Lignin Units Research Articles

Red room temperature phosphorescence from lignin

Materials with red room‐temperature phosphorescence (RTP) derived from sustainable sources are crucial but rarely reported. Here, we produced red RTP materials from lignin. Lignin was covalently modified with Upy (1‐(6‐isocyanatohexyl)‐3‐(6‐methyl‐4‐oxo‐1,4‐dihydropyrimidin‐2‐yl) urea) to obtain Lig‐Upy. The Upy in the Lig‐Upy promoted the interaction between the aromatic units of lignin and reduced energy gaps of these molecules. As a result, Lig‐Upy exhibited red RTP centered at 625 nm with a lifetime of 24.2 ms. Moreover, the hydrogen bonding interactions in Lig‐Upy varied when embedded into different matrices, such as polyvinyl alcohol (PVA) or sodium montmorillonite (MTM), inducing a change in RTP wavelength and lifetime. Utilizing these properties, Lig‐Upy was used as building blocks for producing materials exhibiting time‐dependent phosphorescent colors (TDPCs). Such TDPCs materials have exhibited great potential for visual decorations, information encryption and anti‐counterfeiting logos for medicine bottles.

Red Room Temperature Phosphorescence from Lignin.

Materials with red room-temperature phosphorescence (RTP) derived from sustainable resources are crucial but rarely reported. Here, we produced red RTP materials from lignin. Lignin was covalently modified with Upy (1-(6-isocyanatohexyl)-3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea) to obtain Lig-Upy. The Upy in the Lig-Upy promoted the interaction between the aromatic units of lignin and reduced energy gaps of these molecules. As a result, Lig-Upy exhibited red RTP centered at 625 nm with a lifetime of 24.2 ms. Moreover, the hydrogen bonding interactions in Lig-Upy varied when embedded into different matrices, such as polyvinyl alcohol (PVA) or sodium montmorillonite (MTM), inducing a change in RTP wavelength and lifetime. Utilizing these properties, Lig-Upy was used as building blocks for producing materials exhibiting time-dependent phosphorescent colors (TDPCs). Such TDPCs materials have exhibited great potential for visual decorations, information encryption and anti-counterfeiting logos for medicine bottles.

Synergetic Effects of Soil Organic Matter Components During Interactions with Minerals.

Mineral-associated soil organic matter (SOM) is critical for stabilizing organic carbon and mitigating climate change. However, mineral-SOM interactions at the molecular scale, particularly synergetic adsorption through organic-organic interaction on the mineral surface known as organic multilayering, remain poorly understood. This study investigates the impact of organic multilayering on mineral-SOM interactions, by integrating macroscale experiments and molecular-scale simulations that assess the individual and sequential adsorption of major SOM compounds-lauric acid (lipid), pentaglycine (amino acid), trehalose (carbohydrate), and lignin onto soil minerals. Ferrihydrite, Al-hydroxide, and calcite are exposed to SOM compounds to determine adsorption affinities and binding energies. Results show that lauric acid has 20-40 times higher Kd than pentaglycine, following the order Kd(ferrihydrite) > Kd(Al-hydroxide) ≫ Kd(calcite). Molecular-scale simulations confirm that lauric acid has a higher binding energy (30.8 kcal/mol) on ferrihydrite than pentaglycine (6.0 kcal/mol), attributed to lipid hydrophobicity. The lower binding energy of pentaglycine results from its hydrophilic amide groups, facilitating partitioning into water. Sequential experiments examine how the first layer of lipid or amino acid affects the adsorption of carbohydrate/lignin, which show little or no individual adsorption affinities. Macroscale results reveal that lipid and amino acid adsorption induce ferrihydrite particle repulsion increasing reactive surface area and enhancing carbohydrate/lignin adsorption independently and synergistically through organic multilayering. Molecular-scale results reveal that amino acid adsorbed on ferrihydrite interacts more readily with lignin macroaggregates (preformed in solution) than with individual lignin units, indicating organic multilayering via H-bonding. These findings reveal the molecular mechanisms of SOM-mineral interactions, crucial for enhancing soil carbon stabilization.

The distribution of monolignol glucosides coincides with lignification during the formation of compression wood in Pinus thunbergii.

