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Activation of lignin by demethylation for improving the reactivity has attracted extensive attentions. However, it still faces many challenges, such as the unsatisfied increase of hydroxyl content and the undesired cracking of linear linkages. Here, the efficient demethylations for significantly increasing the hydroxyl content and protecting the structure of industrial lignin were explored using lewis acid as modification reagent. As BBr 3 was used, the phenolic hydroxyl content (Ar-OH) was increased by 80.65 %, but the lignin structure might be destroyed. About 75 % of the β-O-4 linkages could be fortunately retained by using AlCl 3 . This method could also be used for the demethylation of alkaline poplar lignin with up to 171.67 % increase of Ar-OH (from 1.80 to 4.89 mmol/g). After activation, the antioxidant properties were improved 4.64-fold and 2.58-fold for 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals, respectively. This work would provide a theory guidance for activation of lignin and facilitate its high-value application., Competing Interests: Declaration of competing interest The authors declare no known competing financial interests or personal relationships that would appear to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Development of lignin-derived carbon adsorbents with ultrahigh phosphate adsorption activity and rapid adsorption kinetics is of great importance, yet limited success has been achieved. Herein, we develop a CeO 2 functionalized N-doped lignin-derived biochar (Ce@NLC) via a cooperative modification strategy for effective and fast phosphate capture. The novel modification strategy not only contributes greatly to the loading of well-dispersed CeO 2 nanoparticles with a smaller size, but also significantly increases the relative concentration of Ce(III) species on Ce@NLC. Consequently, an enhanced capture capacity for phosphate (196.85 mg g -1 ) as well as extremely rapid adsorption kinetics were achieved in a wide operating pH range (2-10). Interestingly, Ce@NLC exhibited a strong phosphate adsorption activity at even low-concentration phosphorus-containing water. The removal efficiency and final P concentration reached 99.87% and 2.59 μg P L -1 within 1 min at the phosphate concentration of 2 mg P L -1 . Experiments and characterization indicated that Ce(III) species plays a predominant role for the phosphate capture, and ligand exchange, together with electrostatic attraction, are the main adsorption mechanism. This work develops not only an efficient carbon-based adsorbent for phosphate capture, but also promotes the high-value application of industrial lignin., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Due to over-consumption of fossil resources and environmental problems, lignocellulosic biomass as the most abundant and renewable materials is considered as the best candidate to produce biomaterials, biochemicals, and bioenergy, which is of strategic significance and meets the theme of Green Chemistry. Highly efficient and green fractionation of lignocellulose components significantly boosts the high-value utilization of lignocellulose and the biorefinery development. However, heterogeneity of lignocellulosic structure severely limited the lignocellulose fractionation. This paper offers the summary and perspective of the extensive investigation that aims to give insight into the lignocellulose prior-fractionation. Based on the role and structure of lignocellulose component in the plant cell wall, lignocellulose prior-fractionation can be divided into cellulose-first strategy, hemicelluloses-first strategy, and lignin-first strategy, which realizes the selective dissociation and transformation of a component in lignocellulose. Ultimately, the challenges and opportunities of lignocellulose prior-fractionation are proposed on account of the existing problems in the biorefining valorization., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

To achieve a rapid and facile quantitative evaluation of Sudan I illegally added in ketchup, fluorescent carbon quantum dots with excellent stability in acidic environments are required as the actual pH value of ketchup is close to 4.0. In this paper, we developed a green approach to prepare sulfur-doped carbon quantum dots (SCQDs) via hydrothermal treatment of lignin, isolated from pre-hydrolysis liquor, in sulfuric acid solution. The resultant SCQDs from lignin possessed sulfur-containing groups, which exhibited excellent fluorescence with a quantum yield up to 13.5% and good stability in acidic environments with a wide pH range of 0-5.0. Therefore, the SCQDs were successfully employed as a sensor to detect Sudan I in acidic solutions with excellent selectivity and sensitivity. The linear range for Sudan I was 0-40 μM, while the limit of detection was 0.12 μM. In addition, the fluorescent indicator paper functionalized with SCQDs also showed outstanding selectivity to Sudan I. The proposed SCQD sensing system not only displayed application potential for quantitative evaluation of Sudan I dye in practical samples, but also provided a way to convert lignin-based waste into highly valued nanoscale materials.

