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Castor stalk from hemp plants is an attractive lignocellulosic feedstock for biomass refining valorization due to its similar chemical composition to hardwoods. In this study, the castor stalk fibers were pretreated with efficient dual-functional ethanolamine to achieve delignification and swelling of the cellulosic fibers, followed by cellulase enzymatic digestion for biomass conversion. Experimental results showed that ethanolamine pretreatment at 160 °C for 1 h effectively removed 69.20 % of lignin and 43.18 % of hemicellulose. In addition to efficient delignification and removal of hemicellulose, the study also revealed that supramolecular structure of cellulose was another major factor affecting enzymatic hydrolysis performance. The lowered crystallinity (60-70 %) and swelled crystal sizes (2.95-3.04 nm) promoted enzymatic hydrolysis efficiency during the heterogeneous reaction process. Under optimal conditions (160 °C, 1 h; enzyme loading: 15 FPU/g substrate), promoted yields of 100 % glucose and over 90 % xylose were achieved, which were significantly higher than those obtained from untreated castor stalk. These findings highlighted the effectiveness of the dual-functional ethanolamine pretreatment strategy for efficient bioconversion of lignocellulosic feedstocks. Overall, this study provides valuable insights into the development of new strategies for the efficient utilization of biomass resources, which is essential for the sustainable development of our society.

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An innovative binary biol-based deep eutectic solvent (DES), specifically ethylamine hydrochloride-ethylene glycol (EaCl-EG), was developed for efficient pretreatment of eucalyptus biomass. This DES exhibited superior performance in achieving high delignification (85.0%) and xylan removal (80.0%), while preserving a significant amount of cellulose (94.5%) compared to choline chloride-based DES. Notably, the pretreated eucalyptus residues showed a remarkable glucose yield of over 92.5%, representing a substantial enhancement of up to 15 times compared to untreated eucalyptus. Furthermore, the pretreated liquor yielded high-purity lignin with a yield of 97.8%, characterized by well-preserved ß-O-4 structure and nanoscale dimensions. These lignin nanoparticles (LNPs) were subsequently self-assembled into lignin nanobottles (LNBs), adding further value to the pretreatment process. The proposed novel binary EaCl-EG DES presented great potential as an efficient pretreatment solvent for future biomass fractionation processes.

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Cellulose-based aerogels offer exceptional promise for oily wastewater treatment, but the challenge of low mechanical strength and limited application functions persists. Inspired by the graded porous structures in the animal skeleton and bamboo stem, we firstly report here a stepwise solvent diffusion-induced phase separation approach for constructing the gradient pore-density three-dimensional (3D) cellulose scaffold (GPDS). Benefiting from the regulation of competitive hydrogen bonding between the anti-solvents and the ionic liquid (IL) in cellulose solution, GPDS exhibits the decreased major channels size and increased minor pores amount gradually along the solvent diffusion direction. These endow GPDS with the characteristics of low density (0.019 g/cm) and super strength (high up to 870 KPa). The application of GPDS in the field of oil-water separation has achieved remarkable results, including oil/organic solvent absorption (13-25 g/gGPDS), immiscible oil-water mixture separation (high efficiency up to 99.8 %, flux > 2000 L/m2·h), and surfactant-stabilized oil-in-water emulsion (efficiency up to 97.7 %). Moreover, a simple hydrophobic treatment further realizes the efficient separation of water-in-oil emulsion (98.5 % efficiency). The as-fabricated GPDS accordingly achieves the multifunctional application in oil-water separation field. Thus, a new avenue is opened to construct 3D cellulose porous scaffold as adsorbent materials in oily wastewater treatment.

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Given the escalating environmental and safety concerns, friendly protective materials with exceptional mechanical properties, biodegradability, and insensitivity to high temperature have received more and more attention. Here, we report a robust cellulosic gel through the multi-scale integration of cellulose molecular skeleton, nano-reinforced diatomite, and in situ polymerized polyacrylamide molecule. The bottom-up yet cross-scale approach facilitates the formation of cellulosic gel characterized by a highly interconnected hydrogen bond network and nano-enhanced domain, resulting in a tensile strength of up to 13.83 MPa, a Young's modulus exceeding 280 MPa, and an impact strength around 12.38 KJ m-1. Furthermore, this gel exhibits structural stability at temperatures up to 130 °C, good flame retardancy, and complete biodegradability within a span of 35 days. The robust cellulosic gel, acting as a pliable protector, demonstrates exceptional protection for human joints. Our study presents a highly efficient and scalable pathway towards the development of sustainable and robust biomass gels, holding immense potential in intelligent-protective wearables and advanced materials science and engineering.

