Simultaneous production of furfural, lignin and cellulose-rich residue from Eucalyptus urophylla × E. grandis by ChCl/1,2-propanediol/MIBK biphasic system pretreatment.

A facile biphasic system composed of choline chloride (ChCl)-based deep eutectic solvent (DES) and methyl isobutyl ketone (MIBK) was developed to realize the furfural production, lignin separation and preparation of fermentable glucose from Eucalyptus in one-pot. Results showed that the ChCl/1,2-propanediol/MIBK system owned the best property to convert hemicelluloses into furfural. Under the optimal conditions (MRChCl:1,2-propanediol = 1:2, raw materials:DES:MIBK ratio = 1:4:8 g/g/mL, 0.075 mol/L AlCl3·6H2O, 140 °C, and 90 min), the furfural yield and glucose yield reached 65.0 and 92.2 %, respectively. Meanwhile, the lignin with low molecular weight (1250-1930 g/mol), low polydispersity (DM = 1.25-1.53) and high purity (only 0.08-2.59 % carbohydrate content) was regenerated from the biphasic system. With the increase of pretreatment temperature, the ß-O-4, ß-ß and ß-5 linkages in the regenerated lignin were gradually broken, and the content of phenolic hydroxyl groups increased, but the content of aliphatic hydroxyl groups decreased. This research provides a new strategy for the comprehensive utilization of lignocellulose in biorefinery process.

One-step conversion of corn stalk to glucose and furfural in molten salt hydrate/organic solvent biphasic system.

An effective approach for glucose and furfural production by converting cellulose and hemicelluloses from corn stalk in a biphasic system of molten salt hydrate (MSH) and organic solvent using H2SO4 as catalyst was reported. Results showed that the system with LiBr·3H2O and dichloromethane (DCM) had excellent performance in cellulose and hemicelluloses conversion. Under the optimal reaction conditions (corn stalk:LiBr·3H2O:DCM ratio = 0.35:10:20 g/mL/mL, 0.05 mol/L H2SO4, 120 °C, 90 min), 58.9% glucose and 72.5% furfural were yielded. Meanwhile, lignin was obviously depolymerized by the cleavage of ß-O-4' linkages and fractionated with high purity and low molecular weight for potential coproducts. Fluorescence microscopy and confocal Raman microscope displayed that the LiBr·3H2O/DCM treatment caused decreasing intensities in carbohydrate and lignin, suggesting the degradation of the main components of biomass. This research provided a promising biorefinery technology for the comprehensive utilization of corn stalk.

Application of periodontal tissue regeneration combined with orthodontics in oral prosthodontics and its influence and significance on the expressions of IL-1ß, TNF-α and IL-5 in periodontal tissue.

The aim is to investigate the application of periodontal tissue regeneration combined with orthodontics in oral restoration, and explore its effect and significance on the expressions of Interleukin-1ß (IL-1ß), tumor necrosis factor-α (TNF-α) and interleukin-5 (IL-5) in periodontal tissue. The patients in observation group were treated with orthodontics combined with periodontal tissue regeneration, and the control group was treated with periodontal tissue regeneration. The total effective rate, adverse reactions, recurrence rate and treatment satisfaction were compared. The masticatory function, language function, aesthetic level, VAS score, quality of life, gingival index (GI), plaque index (PLI), periodontal pocket probing depth (PD), sulcus bleeding index (SBI), IL-1ß, TNF-α and IL-5 levels were compared. The recurrence rate of observation group was lower than control group, while the treatment satisfaction was higher after treatment. After treatment, the scores of masticatory, language, aesthetics, physiological, social, emotional, cognitive, and emotional functions and overall health score were higher than before treatment. After treatment, the scores of masticatory and language functions, aesthetics and quality of life of observation group were significantly higher than control group. After treatment, the VAS score, GI, PLI, SBI, PD, IL-1ß, TNF-α and IL-5 levels were lower than before. The VAS score, GI, PLI, SBI, PD levels, IL-1ß, TNF-α and IL-5 levels of observation group were lower after treatment. Orthodontics combined with periodontal tissue regeneration can help improve the periodontal condition of patients with periodontitis, reduce inflammatory response, improve the level of efficacy and overall safety, and further improve patients' quality of life and treatment satisfaction.

Microwave-assisted choline chloride/1,2-propanediol/methyl isobutyl ketone biphasic system for one-pot fractionation and valorization of Eucalyptus biomass.