Lignin is a renewable source of aromatics, and the conversion of lignin to chemicals, fuels and materials is very attractive. Herein, a novel lignin-based cation exchange resin (LBR) was easily synthesized through an economical one-pot method. Results demonstrated that the sulfonic acid groups were successfully introduced into the skeleton of the resins, and the S contents and swelling capacity of the prepared LBRs gradually increased with the increment of the sulfonation reagents dosage. A maximum ion-exchange capacity of 2.26 mmol/g was achieved for the LBR obtained at 120 °C for 4 h with a molar ratio of phenol to formaldehyde (P:F) of 1:5 (SSPL-0.50), which was comparable to the commercial phenol type cation exchange resin. Furthermore, the SSPL-0.50 exhibited a high adsorption capacity (167.2 mg/g) for Pb (II) removal. The LBR can be considered as a promising substitute for the petroleum-based ion exchange resin in the purification of wastewater., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The pertinent issue of resources shortage arising from global climate change in the recent years has accentuated the importance of materials that are environmentally friendly. Despite the merits of current material like cellulose as the most abundant natural polysaccharide on earth, the incorporation of lignocellulosic biomass has the potential to value-add the recent development of cellulose-derivatives in drug delivery systems. Lignocellulosic biomass, with a hierarchical structure is comprised of cellulose, hemicellulose and lignin. As an excellent substrate that is renewable, biodegradable, biocompatible and chemically accessible for modified materials, lignocellulosic biomass sets forth a myriad of applications. To date, materials derived from lignocellulosic biomass have been extensively explored for new technological development and applications, such as biomedical, green electronics and energy products. In this review, chemical constituents of lignocellulosic biomass are first discussed before we critically examine the potential alternatives in the field of biomedical application. In addition, the pretreatment methods for extracting cellulose, hemicellulose and lignin from lignocellulosic biomass as well as their biological applications including drug delivery, biosensor, tissue engineering etc. are reviewed. It is anticipated there will be an increasing interest and research findings in cellulose, hemicellulose and lignin from natural resources, which help provide important directions for the development in biomedical applications., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

A sensitive and reversible sensing platform based on fluorescent carbon dots (CDs) allowing capture and detection of metal ions is of significance for developing diagnostic probes and in-situ environmental-monitoring. Here, a simple and effective method for converting biomass lignin into fluorescent CDs is developed. The obtained CDs, with stable fluorescence and excellent water solubility, are fabricated as unique model biosensors to access the metal-induced quenching mechanism. It is demonstrated that selective fluorescence quenching behaviors of lignin CDs are firstly found related to the valence-state of metal ions. Moreover, a reversible control of CDs fluorescence is realized by introducing reducing agents. This novel biosensor and the approach to quenching mechanism may evoke new insight in designing ions-sensor and monitoring biologic redox signal.

An integrated pretreatment process based on hydrothermal pretreatment (HTP) followed by alkaline pretreatment has been applied to treat Eucalyptus. The chemical composition and structure changes of lignin during the pretreatment were comprehensively characterized. The surface morphology of the cell walls and lignin distribution of the pretreated Eucalyptus were detected by scanning electron and confocal Raman microscopies. It was found that the chemical bonds between lignin and hemicelluloses were cleaved during the pretreatment. The results also indicated that the contents of β-O-4', β-β', and β-5' linkages were decreased with the increase of hydrothermal pretreatment temperature and the cleavage of β-O-4' linkages in lignin was accompanied with repolymerization reactions. 31 P NMR analysis showed that the content of aliphatic OH was reduced as the temperature increased and the total phenolic OH was elevated and then declined with the increase of temperature. Raman spectra analysis revealed that the dissolution rate of lignin in the secondary wall regions was faster than that in cell corner middle lamella regions during the pretreatment. These results will enhance the understanding of the cell wall deconstruction during the pretreatment and the mechanism of the integrated pretreatment process acting on Eucalyptus.

Lignin structural studies play an essential role both in understanding the development of plant cell walls and for valorizing lignocellulosics as renewable biomaterials. Dimeric products released by selectively cleaving β-aryl ether linkages between lignin units reflect the distribution of recalcitrant lignin units, but have been neither absolutely defined nor quantitatively determined. Here, 12 guaiacyl-type thioacidolysis dimers were identified and quantified using newly synthesized standards. One product previously attributed to deriving from β-1-coupled units was established as resulting from β-5 units, correcting an analytical quandary. Another longstanding dilemma, that no β-β dimers were recognized in thioacidolysis products from gymnosperms, was resolved with the discovery of two such authenticated compounds. Individual GC response factors for each standard compound allowed rigorous quantification of dimeric products released from softwood lignins, affording insight into the various interunit-linkage distributions in lignins and thereby guiding the valorization of lignocellulosics., (© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

A water-soluble, ratiometric fluorescent pH probe, L-SRhB, was synthesized via grafting spirolactam Rhodamine B (SRhB) to lignosulfonate (LS). As the ring-opening product of L-SRhB, FL-SRhB was also prepared. The pH-response experiment indicated that L-SRhB showed a rapid response to pH changes from 4.60 to 6.20 with a pK a of 5.35, which indicated that L-SRhB has the potential for pH detection of acidic organelle. In addition, the two probes were internalized successfully by living cells through the endocytosis pathway and could distinguish normal cells from cancer cells by different cell staining rates. In addition, L-SRhB showed obvious cytotoxicity to cancer cells, whereas it was nontoxic to normal cells in the same condition. L-SRhB might have potential in cancer therapy. L-SRhB might be a promising ratiometric fluorescent pH sensor and bioimaging dye for the recognition of cancer cells. The results also provided a new perspective to the high-value utilization of lignin.