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Nasal tamponade is a commonly employed and highly effective treatment method for preventing nasal bleeding. However, the current nasal packing hemostatic materials exhibit some limitations, such as low hemostatic efficiency, the potential for causing secondary injury when removed from the nasal cavity, limited intelligence in their design, and an inability to promote the healing of nasal mucosa wounds. Herein, we report the fabrication of a smart cellulose aerogel through the covalent cross-linking of carboxymethyl cellulose (CMC) macromolecules, while incorporating one-dimensional cellulose nanofibers (CNF) and two-dimensional MXene as reinforcing network scaffolds and conductive fillers. The abundant hydrogen and ether bonds in aerogels make them possess high elasticity in both dry and wet states, which can be compressed 100 times at 90 % deformation with a stress loss of <10 % under water. The highly elastic aerogels can be filled into the narrow nasal passages, pressuring the capillaries and reducing the amount of bleeding. Moreover, the strong interface between aerogels and blood can promote red blood cell aggregation, platelet adhesion and activation, activate intrinsic coagulation pathway and accelerate blood coagulation, resulting in excellent hemostatic ability. Furthermore, the aerogels exhibit excellent hemocompatibility and cytocompatibility, making them suitable for wound healing and capable of fully healing wounds within 15 days. Notably, the presence of MXene causes the aerogels to form a conductive network when exposed to blood, enabling them to perform real-time hemostatic monitoring without removing the dressing. This innovative biomedical aerogel, prepared from natural materials, shows excellent potential for applications in rapid nasal hemostasis.

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Sustainable composite hydrogel materials with harsh environmental adaption and tolerance capability have received considerable interests but still remain as challenges. In this work, biomimetic strategy was adapted for construction of three-dimensional galactomannan (GM) hydrogels with intercalation of flexible polymer chains polyethyleneimine (PEI), biomacromolecules tannin acid (TA) and CeO2 nanoparticles (NPs). The hydrogels cross-linked with double-networks (DN) present not only pH-responsive water absorption property, but also boosted mechanical strength with highest toughness of 326 kJ/m3 and Young's modulus of 220 kPa. Self-healing and anti-freezing capabilities were revealed for the hydrogels by maintaining of fracture elongation (23 %) and fracture strength (250 kPa). TA, CeO2 NPs as well as the amide groups in PEI of the hydrogels introduced excellent bacterial prohibition performance on both Bacillus subtilis (B. subtilis) and Escherichia coli (E. coli). Also, due to the existence of the free ions, the hydrogels exhibited electric conductive properties, with wide-range high sensitivity and long-time conductive stability. In addition, various tensile strain degrees were related to the conductive resistance values, and the great recovery performance was proved by cyclic tensile-conductive tests for 3000 times. Therefore, the proposed GM-based hydrogels displayed great potentials as strain sensors that are adaptable and tolerant to various environmental conditions.

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Exploration of functional materials based on sustainable and renewable biomolecules has been of much interest. Herein, nature-inspired photonic films were proposed by incorporation of bio-based lignin nanoparticles (LNPs) into chiral nematic cellulose crystals (CNCs). Evaporation induced self-assembly (EISA) formed oriented and layered structure of the nanocomposites iridescent films with enlarged helix pitches by intercalation of higher amounts of LNPs. Decreased crystallite sizes and expanding layer gaps indicated the homogeneous distribution and hydrophobic interactions between CNCs and LNPs. Distinguished UV absorption capabilities with over 90 % shielding capabilities in UVB region and increased hydrophobicity with the contact angle of 75° were achieved for the composite films due to the presence of hydrophobic lignin. The proposed optical films also showed outstanding cytocompatibility owing to all-natural components introduced into the materials, which may display great potentials in many fields such as stimuli sensing, anti-counterfeiting and wearable devices.

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Exploration of sustainable and functional materials from biomolecules has received much interest, while the limited mechanical property and possible bacterial contamination were proved to be their major shortages. Here, we proposed novel double network (DN) hydrogels based on galactomannan (GM) polysaccharide as backbone. Folic acid (FA) and polyacrylamide (PAM) were introduced to form hydrogen bond linkages and covalent bond networks respectively. The three-dimensional hydrogel networks showed greatly improved mechanical strength. Impressive compressive fatigue resistance was present for 100 cycles' compression forming only 0.7 % shape deformation. The phenomenon was mainly attributed to promoted stress-bearing and energy dissipation from the DN cross-linking. The GM hydrogels also exhibited good electronic conductivity and excellent anti-bacterial capabilities with inhibition against more than 80 % of E. coli., attributing to the tunable attachments of FA. Thus, we provided multi-functional hydrogels of high potential serving as anti-fatigue/bacterial and conductive strain sensors on the fields of wearable devices.

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Lignin, an abundant aromatic biopolymer, has the potential to produce various biofuels and chemicals through biorefinery activities and is expected to benefit the future circular economy. Microwave-assisted efficient degradation of lignin in methanol/formic acid over Ru/C catalyst cooperated with metal chloride was investigated, concerning the effect of type and dosage of metal chloride, dosage of Ru/C, reaction temperature, and reaction time on depolymerized product yield and distribution. Results showed that 91.1 wt% yield of bio-oil including 13.4 wt% monomers was obtained under the optimum condition. Yields of guaiacol-type compounds and 2,3-dihydrobenzofuran were promoted in the presence of ZnCl2. Formic acid played two roles: (1) acid-catalyzed cleavage of linkages; (2) acted as an in situ hydrogen donor for hydrodeoxygenation in the presence of Ru/C. A possible mechanism for lignin degradation was proposed. This work will provide a beneficial approach for efficient depolymerization of lignin and controllable product distribution.