The developing of pretreatment method to break the biomass barrier of lignocellulosic is a challenging task for achieve high value utilization. A fast microwave-assisted choline chloride/1,2-propanediol/methyl isobutyl ketone biphasic system was constructed for pretreating Eucalyptus to the production of furfural and cellulose-rich residues and the extraction of lignin. Results showed that the combination of AlCl3·6H2O and HCl had the best catalytic ability for furfural production among the examined catalysts. Under the optimal conditions (140 °C, 15 min, 0.075 M AlCl3·6H2O, 0.05 M HCl), the furfural yield of 55.4 %, the glucose yield of 90.3 % and the delignification rate of 92.4 % could be achieved. Moreover, the extracted lignin samples with a low polydispersity (1.55-1.73) and molecular weight (1380-2040 g/mol) are promising to act as precursor for the value-add products processing. These findings demonstrated an ultrafast pretreatment process with excellent results in biomass fractionation and comprehensive utilization of biomass components.

Unveiling the Migration and Transformation Mechanism of Lignin in Eucalyptus During Deep Eutectic Solvent Pretreatment.

Deep eutectic solvents (DESs) have unique advantages in biomass conversion. However, the migration and transformation mechanism of lignin in the cell wall during the DES pretreatment is still elusive. In this work, Eucalyptus blocks were pretreated in choline chloride/lactic acid DES to reveal the lignin migration. Meanwhile, the remaining lignin in the pretreated residue, the regenerated DES lignin, and the solubilized degraded lignin in the recovered DES were investigated to decipher the lignin transformation. Results showed that the DES pretreatment resulted in the penetration of DES from the cell lumen to the cell wall, and lignin in the secondary wall was more easily dissolved than that in the cell corner middle lamella. The syringyl unit of lignin was better stabilized in the DES than the guaiacyl unit of lignin. The condensed lignin fraction mainly remained in the pretreated residue, while the solubilized degraded lignin fraction was monomeric aromatic ketone compounds. This study elucidates the fate of lignin during the DES pretreatment, which could also promote the development of a modern lignocellulosic pretreatment technique.

Ultrastructural elucidation of lignin macromolecule from different growth stages of Chinese pine.

Understanding of the morphological changes at different growth stages and lignin accumulation pattern for pine biomass plays the key role in facilitating the further development of value-added utilization and downstream conversion processes. This work systematically revealed the morphological change and lignin accumulation pattern in Chinese pine branches cell walls via confocal Raman microscopy (CRM) technology. Meanwhile, the structural characteristics of isolated lignin samples from different growth stages were synthetically characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) techniques. The results indicated that the content of pith in adult pine new branch was bigger than juvenile trees. With the increase of physiological age, the branches in adult pine could accumulate more lignin both in overall content and the concentration of cell corner middle layer. Moreover, the significantly increases of molecular weights and the ß-O-4, ß-ß linkages content revealed that the lignin macromolecule of pine would polymerize faster in the adult stage (14, 35 years). The panorama generated from the structural and chemical features of pine native lignin not only benefited to understand the biosynthetic pathways and lignin macromolecules structural variation in plant cell walls from different growth stages but also contributed to the valorization and deconstruction of biomass.

Structure of corn bran hemicelluloses isolated with aqueous ethanol solutions and their potential to produce furfural.

The alkali-soluble hemicelluloses extracted with 10% KOH solution from corn bran were further isolated with different concentrations of aqueous ethanol solutions. Herein 92.2% of the original hemicelluloses can be obtained and the cellulase enzymatic hydrolysis rate of the alkali treated corn bran can reach to 97.2%. The corn bran hemicelluloses were mainly glucuronoarabinoxylan, in which xylose (48.4-53.8%) and arabinose (27.8-33.2%) were the main components. More linear hemicelluloses with high molecular weight tended to be precipitated in low concentration aqueous ethanol solutions. Furthermore, the relationship between the structural features of these alkali-soluble corn bran hemicelluloses and their furfural yield was investigated in MIBK (methyl isobutyl ketone)/H2O biphasic system. Results showed that the hemicelluloses with high xylose content are benefit to the furfural production, and the highest furfural yield of 67.7% was obtained.

Ultrafast alkaline deep eutectic solvent pretreatment for enhancing enzymatic saccharification and lignin fractionation from industrial xylose residue.