Due to the enormous abundance of lignin and its unique aromatic nature, lignin has great potential for the production of industrially useful fuels, chemicals, and materials. However, the rigid and compact structure of the plant cell walls significantly blocks the separation of lignin. In this study, wheat straw was hydrothermally pretreated at different temperatures (120-200 °C) followed by post-treatment with 70% ethanol containing 1% NaOH to improve the isolation of lignin. Results demonstrated that the content of associated carbohydrates of the lignin fractions was gradually reduced with the increment of the hydrothermal severity. The structure of the lignins changed regularly with the increase of the pretreatment temperature from 120 to 200 °C. In particular, the contents of β-O-4', β-β', β-5' linkages and aliphatic OH in the lignins showed a tendency of decrease, while the content of phenolic OH and thermal stability of the lignin fractions increased steadily as the increment of the pretreatment temperature.

Lignocellulosic materials are among the most promising alternative energy resources that can be utilized to produce cellulosic ethanol. However, the physical and chemical structure of lignocellulosic materials forms strong native recalcitrance and results in relatively low yield of ethanol from raw lignocellulosic materials. An appropriate pretreatment method is required to overcome this recalcitrance. For decades various pretreatment processes have been developed to improve the digestibility of lignocellulosic biomass. Each pretreatment process has a different specificity on altering the physical and chemical structure of lignocellulosic materials. In this paper, the chemical structure of lignocellulosic biomass and factors likely affect the digestibility of lignocellulosic materials are discussed, and then an overview about the most important pretreatment processes available are provided. In particular, the combined pretreatment strategies are reviewed for improving the enzymatic hydrolysis of lignocellulose and realizing the comprehensive utilization of lignocellulosic materials., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study reports the rapid preparation of silver nanoparticles (AgNPs) from Tollens' reagent under microwave irradiation. In the synthesis, lignin with reducing groups and spatial three-dimensional structure was used as reducing and stabilizing agents without other chemical reagents, and the effects of the ratio of lignin to Ag(+), reaction temperature, and heating time on the synthesis of AgNPs were investigated. The obtained AgNPs were further characterized by UV-vis, Malvern particle size, TEM, XRD, and XPS analyses. The structural changes of lignin before and after reaction were also studied by FT-IR, (1)H NMR, (13)C NMR, and GC-MS. The results revealed that the obtained AgNPs were mostly spherical with diameters of around 24 nm. The optimum reaction conditions were a ratio 50 mg of lignin to 0.3 mM of Ag(+), a microwave irradiation temperature of 60 °C, and a heating time of 10 min. Moreover, AgNPs redispersed well in water and ethanol after centrifugation for the removal of lignin. During the formation of AgNPs, lignin was oxidized, and the side chains of lignin were partly disrupted into small molecules, such as hydrocarbon and alcohol. The resultant lignin-AgNPs showed highly selective sensing detection for Hg(2+), and the color of the lignin-AgNP solution containing Hg(2+) decreased gradually with increasing amounts of Hg(2+) within seconds, but the other 19 metal ions had little effect on the color and surface plasmon absorption band of the lignin-AgNPs. Also, there was a linear relationship between the absorbance and Hg(2+) concentration, with a limit of detection concentration of 23 nM. This study provides not only a new way to take advantage of agricultural and forestry residues, but also a green and rapid method for the synthesis of AgNPs to detect the toxic ion Hg(2+) selectively and sensitively.

Preparation of biopolymer-based catalysts for the conversion of carbohydrate polymers to new energies and chemicals is a hot topic nowadays. With the aim to develop an ecological method to convert xylose into furfural without the use of inorganic acids, a biopolymer-derived catalyst (lignosulfonic acid) was successfully used to catalyze xylose into furfural in ionic acid ([BMIM]Cl). The characteristics of lignosulfonic acid (LS) and effects of solvents, temperature, reaction time, and catalyst loading on the conversion of xylose were investigated in detail, and the reusability of the catalytic system was also studied. Results showed that 21.0% conversion could be achieved at 100 °C for 1.5 h. The method not only avoids pollution from conventional mineral acid catalysts and organic liquids but also maked full use of a byproduct (lignin) from the pulp and paper industry, thus demonstrating an environmentally benign process for the conversion of carbohydrates into furfural.