The distributions of monolignol glucosides (MLGs) in compression and opposite woods of Pinus thunbergii were assessed using cryo-time-of-flight secondary ion mass spectrometry to investigate their involvement in lignification. p-Glucocoumaryl alcohol (PG) was identified in the region of the differentiating xylem adjacent to the cambial zone only in compression wood, whereas coniferin (CF) was similarly localized in both compression and opposite woods. Their distribution from the phloem to the xylem was evaluated by high-performance liquid chromatography (HPLC) using serial tangential sections. Variations in storage amounts of CF and PG in the stem of P. thunbergii agreed with lignification stages of the tracheid, supporting the idea that MLGs act as a storage and transportation form of lignin precursors. The imaging of monolignol (ML)-dependent active lignification sites using fluorescence-tagged MLs supported distinct distribution patterns of MLGs for lignification in compression and opposite woods. Methylation-thioacidolysis was applied to compression and opposite wood samples to examine the structural difference between the guaiacyl (G) and p-hydroxyphenyl (H) units in lignin. Most of the H units in compression wood were detected as lignin end groups via thioacidolysis. PG was detected in opposite wood by HPLC; however, the H unit was not detected by thioacidolysis. The differences in ML and MLG distributions, enzyme activity, and resultant lignin structures between the G and H units suggest the possibility of individual mechanisms regulating the heterogeneous structures of G and H unit in lignin.

Polyphenol Oxidase Activity on Guaiacyl and Syringyl Lignin Units.

The natural heterogeneity of guaiacyl (G) and syringyl (S) compounds resulting from lignin processing hampers their direct use as plant-based chemicals and materials. Herein, we explore six short polyphenol oxidases (PPOs) from lignocellulose-degrading ascomycetes for their capacity to react with G-type and S-type phenolic compounds. All six PPOs catalyze the ortho-hydroxylation of G-type compounds (guaiacol, vanillic acid, and ferulic acid), forming the corresponding methoxy-ortho-diphenols. Remarkably, a subset of these PPOs is also active towards S-compounds (syringol, syringic acid, and sinapic acid) resulting in identical methoxy-ortho-diphenols. Assays with 18O2 demonstrate that these PPOs in particular catalyze ortho-hydroxylation and ortho-demethoxylation of S-compounds and generate methanol as a co-product. Notably, oxidative (ortho-)demethoxylation of S-compounds is a novel reaction for PPOs, which we propose occurs via a distinct reaction mechanism compared to aryl-O-demethylases. We further show that addition of a reducing agent can steer the PPO reaction to form methoxy-ortho-diphenols from both G- and S-type substrates rather than reactive quinones that lead to unfavorable polymerization. Application of PPOs opens for new routes to reduce the heterogeneity and methoxylation degree of mixtures of G and S lignin-derived compounds.

Exploring the relationship between lignin structure and antioxidant property using lignin model compounds

Lignin has a natural polyphenol structure that is expected to replace chemically synthesized antioxidants as a native antioxidant with biodegradable and convenient source characteristics. However, the improvement of the antioxidant property of lignin and its application as an antioxidant are still somewhat limited due to the lack of understanding of the relationship between specific lignin structures and antioxidant property. Therefore, the study of the relationship between lignin structure and antioxidant property is crucial to realize the high-quality application of lignin. In this experiment, the scavenging ability of free 1,1-diphenyl-2-picrylhydrazyl (DPPH·) radicals was determined for different grades of acetylated tannins, typical lignin model compounds and different structural units of milled wood lignin to investigate the relationship between lignin structure and antioxidant property. Based on the experimental results, some structure-activity relationships were proposed and the mechanism of the antioxidant property of lignin was discussed. The number of phenolic hydroxyl groups was linearly and positively correlated with antioxidant property, and the scavenging of DPPH radicals increased significantly with the increase in the number of methoxy groups in the model compounds. Moreover, aldehyde and carboxyl groups had a negative effect on the antioxidant property of lignin, while methoxy, alkyl and alcohol hydroxyl groups played a positive role. The guaiacyl (G) and syringyl (S) units favored the antioxidant property, so the difference in the content of structural units in lignin under certain conditions of phenolic hydroxyl content also affected the antioxidant property. Therefore, the antioxidant property of aspen milled lignin was higher than that of other milled lignin from different wood species. Finally, the mechanism of DPPH free radical scavenging by lignin was revealed to better understand the relationship between lignin structure and antioxidant property.

Expression of laccase and ascorbate oxidase affects lignin composition in Arabidopsis thaliana stems.