An aspirational pretreatment method for efficient fractionation and tailored valorization of large industrial biomass can ensure the realizability of sustainable biorefinery strategies. In this study, an ultrafast alkaline deep eutectic solvents (DES) pretreatment strategy was developed to efficiently extract the lignin nanoparticles and retain cellulose residues that could be readily enzymatic saccharified to obtain fermentative glucose for the bioenergy production from industrial xylose residue. Results showed that the DES pretreatment had excellent delignification performance and the regenerated DES lignin nanoparticles exhibited well-preserved structures and excellent antioxidant activity, as well as low molecular weights and relatively uniform size distribution, which could facilitate downstream catalytic degradation for production of chemicals and preparation of lignin-based materials. Under the optimal condition (DES pretreatment: 80 °C, 10 min; saccharification: 10 FPU/g, 5 wt%, 100 mg/g Tween 80), the glucose yield of 90.12% could be achieved, which was dramatically increased compared to raw materials.

Exploration of deep eutectic solvent-based biphasic system for furfural production and enhancing enzymatic hydrolysis: Chemical, topochemical, and morphological changes.

Developing a biorefinery process for a highly integrated valorization and fractionation of lignocellulose is crucial for its utilization. Herein, a biphasic system comprising choline chloride/lactic acid and 2-methyltetrahydrofuran with Al2(SO4)3 and H2SO4 as catalysts was applied to pretreat Eucalyptus. Results showed that under the optimized conditions (150 °C, 30 min, 0.2 M Al2(SO4)3, 0.075 M H2SO4), the furfural yield and enzymatic hydrolysis efficiency could reach 54.7% and 97.0%, respectively. The efficient cellulose conversion was attributed to remarkable removal of lignin (91.0%) and hemicelluloses (100.0%), thereby causing the disruption of cell wall structure and enhancement of cellulose accessibility. Meanwhile, confocal Raman microscope and atomic force microscope displayed that the pretreatment resulted in the decreasing intensities of carbohydrates and lignin different regions of cell walls, and exposing of the embedded microfibers from noncellulosic polymers. Overall, the deep eutectic solvent-based biphasic system displayed high performance for effective utilization of carbohydrate components in lignocellulose.

Effects of hydrothermal pretreatment on the dissolution and structural evolution of hemicelluloses and lignin: A review.

Exploration of lignocellulosic biomass provides a sustainable and eco-friendly route for producing liquid fuels, materials, and chemicals. However, direct utilization of lignocelluloses is limited by the stable and complicated cross-linking structure of the plant cell wall. Hydrothermal pretreatment (HTP) is a green and cost-effective technology because it can disrupt lignin-carbohydrate complex (LCC) linkages, dissolve hemicelluloses and lignin, and redistribute lignin in the cell wall layers without utilization of any chemicals. Thus, HTP is expected to achieve industrial scale in second-generation biorefineries and circular bioeconomies. This review analyzed the deconstruction of lignocelluloses by HTP, with particular emphasis on the formation mechanism of hemicellulose degradation products and the structural evolution of hemicelluloses and lignin accompanying HTP. Meanwhile, the formation mechanism of pseudolignin and its effect on the enzymatic hydrolysis of cellulose as well as strategies for inhibiting lignin recondensation were discussed.

Severity factor kinetic model as a strategic parameter of hydrothermal processing (steam explosion and liquid hot water) for biomass fractionation under biorefinery concept.

Hydrothermal processes are an attractive clean technology and cost-effective engineering platform for biorefineries based in the conversion of biomass to biofuels and high-value bioproducts under the basis of sustainability and circular bioeconomy. The deep and detailed knowledge of the structural changes by the severity of biomasses hydrothermal fractionation is scientifically and technological needed in order to improve processes effectiveness, reactors designs, and industrial application of the multi-scale target compounds obtained by steam explosion and liquid hot water systems. The concept of the severity factor [log10 (Ro)] established>30 years ago, continues to be a useful index that can provide a simple descriptor of the relationship between the operational conditions for biomass fractionation in second generation of biorefineries. This review develops a deep explanation of the hydrothermal severity factor based in lignocellulosic biomass fractionation with emphasis in research advances, pretreatment operations and the applications of severity factor kinetic model.

Enzymatic response of ryegrass cellulose and hemicellulose valorization introduced by sequential alkaline extractions.