In order to investigate the pyrolysis differences among lignocellulose and its major components, the biochars and volatiles of lignocellulose (bamboo), lignin, hemicellulose and holocellulose (from bamboo), and cellulose (from cotton linter) were studied using elemental analysis, FTIR, XRD, SEM, Py-GC/MS and TGA-FTIR. Result showed that the biochar yield of lignin (48.8%) was much higher than those of hemicellulose (21.1%), cellulose (8.3%), holocellulose (20.4%) and bamboo (15.1%), while no obvious elemental difference among these biochars was found. Results from Py-GC/MS indicated that carbonyl compounds, ethers and alcohols were the major volatiles of polysaccharide component pyrolysis, while aromatic compounds were the major volatiles of lignin pyrolysis. The pyrolysis of polysaccharide component mainly occurred at 200-400°C, while the pyrolysis of lignin happened at 300-700°C., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Pinoresinol structures, featuring a β-β'-linkage between lignin monomer units, are important in softwood lignins and in dicots and monocots, particularly those that are downregulated in syringyl-specific genes. Although readily detected by NMR spectroscopy, pinoresinol structures largely escaped detection by β-ether-cleaving degradation analyses presumably due to the presence of the linkages at the 5 positions, in 5-5'- or 5-O-4'-structures. In this study, which is aimed at helping better understand 5-linked pinoresinol structures by providing the required data for NMR characterization, new lignin model compounds were synthesized through biomimetic peroxidase-mediated oxidative coupling reactions between pre-formed (free-phenolic) coniferyl alcohol 5-5'- or 5-O-4'-linked dimers and a coniferyl alcohol monomer. It was found that such dimers containing free-phenolic coniferyl alcohol moieties can cross-couple with the coniferyl alcohol producing pinoresinol-containing trimers (and higher oligomers) in addition to other homo- and cross-coupled products. Eight new lignin model compounds were obtained and characterized by NMR spectroscopy, and one tentatively identified cross-coupled β-O-4'-product was formed from a coniferyl alcohol 5-O-4'-linked dimer. It was demonstrated that the 5-5'- and 5-O-4'-linked pinoresinol structures could be readily differentiated by using heteronuclear multiple-bond correlation (HMBC) NMR spectroscopy. With appropriate modification (etherification or acetylation) to the newly obtained model compounds, it would be possible to identify the 5-5'- or 5-O-4'-linked pinoresinol structures in softwood lignins by 2D HMBC NMR spectroscopic methods. Identification of the cross-coupled dibenzodioxocin from a coniferyl alcohol 5-5'-linked moiety suggested that thioacidolysis or derivatization followed by reductive cleavage (DFRC) could be used to detect and identify whether the coniferyl alcohol itself undergoes 5-5'-cross-linking during lignification., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

To investigate the potential for the utilization of cotton stalk, ammonia hydrothermal treatment was applied to fractionate the samples into aqueous ammonia-soluble and ammonia-insoluble portions. The ammonia-soluble portion was purified to yield lignin fractions. The lignin fractions obtained were characterized by wet chemistry (carbohydrate analysis) and spectroscopy methods (FT-IR, 13C and 1H-13C HSQC NMR spectroscopy) as well as gel permeation chromatography (GPC). The results showed that the cotton stalk lignin fractions were almost absent of neutral sugars (0.43%-1.29%) and had relatively low average molecular weights (1255-1746 g/mol). The lignin fractions belonged to typical G-S lignin, which was composed predominately of G-type units (59%) and noticeable amounts of S-type units (40%) together with a small amount of H-type units (~1%). Furthermore, the ammonia-extractable lignin fractions were mainly composed of β-0-4' inter-unit linkages (75.6%), and small quantities of β-β' (12.2%), together with lower amounts of β-5' carbon-carbon linkages (7.4%) and p-hydroxycinnamyl alcohol end groups.

Kraft-AQ pulping lignin was sequentially fractionated by organic solvent extractions and the molecular properties of each fraction were characterized by chemical degradation, GPC, UV, FT-IR, (13)C-NMR and thermal analysis. The average molecular weight and polydispersity of each lignin fraction increased with its hydrogen-bonding capacity (Hildebrand solubility parameter). In addition, the ratio of the non-condensed guaiacyl/syringyl units and the content of β-O-4 linkages increased with the increment of the lignin fractions extracted successively with hexane, diethylether, methylene chloride, methanol, and dioxane. Furthermore, the presence of the condensation reaction products was contributed to the higher thermal stability of the larger molecules.

Original lignin and hemicelluloses were sequentially extracted with high yield/purity, using acidic dioxane/water solution and dimethyl sulfoxide, from ball-milled wheat straw. The acidic dioxane lignin fraction is distinguished by high beta-O-4' structures and by low amounts of condensed units (beta-5', 5-5', and beta-1'). Hemicelluloses contain arabinoxylans as the major polysaccharides, which are substituted by alpha-l-arabinofuranose, 4-O-methylglucuronic acid, acetyl group (DS = 0.1), and xylose at O-3 and/or O-2 of xylans. It was found that arabinoxylans form cross-links with lignins through ferulates via ether bonds, glucuronic acid via ester bonds, and arbinose/xylose via both ether and glycosidic bonds, respectively, in the cell walls of wheat straw. Diferulates are also incorporated into cross-links between lignin and hemicelluloses as well as lignification of wheat straw cell walls. The guaiacyl unit is considered to be a significant condensed structural constructor in extracted lignin and a connector between lignin and carbohydrates.

An investigation of the acetylation of rice straw with acetic anhydride at 100 and 120 degrees C for 1-4 h with four tertiary amine catalysts (pyridine, 4-dimethylaminopyridine, N-methylpyrrolidine, and N-methylpyrrolidinone) or without catalyst in a solvent-free system was undertaken, and the extent of acetylation was measured by weight percent gain, which increased with the extent of reaction time and temperature and the amounts of catalyst used. 4-Dimethylaminopyridine was found to be the most effective catalyst of those studied. At a concentration of 7% of the catalyst in acetic anhydride, a weight percent gain of 15.4% was realized, compared with 11.2% for the noncatalyst reaction, after 0.5 h of exposure to the system at 120 degrees C. Characterization of acetylated straw was performed by FT-IR, CP MAS (13)C NMR, and thermal studies. Interestingly, the acetylated straw is significantly hydrophobic and does not get wet with water, thereby offering potential for the better utilization of cheap waste materials as natural sorbents in oil cleanup.