Lignin is a phenolic polymer that is a major source of biomass. Oxidative enzymes, such as laccase and peroxidase, are required for lignin polymerisation. Laccase is a member of the multicopper oxidase family and has a high amino acid sequence similarity with ascorbate oxidase. However, the process of functional differentiation between the two enzymes remains poorly understood. In this study, the common ancestry sequence of laccase and ascorbate oxidase (AncMCO) was predicted via phylogenetic reconstruction, and its in vivo effect on lignin biosynthesis in Arabidopsis thaliana was assessed. The estimated AncMCO sequence conserved key residues that coordinate with copper ions, implying that the electron transfer system is likely to be conserved in AncMCO. However, multiple insertions/deletions corresponding to protein surface structures have been found between laccase, ascorbate oxidase, and AncMCO. The overexpression of canonical laccase (AtLAC4) and ascorbate oxidase (AtAAO1) in A. thaliana resulted in notable increases of syringyl/guaiacyl lignin unit ratio in stems, whereas, in contrast, the overexpression of AncMCO did not show any detectable change in lignin deposition. Transcriptomic analysis revealed that the AtAAO1-overexpressing line exhibited significant changes in the expression of a wide range of cell wall biosynthesis genes. These results highlight the importance of the molecular evolution of multicopper oxidase, which drives lignin biosynthesis during plant evolution.

Sustainable Lignin Extraction Using a Mild Acidic γ-Valerolactone Process for the Identification of White and Red Oaks.

Current wood identification struggles to differentiate white and red oak (Quercus alba and Quercus rubra) due to highly similar microstructures, as demonstrated by morphological microscope analysis. The present research explores lignin composition as a potential discriminating factor. Here, a rapid and sustainable method for extracting high-quality lignin from oak samples using acidic γ-valerolactone (GVL) under mild conditions is described. As-extracted lignin is thoroughly characterized using various analytical methods, and results reveal a distinct structural difference between the lignin from the two species. White oak lignin possesses a unique "Hibbert ketone" unit detectable by nuclear magnetic resonance spectroscopy (NMR), which is absent in red oak lignin. In addition, infrared spectroscopy differentiates the species based on specific carbonyl groups present in their lignin. These findings suggest that identifying the presence of the Hibbert ketone unit in lignin may offer a highly efficient and reliable method for differentiating white and red oak, opening new avenues for wood identification.

Maximizing Degumming Efficiency for Firmiana simplex Bark Using Deep Eutectic Solvents.

Degumming is a critical process in the purification of natural fibers, essential for enhancing their quality and usability across various applications. Traditional degumming methods employed for natural fibers encounter inherent limitations, encompassing prolonged procedures, excessive energy consumption, adverse environmental impact, and subpar efficiency. To address these challenges, a groundbreaking wave of degumming technique has emerged, transcending these constraints and heralding a new era of efficiency, sustainability, and eco-friendly techniques. This study represents the Firmiana simplex bark (FSB) fiber's delignification by using deep eutectic solvents (DESs). The study explores the application of deep eutectic solvents, by synthesizing different types of DES using a hydrogen bond acceptor (HBA) and four representative hydrogen bond donors (HBDs) for FSB fiber degumming. This study investigates the morphologies, chemical compositions, crystallinities, and physical properties of Firmiana simplex bark fibers before and after the treatment. Furthermore, the effects and mechanisms of different DESs on dispersing FSB fibers were examined. The experimental results showed that choline chloride-urea (CU)-based DES initiates the degumming process by effectively disrupting the hydrogen bond interaction within FSB fibers, primarily by outcompeting chloride ions. Following this initial step, the DES acts by deprotonating phenolic hydroxyl groups and cleaving β-O-4 bonds present in diverse lignin units, thereby facilitating the efficient removal of lignin from the fibers. This innovative approach resulted in significantly higher degumming efficiency and ecofriendly as compared to traditional methods. Additionally, the results revealed that CU-based DES exhibits the utmost effectiveness in degumming FSB fibers. The optimal degumming conditions involve a precise processing temperature of 160 °C and a carefully controlled reaction time of 2 h yielding the most favorable outcomes. The present study presents a novel straightforward and environmentally friendly degumming method for Firmiana simplex bark, offering a substantial potential for enhancing the overall quality and usability of the resulting fibers. Our findings open new pathways for sustainable fiber-processing technologies.