BACKGROUND: In view of the natural resistance of hemicelluloses in lignocellulosic biomass on bioconversion of cellulose into fermentable sugars, alkali extraction is considered as an effective method for gradually fractionating hemicelluloses and increasing the bioconversion efficiency of cellulose. In the present study, sequential alkaline extractions were performed on the delignified ryegrass material to achieve high bioconversion efficiency of cellulose and comprehensively investigated the structural features of hemicellulosic fractions for further applications. RESULTS: Sequential alkaline extractions removed hemicelluloses from cellulose-rich substrates and degraded part of amorphous cellulose, reducing yields of cellulose-rich substrates from 73.0 to 27.7% and increasing crystallinity indexes from 31.7 to 41.0%. Alkaline extraction enhanced bioconversion of cellulose by removal of hemicelluloses and swelling of cellulose, increasing of enzymatic hydrolysis from 72.3 to 95.3%. In addition, alkaline extraction gradually fractionated hemicelluloses into six fractions, containing arabinoxylans as the main polysaccharides and part of ß-glucans. Simultaneously, increasing of alkaline concentration degraded hemicellulosic polysaccharides, which resulted in a decreasing their molecular weights from 67,510 to 50,720 g/mol. CONCLUSIONS: The present study demonstrated that the sequential alkaline extraction conditions had significant effects on the enzymatic hydrolysis efficiency of cellulose and the investigation of the physicochemical properties of hemicellulose. Overall, the investigation the enzymatic hydrolysis efficiency of cellulose-rich substrates and the structural features of hemicelluloses from ryegrass will provide useful information for the efficient utilization of cellulose and hemicelluloses in biorefineries.

Effect of integrated treatment on improving the enzymatic digestibility of poplar and the structural features of isolated hemicelluloses.

Herein, a two-step hydrothermal pretreatment combined with alkali extraction method was applied to deconstruct the poplar cell walls for enzymatic hydrolysis. Results revealed that 88.1 % of hemicelluloses and 77.6 % of lignin were removed during the integrated treatment performed at 180 °C and a maximum enzymatic hydrolysis efficiency of 96.1 % was achieved. Confocal Raman microscopy suggested that the removal of hemicelluloses from cell walls was inhomogeneous, and most hemicelluloses were released from the secondary wall. In addition, 35.2-56.8 % of hemicelluloses were isolated from the integrated treatment. Detailed structural analysis revealed that the water-soluble hemicelluloses possessed more branched structure than the alkali-soluble hemicelluloses and the hemicelluloses isolated from the poplar were mainly composed of a linear backbone of (1→4)-ß-d-Xylp with 4-O-Me-α-d-GlcpA attached as side chains. This work provides an efficient pathway to transform poplar into fermentable sugars and hemicelluloses with considerable yield.

Simultaneous and Efficient Production of Furfural and Subsequent Glucose in MTHF/H2O Biphasic System via Parameter Regulation.

Efficient production of furfural from cornstalk in 2-Methyltetrahydrofuran/aqueous (MTHF/H2O) biphasic system via parameter regulation (e.g., VMTHF/VH2O, temperature, time, and H2SO4 concentration) was proposed. The resulting solid residues achieved from the different MTHF/H2O system conditions for furfural production were also to prepare glucose by adding cellulases to increase the high-value applications of cornstalk. A maximum furfural yield (68.1%) was obtained based on reaction condition (VMTHF:VH2O = 1:1, 170 °C, 60 min, 0.05 M H2SO4). Among these parameters, the concentration of H2SO4 had the most obvious effect on the furfural production. The glucose yields of the residues acquired from different MTHF/H2O processes were enhanced and then a maximum value of 78.9% based on the maximum furfural production conditions was observed. Single factor may not be sufficient to detail the difference in glucose production, and several factors affected the hydrolysis efficiency of the residues. Overall, the MTHF/H2O system effectively converted cornstalk into furfural and glucose via a simple and environment-friendly process, thus was an ideal manner for the food industries.

Multiple Analysis and Characterization of Novel and Environmentally Friendly Feather Protein-Based Wood Preservatives.

In this study, feather was used as the source of protein and combined with copper and boron salts to prepare wood preservatives with nano-hydroxyapatite or nano-graphene oxide as nano-carriers. The treatability of preservative formulations, the changes of chemical structure, micromorphology, crystallinity, thermal properties and chemical composition of wood cell walls during the impregnation and decay experiment were investigated by retention rate of the preservative, Fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy-energy dispersive spectrometer (SEM-EDS), X-ray diffraction (XRD), thermoanalysis (TG), and confocal Raman microscopy (CRM) techniques. Results revealed that the preservatives (particularly with nano-carrier) successfully penetrated wood blocks, verifying the enhanced effectiveness of protein-based preservative with nano-carrier formulations. Decay experiment demonstrated that the protein-based wood preservative can remarkably improve the decay resistance of the treated wood samples, and it is an effective, environmentally friendly wood preservative. Further analysis of these three preservative groups confirmed the excellent function of nano-hydroxyapatite as a nano-carrier, which can promote the chelation of preservatives with higher content of effective preservatives.