Treatment of the dewaxed wheat straw with 0.5 M KOH at 35 degrees C for 2.5 h without ultrasonic irradiation and with ultrasound assistance for 5, 10, 15, 20, 25, 30, and 35 min resulted in a dissolution of 43.9%, 43.9%, 43.9%, 44.4%, 44.4%, 45.6%, 46.8%, and 49.1% of the original lignin, respectively. Much better results were achieved under the ultrasonic irradiation time for 35 min where nearly 50% of the original lignin was solubilized at 35 degrees C for 2.5 h. The purity of the lignin preparations isolated by alkali with ultrasound assistance was higher than that of the lignin fraction obtained by alkali without ultrasonic irradiation, and their purity increased with an increment of irradiation time between 5 and 35 min, in which the content of associated polysaccharides in the former lignin preparations (0.87-1.06%) was lower than that of the latter lignin fraction (1.16%). In addition, the lignins isolated by alkali with ultrasonic irradiation time between 5 and 30 min showed a slightly higher molecular weight and thermal stability than the lignin obtained by alkali without ultrasound assistance. No substantial differences in the main structure features between the lignin preparations isolated by alkali and ultrasound-assisted alkali extractions were found.

In this series of articles, the board members of ChemSusChem discuss recent research articles that they consider of exceptional quality and importance for sustainability. This entry features Prof. R. C. Sun, who highlights the fabrication of lignin nanoparticles and their application in composites, suggesting that further studies and discoveries of the structures and inherent properties of lignin will contribute to extensive and standardized applications of this new green nanomaterial. [ABSTRACT FROM AUTHOR]

DewaxedCalamagrostis angustifoliaKom was pretreated with hot water at 60 and 90°C for 3 h, and then the residue obtained was successively treated with 70% ethanol, and 70% ethanol containing 0.2%, 1.0%, 2.0%, 4.0%, and 8.0% NaOH at 80°C for 3 h. The dissolved components were subjected to further separation to get eight lignin fractions, which were characterized by gel permeation chromatography, Fourier transform infrared, and sugar analysis. All the lignin fractions had small weight-average molecular weights between 810 and 2580 g/mol. Two typical lignins, L3(prepared with 70% ethanol) and L5(prepared with 70% ethanol containing 1.0% NaOH), were further analyzed using1H,13C NMR and HSQC spectroscopy. Signals from guaiacyl (G), syringyl (S), andp-hydroxyphenyl (H) units observed in aromatic/olefinic region of HSQC spectra indicated that the lignin fromCalamagrostis angustifoliaKom could be classified as “GSH” lignin. In aliphatic-oxygenated region, β-O-4′ together with small amounts of β-5′, β-β′, andp-hydroxycinnamyl alcohol end group were the main interunit linkages observed. Aqueous ethanol, which could avoid the cleavage of ether bonds in lignin at neutral condition, was more effective than water on lignin extraction. [ABSTRACT FROM AUTHOR]

Post-treatment of ultrasonic irradiated and alkali pre-treated wheat straw with TAED activated peroxide at pH 11.8 for 12 h at 48 °C resulted in a dissolution of 43.3–46.2% of the original lignin and 27.1–28.1% of the original hemicelluloses, respectively. The isolated acid-insoluble lignin preparations were analysed by both destructive methods such as alkaline nitrobenzene oxidation and non-destructive techniques such as UV, FT-IR, and 13C NMR spectroscopy as well as GPC. Total polysaccharide content of isolated lignin preparations ranged from 0.79 to 1.01%. Nitrobenzene oxidation analysis showed that the molar ratio of V:S:H in the eight lignin preparations was 6:5:1. In addition, the residual lignins isolated by TAED activated peroxide showed a higher molecular weight and thermal stability than the lignins released during the pre-treatment with alkali combining with or without ultrasonic assistance. Furthermore, it was found that more hydroxyl, aldehyde and ketone groups and aryl ethers in the lignin side chains were attacked with the use of TAED. [Copyright &y& Elsevier]

Photothermal elastomers are recognized as smart flexible materials that can rapidly and effectively convert light energy into heat energy. However, there has been a lack of adequate focus on tackling the sustainability challenges of photothermal elastomers, particularly in terms of material selection, the integration of complex functionalities, and final disposal. A fully bio‐derived photothermal elastomer (BPTE) produced through a simple and chemical‐free approach is introduced, utilizing alkali lignin, lipoic acid, and phytic acid as bio‐derived feedstocks. The BPTE exhibits an adaptive polymeric network crosslinked by dynamic covalent disulfide bonds and multiple hydrogen bonds, endowing it with dual‐mode photothermal conversion capability, robustness, stretchability, rapidly self‐healing property, hydrophobicity, swelling resistance, self‐adhesion, full recyclability, and degradability. The BPTE is further demonstrated as a next‐generation solution for photothermal generators, light‐driven actuators, photothermal antibacterial dressings, and photothermal fibers. The versatility of BPTE opens avenues for innovative smart devices and systems with significant potential in energy conversion, soft robotics, medical treatment, and smart clothing. With outstanding photothermal performances, full recyclability, and biodegradability, these fully bio‐based elastomers present an attractive prospect for the development of the advanced smart photothermal products. [ABSTRACT FROM AUTHOR]