Upgrading lignocellulosic biomass to high-value products through the pretreatment driven by bio-based ethylene glycol solvent

Sustainable processing of lignocellulosic biomass is meaningful for comprehensive biomass conversion. Here, a ball milling (BM) assisted biomass-derived ethylene glycol (BEG) pretreatment is proposed to removes nearly 90 % of the lignin and increases cellulose accessibility by 3 times than raw biomass, facilitating subsequent enzymatic saccharification or catalytic conversion for 5-hydroxymethylfurfural (HMF), achieving yields of 92.9 % and 32.6 %. The synergistic effect of BM/BEG positively impacted delignification, followed by saccharification and HMF conversion. Introduction of biomass-derived solvent recovers the lignin with a well-preserved chemical structure, uniform molecular weight, short side chains, and high purity, making it highly suitable for downstream utilization. Density functional theory revealed hydrogen bonding and good miscibility between BEG and lignin units, suggesting reaction mechanisms and pathways. Molecular dynamics simulations showed that the solubilizing effect of BEG on lignin promoted cellulase-cellulose binding, thereby enhancing saccharification efficiency. The successful use of BEG solvents to maximize the biomass value is conducive to achieve closed-loop biorefinery approaches.

Hydrogen peroxide assisted oxidative liquefaction of alkaline lignin over cobalt-nickel loaded zirconia catalysts

Research toward the oxidative fractionation of lignin is gaining attention due to the selective breaking of a sub-aromatic unit of lignin's complex structure into monomeric phenolic. This study aims to investigate the liquefaction tendency of alkaline lignin by screening the synergistic effect of Co and Ni loaded on synthesized (syn) ZrO2 catalyst under the applied mild oxidative reaction conditions of molecular oxygen and hydrogen peroxide. Compared to the non-catalytic reaction (38.1 wt%), a significant improvement in the bio-oil yield (53.7 wt%) was obtained with the 5Co–5Ni/ZrO2-syn catalyst under the oxidative condition of molecular oxygen. However, only 44.3 wt% bio-oil was observed with commercial (com) 5Co–5Ni/ZrO2-com catalyst. The synergistic study of Co and Ni metal exhibited a diverse impact on the fractionation of lignin into respective product yields (bio-oil, gas, and char). Notably, adding a catalytic amount of hydrogen peroxide showed a remarkable improvement in liquefaction. The maximum bio-oil yield (72.1 wt%), and a maximum conversion (77.9%) were noticed with 0.5 mL H2O2 at 120 °C/30 min under the atmospheric molecular oxygen. The GC-MS analysis of bio-oil (5Co–5Ni/ZrO2-syn-HP) attributed to a high quantity of guaiacyl phenolic with a maximum proportion of benzaldehyde-3-hydroxy-4-methoxy (65.3%). The 5Co–5Ni/ZrO2-syn catalyst was also examined for the three catalytic cycles, which did not show any significant loss in product yield.

Processing natural bamboo into white bamboo through photocatalyzed lignin oxidation

Scalable and highly efficient bamboo whitening remains a great challenge. Herein, an effective bamboo whitening strategy is proposed based on photocatalyzed oxidation, which involves H2O2 infiltration and UV illumination. The as-prepared white bamboo well maintains the nature structure of natural bamboo and demonstrates high whiteness and superior mechanical properties. The absorbance value is significantly decreased to 3.5 and the transmittance is increased to 0.04 % in UV–visible wavelength range due to the removal of light-absorbing chromospheres of lignin, resulting in a high whiteness when the UV illumination time is 8 h. In addition, the white bamboo displays a high tensile strength of 30 MPa and a high flexural strength of 36 MPa due to the well-preserved lignin units (lignin preservation is about 89 %). XRD patterns and analysis show that photocatalyzed oxidation has no effect on the crystal parameters of cellulose. Compared with the traditional bamboo whitening technology, our photocatalyzed oxidation strategy demonstrates significant advantage including chemical and time conservation, high efficiency, environment friendliness, and mechanical robustness. This highly efficient and environmentally friendly photocatalyzed oxidation strategy for the fabrication of white bamboo may pave the way of bamboo-based energy-efficient structural materials for engineering application.

Seasonal studies of aquatic humic substances from Amazon rivers: characterization and interaction with Cu (II), Fe (II), and Al (III) using EEM-PARAFAC and 2D FTIR correlation analyses.

Aquatic humic substances (AHS) are defined asan important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (KML ranged from 0.3 to 7.9 × 105) than C2 (KML ranged from 3.1 to 10.0 × 105). 2D-COS FTIR showed that the COO- and C-O in phenolic were the most important functional groups for interaction with studied metallic ions.