Engineering aspects of hydrothermal pretreatment: From batch to continuous operation, scale-up and pilot reactor under biorefinery concept.

Different pretreatments strategies have been developed over the years mainly to enhance enzymatic cellulose degradation. In the new biorefinery era, a more holistic view on pretreatment is required to secure optimal use of the whole biomass. Hydrothermal pretreatment technology is regarded as very promising for lignocellulose biomass fractionation biorefinery and to be implemented at the industrial scale for biorefineries of second generation and circular bioeconomy, since it does not require no chemical inputs other than liquid water or steam and heat. This review focuses on the fundamentals of hydrothermal pretreatment, structure changes of biomass during this pretreatment, multiproduct strategies in terms of biorefinery, reactor technology and engineering aspects from batch to continuous operation. The treatise includes a case study of hydrothermal biomass pretreatment at pilot plant scale and integrated process design.

One-pot preparation and characterization of lignin-based cation exchange resin and its utilization in Pb (II) removal.

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.

Effect of various pretreatments on improving cellulose enzymatic digestibility of tobacco stalk and the structural features of co-produced hemicelluloses.

Hereon, tobacco stalk was deconstructed by lyophilization, ball-milling, ultrasound-assisted alkali extraction, hydrothermal pretreatment (HTP), and alkali presoaking, respectively, followed by dilute alkali cooking to both improve its enzymatic digestibility and isolate the hemicellulosic streams. It was found that a maximum cellulose saccharification rate of 93.5% was achieved from the integrated substrate by ball-milling and dilute alkali cooking, which was 4.4-fold higher than that from the raw material. Interestingly, in this case, 76.9% of hemicelluloses were simultaneously recovered during the integrated treatment. Structural determination indicated that the hemicelluloses released from tobacco stalk by dilute alkali cooking were mixed polysaccharides, and the (1 â†’ 4)-linked ß-D-Xylp backbone branched with L-Araf units at O-2/O-3 and 4-O-Me-α-D-GlcpA units at O-2 of the xylose residues was the main structure. In comparison, ultrasound-assisted alkali extraction, ball-milling, and HTP favored the extraction of hemicelluloses with less branched structure and lower molecular weights in the following alkali cooking.

Carbon microspheres prepared from the hemicelluloses-rich pre-hydrolysis liquor for contaminant removal.

Pre-hydrolysis liquor (PHL) from the kraft-based dissolving pulp process contains large amounts of hemicelluloses, which is usually treated as an effluent and further efforts have to be involved to eliminate the pollution disposal. However, the hemicelluloses-rich PHL is a promising candidate for the production of carbon microspheres via hydrothermal carbonization. The yield of the carbon microspheres directly derived from the hydrothermal carbonization of the hemicelluloses-rich PHL (22.1%) was almost twice than that from xylose (13.1%). Furthermore, sulfuric acid and the lignin in the PHL could significantly improve the yield and change the size of the carbon microspheres obtained from the PHL. Additionally, the activated carbon microspheres functionalized with acrylic acid showed improved adsorption capacities for Pb(II) ion (273.4 mg/g) and methylene blue (701.3 mg/g). The hydrothermal carbonization of the PHL not only utilizes the hemicelluloses in the PHL, but also reduces the pollution load of the PHL significantly.

Biphasic 2-methyltetrahydrofuran/oxalic acid/water pretreatment to enhance cellulose enzymatic hydrolysis and lignin valorization.

A biphasic pretreatment was adopted to disturb the recalcitrant structure of bamboo for further enzymatic hydrolysis and to obtain easily valorized lignin by-product. The biphasic system consisted of biomass-derived chemicals-2-methyltetrahydrofuran and oxalic acid as well as water, and the reactions were conducted at 120-180°C for 20min. The treatment resulted in notable removal of hemicelluloses and lignin. After the pretreatment, the cellulose conversion rate during enzymatic hydrolysis was enhanced by 6.7-fold as compared to the unpretreated raw material. Comprehensive analysis of the lignin product indicated that it exhibited representative structure (such as ß-O-4, ß-ß linkages) as compared to native lignin, contained a very low amount of contaminated sugars (0.67-2.39%), and had a relatively medium molecular weight (Mw 2240-3730g/mol) and good solubility in many organic solvents. This indicated that the lignin showed great potential application in conversion into materials and liquid fuels.