In this work, low-cost lignin nanospheres were fabricated and further applied as an efficient and sustainable support for preparing cuprous oxide (Cu2O) “green” catalyst by using electrospraying technology. The unalloyed lignin, a special three-dimensional molecular structure, was successfully processed into uniform nanospheres under an electrospraying condition. The synthesized lignin-supported Cu2O catalyst had a well-defined nanosphere structure, and Cu2O nanoparticles with sizes less than 30 nm were supported by exposed layers of lignin nanospheres. There were C–O–Cu bonds formed between the lignin nanospheres and the metallic nanoparticles. The lignin nanospheres and the lignin nanosphere-supported catalyst werfe characterized by utilizing XRD, SEM, TEM, XPS, EDS, and TGA. The immobilization of Cu2O nanoparticles on the lignin nanospheres was beneficial for dispersion of the Cu2O nanoparticles and preventing their aggregation, which could cause catalyst deactivation, which favored the Huisgen [3+2] cycloaddition reaction. The triazole synthesis results indicated that the lignin nanosphere-supported Cu2O catalyst had a high catalytic performance with 99% yield under solvent-free conditions. Furthermore, the as-synthesized catalyst could be recycled for four times without significantly losing its catalytic activity. [ABSTRACT FROM AUTHOR]

• One-pot molten method for preparing lignin-based photothermal elastomer. • Lignin significantly enhances mechanical performance of elastomer. • Elastomer can be completely recovered and reused by simple thermal remodeling. • Dynamic networks impart elastomer with self-healing and self-adhesion properties. • Elastomers exhibit photothermal conversion and photo-driven shape memory. Utilizing renewable biomass as an alternative to petroleum-based products for the development of smart materials emerges as a pivotal strategy for sustainable development. However, the straightforward, rapid, and cost-effective deployment of biomass for novel smart material synthesis remains a formidable challenge. Herein, we employ a facile solvent-free one-pot strategy to develop a multifunctional smart biomass photothermal elastomer, which synthesized from the natural small molecule of α-lipoic acid (LA) and renewable lignin biopolymer without any chemical modification. The incorporation of lignin confers to the obtained elastomers superior mechanical strength, photothermal responsiveness, photothermal self-healing, and adhesive capabilities. Notably, the photothermal elastomers can be fully recycled and reused by simple thermal remodeling. As a proof of concept, the temperature difference generator can be driven to generate electricity utilizing the excellent photothermal effect of elastomers, highlighting its excellent light-heat-electricity conversion capability. Intriguingly, the photothermal elastomers exhibit light-driven shape memory effect, enabling to grasp objects by shape-programmed four-arm soft gripper under selective irradiation. This pioneering work not only demonstrates significant progress in high-value utilization of bio-derived lignin, but also opens up a new avenue for sustainable and innovative applications in advanced energy management devices and soft actuators. [ABSTRACT FROM AUTHOR]

Abstract: Dewaxed wheat straw was treated with acetic acid–H2O (65/35, v/v), acetic acid–H2O (80/20, v/v), acetic acid–H2O (90/10, v/v), formic acid–acetic acid–H2O (20/60/20, v/v/v), formic acid–acetic acid–H2O (30/60/10, v/v/v), methanol–H2O (60/40, v/v) and ethanol–H2O (60/40, v/v) using 0.1% HCl as a catalyst at 85°C for 4h, in which 78.2, 80.0, 88.2, 89.4, 94.1, 23.5 and 37.4% of the original lignin, and 42.4, 58.7, 70.0, 65.1, 76.5, 14.2 and 22.2% of the original hemicelluloses was released, respectively. Lignins obtained were characterized by their content of hemicelluloses, composition of phenolic acids and aldehydes, molecular weight, thermal stability and by UV, Fourier transform infrared (FT-IR), 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. The results showed that aqueous organic acid was more effective than aqueous organic alcohol for extensive delignification and selective fractionation of cellulose, lignin and hemicelluloses from the straw. In particular, the addition of formic acid gave a significant effect on the dissolution of lignin. All the acid-insoluble lignin fractions contained small amounts of contaminated hemicelluloses as shown by their content of neutral sugars, 0.9–4.3%, and had weight-average molecular weight between 3960 and 4340gmol−1. An increase in concentration of acetic acid or formic acid in organosolv resulted in an increment in release of guaiacyl units and in lignin condensation. However, the lignin preparations released during the treatment with aqueous organic alcohol without organic acid contained almost equal amounts of non-condensed guaiacyl and syringyl units with fewer p-hydroxyphenyl units. The β-O-4 ether bonds together with β-β, β-5 and 5-5′ carbon–carbon linkages were identified to be present in lignin substructures. [Copyright &y& Elsevier]

