants, catechol lignin (DAL) is constructed by one-step demethylation, which endows the lignin with a mussel-like bioadhesion, good reducibility, as well as a high ultraviolet absorption. The DAL is then applied to reduced graphene oxide, and the products-the oxidized DAL and the reduced graphene oxide mixture (DAL/rGO) is added into a sodium alginate/polyacrylamide (SA/PAM) double network hydrogel. Based on the Schiff base reaction between the quinone of the oxidized DAL and the amino of the skin, the DAL/rGO incorporated hydrogels could stably adhere to the skin, and sensitively respond to physiological signals. In addition, the DAL could provide the hydrogels with long-active sunscreen property when applied to real skin. These DAL based hydrogels have potential for on-skin sensing and outdoor sport equipment.

Evolution of a Biomass-Fermenting Bacterium To Resist Lignin Phenolics.

Increasing the resistance of plant-fermenting bacteria to lignocellulosic inhibitors is useful to understand microbial adaptation and to develop candidate strains for consolidated bioprocessing. Here, we study and improve inhibitor resistance in Clostridium phytofermentans (also called Lachnoclostridium phytofermentans), a model anaerobe that ferments lignocellulosic biomass. We survey the resistance of this bacterium to a panel of biomass inhibitors and then evolve strains that grow in increasing concentrations of the lignin phenolic, ferulic acid, by automated, long-term growth selection in an anaerobic GM3 automat. Ultimately, strains resist multiple inhibitors and grow robustly at the solubility limit of ferulate while retaining the ability to ferment cellulose. We analyze genome-wide transcription patterns during ferulate stress and genomic variants that arose along the ferulate growth selection, revealing how cells adapt to inhibitors through changes in gene dosage and regulation, membrane fatty acid structure, and the surface layer. Collectively, this study demonstrates an automated framework for in vivo directed evolution of anaerobes and gives insight into the genetic mechanisms by which bacteria survive exposure to chemical inhibitors.IMPORTANCE Fermentation of plant biomass is a key part of carbon cycling in diverse ecosystems. Further, industrial biomass fermentation may provide a renewable alternative to fossil fuels. Plants are primarily composed of lignocellulose, a matrix of polysaccharides and polyphenolic lignin. Thus, when microorganisms degrade lignocellulose to access sugars, they also release phenolic and acidic inhibitors. Here, we study how the plant-fermenting bacterium Clostridium phytofermentans resists plant inhibitors using the lignin phenolic, ferulic acid. We examine how the cell responds to abrupt ferulate stress by measuring changes in gene expression. We evolve increasingly resistant strains by automated, long-term cultivation at progressively higher ferulate concentrations and sequence their genomes to identify mutations associated with acquired ferulate resistance. Our study develops an inhibitor-resistant bacterium that ferments cellulose and provides insights into genomic evolution to resist chemical inhibitors.

Solution-State 2D NMR Spectroscopy of Plant Cell Walls Enabled by a Dimethylsulfoxide-d6/1-Ethyl-3-methylimidazolium Acetate Solvent

Lignocellulosic biomass is composed of the polysaccharides cellulose and hemicellulose and the polyphenol lignin. Many current methods for analyzing the structure of lignocelluloses involve a sequential extraction of the material and subsequent analysis of the resulting fractions, which is labor-intensive and time-consuming. The work presented here assesses the dissolution of whole lignocellulosic material, focusing on biomass derived from the perennial bioenergy grass Miscanthus. The solvent dimethylsulfoxide (DMSO)-d6 containing 1-ethyl-3-methylimidazolium acetate ([Emim]OAc) was able to dissolve lignocellulosic material completely and gave high-resolution 2D heteronuclear single quantum coherence (HSQC) NMR spectra of the entire array of wall polymers. Extrapolated time-zero HSQC was applied using DMSO-d6/[Emim]OAc-d14 and enabled quantitative analysis of structural traits of lignocellulose components.

Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels

Phenylpropanoid metabolism yields a mixture of monolignols that undergo chaotic, non-enzymatic reactions such as free radical polymerization and spontaneous self-assembly in order to form the polyphenolic lignin which is a barrier to cost-effective lignocellulosic biofuels. Post-synthesis lignin integration into the plant cell wall is unclear, including how the hydrophobic lignin incorporates into the wall in an initially hydrophilic milieu. Self-assembly, self-organization and aggregation give rise to a complex, 3D network of lignin that displays randomly branched topology and fractal properties. Attempts at isolating lignin, analogous to archaeology, are instantly destructive and non-representative of in planta. Lack of plant ligninases or enzymes that hydrolyze specific bonds in lignin-carbohydrate complexes (LCCs) also frustrate a better grasp of lignin. Supramolecular self-assembly, nano-mechanical properties of lignin-lignin, lignin-polysaccharide interactions and association-dissociation kinetics affect biomass deconstruction and thereby cost-effective biofuels production.