Comparison of effects of carbocation scavengers assisted acid pretreatment on improving enzymatic digestibility of masson pine and poplar

To investigate the disparate effects of carbocation scavengers on promoting the enzymatic hydrolysis of softwood and hardwood, five carbocation scavengers were supplemented during acid pretreatment of masson pine and poplar in this study, including 2-naphthol (2 N), 2-naphthol-7-sulfonate (NS), p-hydroxybenzoic acid (PB), vanillic acid (VA) and syringic acid (SA). The results showed that naphthols (2 N and NS) with only one nucleophilic site enhanced delignification and enzymatic hydrolysis more significantly than the monophenols with several reactive sites. Adding 2 N and NS increased the hydrolysis yield of acid-pretreated masson pine (AM) from 14.87% to 20.58% and 35.52%, respectively. Correspondingly, the hydrolysis yield of acid-pretreated poplar (AP) improved from 56.54% to 80.47% and 86.9%, respectively. Moreover, as pretreatment severity increased, the enzymatic digestibility of AM and AP first increased and then decreased. However, the naphthols modification retarded this decline, especially for the enzymatic hydrolysis of pretreated poplar. The structure of carbocation scavengers and the lignin unit composition jointly determined the improvement on enzymatic hydrolysis of woody biomass by carbocation scavengers. Furthermore, the naphthols promoted the enzymatic hydrolysis mainly by alleviating enzyme non-productive binding.

Temporal dynamics of lignin degradation in Quercus acutissima sawdust during Ganoderma lucidum cultivation

Despite a fair amount of lignin conversion during mycelial growth, previous structural analyses have not yet revealed how lignin changes continuously and what the relationship is between lignin and ligninolytic enzymes. To clarify these aspects, Quercus acutissima sawdust attaching Ganoderma lucidum mycelium collected from different growth stage was subjected to analysis of lignin structure and ligninolytic enzyme activity. Two key periods of lignin degradation are found during the cultivation of G. lucidum: hypha rapid growth period and primordium formation period. In the first stage, laccase activity is associated with the opening of structures such as methoxyls, β-O-4′ substructures and guaiacyl units in lignin, as well as the shortening of lignin chains. Manganese peroxidases and lignin peroxidases are more suitable for degrading short chain lignin. The structure of phenylcoumarans and syringyl changes greatly in the second stage. The results from sawdust attaching mycelium provide new insights to help improve the cultivation substrate formulation of G. lucidum and understand biomass valorization better.

Selective lignin extraction by deep eutectic solvents for the green preparation of bagasse fibers with different lignin contents

In this work, a series of deep eutectic solvents (DES) were prepared using varying proportions of choline chloride and lactic acid. The DES were then employed to selectively extract lignin from bagasse fibers, resulting in bagasse fibers with varying lignin contents. By manipulating the lactic acid composition, bagasse fibers with lignin content ranging from 3.79 to 11.73 wt% of the total weight of the original bagasse were successfully produced, retaining most of the cellulose. Furthermore, the dissolution mechanism of the DES was experimentally characterized. These findings indicate that an increase in the lactic acid level leads to a finer particle size and dissolved cellulose shape. Furthermore, the mechanism by which lactic acid content influences the extraction of lignin units was investigated along with the morphological and elemental changes of cellulose within bagasse fibers after extraction. Additionally, the changes in structural composition, molecular weight, and β-d-xylopyranoside content of lignin were analyzed. This study offers novel perspectives on the environmentally friendly processing of cellulosic material with various lignin contents.

Quantitative structural elucidation of original lignins in different varieties of waste Gleditsia sinensis Lam. pods

Obtaining new materials, industrial chemicals, and energy from the conversion of agricultural and forestry biomass to fill the gap of non-renewable fossil energy has become a growing trend. As a waste biomass, the G. sinensis pods (GSP) after saponin extraction are always discarded due to lack of industrial/high value-added utilization. Herein, in order to lay a foundation for the selection of pretreatment strategies of GSP and the valorization of GSP lignin, the lignins from the different varieties of GSP were isolated by double enzymatic method and quantitatively characterized. Results indicated that GSP lignin was of the GS-type (S/G, 1.1–1.4) and the interunit linkages were mainly β-O-4′ linkage, along with a certain amount of carbon-carbon linkages (≈35/Ar). L1 showed higher β-O-4′ linkage content (61.3/100 Ar) and relative molar mass (12190 mol/g). Some atypical lignin units, such as cinnamyl aldehyde end-group, cinnamyl alcohol end-groups, and ferulates, were also revealed in GSP lignins. Finally, the potential molecular structure graphs of the GSP lignin were depicted on the basis of the quantitative results. Overall, comprehensive research of the structural characteristics of GSP lignin is essential for efficiently deconstructing GSP and transforming the utilization of the cell wall components.