Graphical abstract Highlights • Hydrothermal acid hydrolysis was applied to treat the pre-hydrolysis liquor. • A maximum lignin removal rate of 57.1% was achieved by hydrothermal acid hydrolysis. • Most hemicelluloses were converted into xylose after hydrothermal acid hydrolysis. • The obtained lignin showed high surface hydrophilicity and thermal stability. Abstract In this study, the effect of traditional acidification and hydrothermal acid hydrolysis on the separation of lignin and xylose from the pre-hydrolysis liquor (PHL) of kraft pulping process was comparatively evaluated. The PHL was acidified at room temperature or hydrothermally treated under acidic conditions to isolate lignin and xylose. As compared with the lignin removal rate of 26.8–32.7% by traditional acidification method, a much higher lignin removal rate of 57.1% was achieved by hydrothermal acid hydrolysis. Meanwhile, the content of xylose in the PHL increased dramatically from 7.91 to 13.91–34.82 g/L after the hydrothermal acid hydrolysis. The hydrophilicity of the obtained lignin gradually increased as evidenced by the decrease of the corresponding water contact angel. Additionally, the thermal stability of the lignin sample increased steadily with the increment of acid dosage. The hydrothermal acid hydrolysis provides an effective approach to fractionate lignin and xylose from PHL. [ABSTRACT FROM AUTHOR]

Compressive, ultralight and fire-resistant graphene aerogel is facilely modified by renewable lignin biomass with hydrophobic and porous skeletons. The lignin-modified graphene aerogel (LGA) show highly efficient absorption of not only petroleum oils, but also toxic solvents such as toluene, chloroform and carbon tetrachloride (up to 350 times of its own weight), which is superior to that of graphene aerogel (GA) and among the highest in previous reported absorbents. Even after several compressive and release cycles, their absorption capacity are also maintained at 96%. Moreover, the absorption capacity can be further improved by carbonation treatment maximum up to 522 times of its own weight. Importantly, the LGA can be regenerated by repeated heat treatment and squeezing method, yielding almost full release of adsorbates. Such a high efficient, recyclable and renewable LGA exhibits it a potential candidate for applications in oil-water separation and also paves way to high-valued utilization of biomass waste. [ABSTRACT FROM AUTHOR]

Lignin is the renewable source of aromatics in nature, and the conversion of lignin into vanillin is very attractive. However, the vanillin yield is closely related to the resource of lignin and its isolation process, and relatively low yield of vanillin is always obtained from lignin. In order to improve the vanillin yield from lignin, in this work, the relationship between lignin linkages and vanillin yield was explored. Five lignins (kraft lignin, alkali lignin, lignosulfonate, and two enzymatic lignins) and various lignin model compounds (monomers, dimers, and polymers) were characterized by NMR spectroscopy and oxidized to prepare vanillin. Results indicated that the interunit linkages of the lignin had a significant influence on the vanillin yield. The more β- O -4 linkages in lignin, the higher yield of corresponding aldehydes was obtained. It is believed that the vanillin yield can be significantly improved by using lignins with high content of β- O -4 linkages. [ABSTRACT FROM AUTHOR]

Reduced graphene oxide (RGO)-based materials have shown excellent performance as electrodes, but the green reduction and stabilization for RGO remains a great challenge. Here, lignin, the by-product of paper industry, was used as a green reductant for the synthesis of RGO and then acted as the morphology directing agent for the fabrication of 3D RGO-based composite. The effect of lignin on the reduction of GO was firstly illustrated. In comparison with those RGO solutions obtained by traditional reductants (ascorbic acid, sodium borohydride and hydrazine), the RGO solution obtained by lignin was the most stable, because lignin can prevent the aggregation of RGO sheets by π–π interaction. Moreover, lignin can modify the pore structure and give the 3D RGO-based composite with high specific surface area via hydrothermal carbonization. At last, the 3D lignin-RGO composite was employed as electrode and exhibited a good rate capability with high capacitance of 190 F g − 1 at 0.5 A g − 1 and 133.9 F g − 1 at 10 A g − 1 , which is higher than those of biomass-based graphene materials and comparable to those of lignin-based carbon materials. Noteworthily, due to spatial structure modified by lignin, after 10,000 continuous cycles of galvanostatic charge/discharge, the 3D lignin-RGO electrode retained 86.5% of its specific capacitance. [ABSTRACT FROM AUTHOR]

A catalytic method for the isolation of lignin in high purity from cotton stalk was presented in this study. Lignin fractions were obtained by the extraction of cotton stalk under catalytic hydrothermal conditions in the presence of metal chlorides including AlCl 3 , CrCl 3 , FeCl 3 and ZnCl 2 as catalysts. Structural elucidation of these lignin samples was investigated by high-performance anion-exchange chromatography (HPAEC), gel permeation chromatography (GPC), and 2D HSQC NMR spectroscopy. The results showed that the separated lignin fractions possessed higher purities than milled wood lignin (MWL). 2D NMR spectra demonstrated that guaiacyl ( G ) and syringyl ( S ) units were predominant in these lignin fractions, similar to the typical lignin types of hardwood. Moreover, the obtained lignin fractions consisted mainly of β- O -4′ aryl ether linkages, followed by resinol and phenylcoumaran structures. It was also found that the cleavages of β- O -4′ linkages occurred remarkably due to the presence of catalysts, and their decreasing severities were consistent with the acidity of the metal chlorides. In addition, the degradation was accompanied by a mild repolymerization during the catalytic hydrothermal pretreatment. In consideration of the relatively high yield and purity, isolation of lignin from raw materials by using catalytic hydrothermal pretreatment catalyzed by AlCl 3 provided us a more effective approach for biomass pretreatment. [ABSTRACT FROM AUTHOR]