Comprehensive Compositional Analysis of Plant Cell Walls (Lignocellulosic biomass) Part I: Lignin

The need for renewable, carbon neutral, and sustainable raw materials for industry and society has become one of the most pressing issues for the 21st century. This has rekindled interest in the use of plant products as industrial raw materials for the production of liquid fuels for transportation1 and other products such as biocomposite materials7. Plant biomass remains one of the greatest untapped reserves on the planet4. It is mostly comprised of cell walls that are composed of energy rich polymers including cellulose, various hemicelluloses (matrix polysaccharides, and the polyphenol lignin6 and thus sometimes termed lignocellulosics. However, plant cell walls have evolved to be recalcitrant to degradation as walls provide tensile strength to cells and the entire plants, ward off pathogens, and allow water to be transported throughout the plant; in the case of trees up to more the 100 m above ground level. Due to the various functions of walls, there is an immense structural diversity within the walls of different plant species and cell types within a single plant4. Hence, depending of what crop species, crop variety, or plant tissue is used for a biorefinery, the processing steps for depolymerization by chemical/enzymatic processes and subsequent fermentation of the various sugars to liquid biofuels need to be adjusted and optimized. This fact underpins the need for a thorough characterization of plant biomass feedstocks. Here we describe a comprehensive analytical methodology that enables the determination of the composition of lignocellulosics and is amenable to a medium to high-throughput analysis. In this first part we focus on the analysis of the polyphenol lignin (Figure 1). The method starts of with preparing destarched cell wall material. The resulting lignocellulosics are then split up to determine its lignin content by acetylbromide solubilization3, and its lignin composition in terms of its syringyl, guaiacyl- and p-hydroxyphenyl units5. The protocol for analyzing the carbohydrates in lignocellulosic biomass including cellulose content and matrix polysaccharide composition is discussed in Part II2.

Comprehensive Compositional Analysis of Plant Cell Walls (Lignocellulosic biomass) Part I: Lignin

The need for renewable, carbon neutral, and sustainable raw materials for industry and society has become one of the most pressing issues for the 21st century. This has rekindled interest in the use of plant products as industrial raw materials for the production of liquid fuels for transportation1 and other products such as biocomposite materials7. Plant biomass remains one of the greatest untapped reserves on the planet4. It is mostly comprised of cell walls that are composed of energy rich polymers including cellulose, various hemicelluloses (matrix polysaccharides, and the polyphenol lignin6 and thus sometimes termed lignocellulosics. However, plant cell walls have evolved to be recalcitrant to degradation as walls provide tensile strength to cells and the entire plants, ward off pathogens, and allow water to be transported throughout the plant; in the case of trees up to more the 100 m above ground level. Due to the various functions of walls, there is an immense structural diversity within the walls of different plant species and cell types within a single plant4. Hence, depending of what crop species, crop variety, or plant tissue is used for a biorefinery, the processing steps for depolymerization by chemical/enzymatic processes and subsequent fermentation of the various sugars to liquid biofuels need to be adjusted and optimized. This fact underpins the need for a thorough characterization of plant biomass feedstocks. Here we describe a comprehensive analytical methodology that enables the determination of the composition of lignocellulosics and is amenable to a medium to high-throughput analysis. In this first part we focus on the analysis of the polyphenol lignin (Figure 1). The method starts of with preparing destarched cell wall material. The resulting lignocellulosics are then split up to determine its lignin content by acetylbromide solubilization3, and its lignin composition in terms of its syringyl, guaiacyl- and p-hydroxyphenyl units5. The protocol for analyzing the carbohydrates in lignocellulosic biomass including cellulose content and matrix polysaccharide composition is discussed in Part II2.

Bioconversion of Egyptian lignocelluloses by microbial treatment, using Streptomyces viridosporus added to highly reactive polymeric acidified lignin

AbstractStreptomyces viridosporus degraded lignin and lignocellulose, producing low molecular weight phenolic compounds for potential industrial use.The main portion of lignin in the residues was released into the growth medium as a water soluble modified polymer. The polymer, an acid precipitable polyphenolic lignin (APPL), was recovered from spent culture media by an acid precipitation, and was shown to be mostly free of non‐lignin components, as compared to native lignin. Elemental and functional group analysis showed that APPL contained a higher hydrogen and oxygen content, lower carbon and also lower methoxyl group and higher phenolic content, than native lignin. From IR spectra, an absorption peak at 1,720 cm−1 appeared in the infrared spectra of APPL. The ratio of the absorbance at 1,720 cm−1 to the absorbance at 1.630 cm−1 increased, due to higher levels of carbonyl and carboxyl groups.