Ether Bond Cleavage of a Phenylcoumaran β-5 Lignin Model Compound and Polymeric Lignin Catalysed by a LigE-type Etherase from Agrobacterium sp.

A LigE-type beta-etherase enzyme from lignin-degrading Agrobacterium sp. has been identified, which assists degradation of polymeric lignins. Testing against lignin dimer model compounds revealed that it does not catalyse the previously reported reaction of Sphingobium SYK-6 LigE, but instead shows activity for a β-5 phenylcoumaran lignin dimer. The reaction products did not contain glutathione, indicating a catalytic role for reduced glutathione in this enzyme. Three reaction products were identified: the major product was a cis-stilbene arising from C-C fragmentation involving loss of formaldehyde; two minor products were an alkene arising from elimination of glutathione, and an oxidised ketone, proposed to arise from reaction of an intermediate with molecular oxygen. Testing of the recombinant enzyme against a soda lignin revealed the formation of new signals by two-dimensional NMR analysis, whose chemical shifts are consistent with the formation of a stilbene unit in polymeric lignin.

Double in-situ lignin modification in surfactant-assisted glycerol organosolv pretreatment of sugarcane bagasse towards efficient enzymatic hydrolysis

Organosolv pretreatment effectively fractionates lignocellulosic biomass for efficient enzymatic hydrolysis, yielding fermentable sugars. However, substantial lignin redeposition on the substrate surface and residual lignin content exacerbate lignin’s inhibitory effects on subsequent enzymatic hydrolysis. An in-situ lignin modification is proposed to address this challenge by incorporating polyethylene glycol (PEG) series into glycerol organosolv (GO) pretreatment. According to the results obtained, PEG-assisted GO pretreated substrate exhibited significantly increased sugar yield during enzymatic hydrolysis, particularly with PEG 4000, showing 35.4% higher glucose yield over 72 h. The improved glucose yield with PEG could be attributed to changes in the physicochemical structure and properties of residual lignin, mitigating its non-productive interaction with cellulase enzymes. PEG's presence in GO pretreatment also increased β-O-4 linkages preservation by 55% and reduced phenolic hydroxyl groups by 28% in lignin fragments versus no surfactants. This outcome resulted from introducing glycerol and PEG hydroxyl tails into the lignin structure, forming α-etherified lignin and rendering it more hydrophilic. Simulations confirmed strong Van Der Waals and hydrogen bonding interactions between lignin units and PEG, hindering lignin fragments repolymerization. Incorporating PEG in the organosolv pretreatment proves highly beneficial for cellulase-mediated lignocellulosic biorefinery, resembling a lignin-first strategy. The optimized process enables efficient biomass utilization for sustainable fuels and chemicals production.

Biomass characterization and solvent extraction as tools to promote phenol production from urban pruning

Nowadays, leaves, bark, and branches are generated from the tree-pruning process in urban places, where their management is a problem because of the necessity of disposal. These wastes are lignocellulosic biomasses with poor properties for use in biofuel production, but with interesting projections for building block products such as phenol compounds. Therefore, extensive biomass characterization of urban pruning from Liquidambar styraciflua L. was developed to evaluate its composition as a tool for phenol production through thermal processing, in which solvent extraction is a complementary tool for selectivity improvement. The results showed high lignin content in bark and leaves at 45 and 28 %, respectively, compared with that in branches (14 %). Additionally, high extractives in leaves (14 %) could be an additional source of phenols. The lignin units were analyzed by Raman dispersion, revealing p–hydroxyphenyl (H) units in the bark, guaiacyl (G) units in the bark and leaves, and syringyl (S) units only in the branches. Furthermore, the micropyrolysis coupled with gas chromatography/mass spectrometry assay realized at 600 °C showed high presence of phenolic compounds in the three biomass investigated, where a high phenol concentration was identified in leaves, probably due to the S unit degradation during pyrolysis. With these results, an assay for bio-oil production was performed in a low-temperature pyrolysis reactor using leaves as feedstock, reaching a low bio-oil yield with high water content favored for the high inorganic content of leaves (13 %). The produced bio-oil was used for liquid–liquid extraction evaluation, where 1-octanol and methyl isobutyl ketone were identified as interesting solvents for catechol and phenol extraction, respectively. This article presents the challenge of characterizing each part of urban trees, which could be a tool to promote the use of urban pruning by studying the thermal degradation mechanism to implement processes for high-value products, such as phenols produced from L. styraciflua L.