Highlights: [•] Expanded treatment made contribution on lignin separation from agricultural waste. [•] Mild condensation took place between lignin units during the expansion processing. [•] The tricin structure was detected in lignin from rice straw but not in rice husk. [Copyright &y& Elsevier]

The novel sulfomethylated lignin-grafted-polyacrylic acid (SL-g-PAA) hydrogel was fabricated in this work via a facile and green synthetic strategy for the efficient removal of heavy metal ions from wastewater, and then successively reused for chemiluminescence (CL). The sulfomethylation of lignin was first performed to improve its water solubility and introduce numerous active sites for adsorption of heavy metal ions. The as-synthesized SL-g-PAA hydrogel with high content of lignin exhibited the highly efficient and rapid removal of various metal ions from simulated wastewater. More importantly, the spent hydrogel (M2+@SL-g-PAA) after adsorption was reused for the first time to develop a new CL system by an ingenious strategy, in which these metal ions adsorbed on M2+@SL-g-PAA act as heterogeneous catalytic sites to catalyze the CL reaction between N-(4-aminobutyl)-N-ethylisoluminol (ABEI) and H 2 O 2. The resultant CL system displayed high CL intensity and long duration time, which could be observed by naked eye in the dark and lasted for > 24 h. The combination of facile fabrication process, renewable raw materials, and ingenious strategy for successive application in adsorption and CL endows this lignin-based composite hydrogel with a great potential for application in wastewater treatment, biological imaging and cold light sources. [Display omitted] • A lignin-based hydrogel was fabricated by a facile and green synthetic strategy. • SL-g-PAA exhibited efficient and rapid removal of heavy metal ions from wastewater. • Spent hydrogel after adsorption was reused for the first time to develop CL system. • A highly intensive and long-lasting CL system was obtained by an ingenious design. • A new strategy for successive application of lignin-based hydrogels was presented. [ABSTRACT FROM AUTHOR]

Abstract: The steam pre-treatment with low severity preserves valuable biomass components, and further delignification with alkaline peroxide could improve hydrolysis. A combination of low severity steam pretreatment and alkaline peroxide post-treatment of Lespedeza stalks was investigated. The post-treatment of steam-pretreated Lespedeza stalks with alkaline peroxide significantly increased the cellulose content and changed the structure of the cellulose-rich fractions. A glucose yield of 503.5mgg−1 raw material from enzyme hydrolysis was obtained when the steam-pretreated material (184°C for 4min) was post-treated with 2% hydrogen peroxide at 60°C for 24h with a substrate concentration of 3.3%. Its hydrolysis yield is 88.8%, which is higher than that of samples processed by steam pretreatment alone (63.7%). The samples obtained by post-treatment with alkaline peroxide were found to have a smoother surface and looser structure in scanning electron microscopy images. The isolated lignin preparations had a yield range from 10.9 to 14.7 (% dry matter). The lignin was characterized by thermogravimetric analysis/differential thermal analysis, Fourier transform infrared spectroscopy, and gel permeation chromatography. Alkaline peroxide treatment increased the thermal stability of lignin, and decreased the amounts of all functional groups. Depolymerization and repolymerization occurred during the alkaline peroxide treatment. [Copyright &y& Elsevier]

Abstract: Seven lignin fractions were isolated from dewaxed sweet sorghum stem and their physicochemical features were investigated. The dewaxed sweet sorghum stem was extracted sequentially with hot water, 50% dioxane and dimethyl sulfoxide (DMSO), and various concentrations of NaOH. The treatments resulted in dissolution of 0.5, 0.7, 0.2, 1.3, 1.6, 0.8, and 0.5% lignin, corresponding to release of 8.9, 12.5, 3.6, 23.2, 28.6, 14.3, and 8.9% of the total solubilized lignin, respectively. The seven lignin fractions were comparatively characterized by chemical composition, structural features, and molecular weights using alkaline nitrobenzene oxidation, acid hydrolysis, UV, FT-IR, 1H and 13C NMR spectroscopy, and GPC. The purity of the lignin fractions isolated by 50% dioxane and alkali was higher than that of the lignin preparations obtained by hot water and DMSO, in which the content of associated polysaccharides in the former lignin fractions (0.16–2.12%) was much lower than those of the latter lignin preparations (10.39 and 37.03%). It was found that the seven lignin fractions contained substantial amounts of non-condensed guaiacyl and syringyl units with fewer p-hydroxyphenyl units, and had weight-average molecular weights between 1270 and 3590gmol−1. No substantial differences in the main structural features between the lignin preparations isolated with 50% dioxane and alkali were found and these treatments did not result in significant changes in lignin composition and its structure. [Copyright &y& Elsevier]