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γ-Valerolactone (GVL), a biomass-derived green chemical, offers an environmentally responsible solvent for conversion of lignocellulose to high value-added chemicals. Herein, we report a two-step process for directly producing cellulosic residual, furfural and lignin from Miscanthus × giganteus (M. × giganteus) bypassing the isolation of xylose, which exhibits promising advantage in energy reduction. The optimized pretreatment (100 mM FeCl3 at 160 °C for 60 min) induced significant xylan removal (98.4%), resulting in rugged fibre surface, thus leading to the peak cellulose conversion of 99.3%. Furfural yield in the second step reached to 76.6% after 100 mM FeCl3 catalyzed GVL/H2O treatment at 180 °C for 10 min without addition of any chemical. The extracted lignin showed representative structure (such as ß-O-4', ß-ß' linkages) and medium molecular weight (4275.5 g/mol). 79.6% of furfural can be recovered by distillation. This study proposes a systematic and energy efficient approach for maximizing biomass utilization.

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Deep eutectic solvents (DESs) have received considerable interests as pretreatment solvents for biorefinery. In the present work, five kinds of dicarboxylic acids based DESs were introduced to pretreatments on moso bamboo (MB) with microwave irradiation assistance. Factors influencing the enzymatic conversion of MB cellulose to glucose were determined. With the fast heating, pretreated samples all present significant delignification and hemicelluloses matrix removal, thus improving the enzymatic conversion yield from 15% of MB to ~60%. For the DESs, hydrogen donors with less carbon atoms (oxalic acid) and more hydroxyl groups (tartaric acid) displayed higher efficiency due to separation of aggregated cellulose microfibrils. The microwave assisted DESs (MW-DESs) pretreatments also contributed to cellulose crystal variations including decrystallization and more exposure of hydrophobic surfaces, which are beneficial for followed cellulase adsorption and hydrolysis. The exploration of fast MW-DESs pretreatments may expand the potentials of lignocellulose biomass on effective and applicable biorefinery.

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In this study, an alkaline-catalyzed sulfolane/water solvent system was developed for isolating high-purity and antioxidative lignin from willow (Salix matsudana cv. Zhuliu). Optimization of the pretreatment conditions such as temperature, sulfolane/water ratio, and alkaline catalyst (NaOH) dosage were comprehensively investigated for effective lignin extraction from willow. The 44.4% of lignin was recovered from the biomass with 54% of delignification in 50/50 (w/w) sulfolane/water system at 170 °C. As the addition of the alkaline catalyst (NaOH) increased to 4%, the delignification yield was increased up to 94% with about 70% of lignin recovery yield. The recovered lignin was comparatively investigated with its control, milled wood lignin (MWL). The ß-O-4 linkages and phenolic hydroxyl were well preserved in the extracted lignin fractions with the sulfolane/water system. Furthermore, excellent radical scavenging ability was observed with the extracted lignins by sulfolane/water pretreatments owing to rich phenolic hydroxyl groups in the lignins. Hence, systematical investigation on the lignin properties and potential applications under sulfolane organosolv pretreatment would promote the utilization of lignin in biorefinery processes.

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Microwave-assisted degradation of alkaline lignin in methanol/formic acid media was investigated, concerning the effect of formic acid (FA) amount, reaction temperature, and reaction time on lignin depolymerization. The highest bio-oil yield of 72.0 wt% including 6.7 wt% monomers was achieved at 160 °C and a FA-to-lignin mass ratio of 4 after a reaction time of 30 min. Among the monomers, the yield of 2,3-dihydrobenzofuran was the highest (3.00 wt%), followed by p-coumaric acid (1.59 wt%). Formic acid acted mainly through acid-catalyzed cleavage of the linkages in lignin. Oligomers in bio-oil were mainly composed of dimers (molecular weight: 253-378) and trimers (molecular weight: 379-510) according to the Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) analysis. A possible mechanism about microwave-assisted depolymerization of lignin in methanol/formic acid media was proposed. This study will provide an efficient approach for lignin depolymerization.

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BACKGROUND: Solid acid catalyzed inexpensive ionic liquid (IL) pretreatment is promising because of its effectiveness at decreasing biomass recalcitrance to subsequent enzymatic hydrolysis or in situ hydrolysis of carbohydrate oligomers. However, the conventional strategy was limited by the complex non-isothermal process and considering only one aspect of sugar recovery. In this study, facile isothermal pretreatments using Amberlyst 35DRY catalyzed 1-n-butyl-3-methylimidazolium chloride ([C4mim]Cl) at mild conditions were developed on bioenergy crop Arundo donax Linn. to enhance the combined sugars released. The physicochemical differences, enzymatic digestibility, and sugars released in situ were evaluated and compared to define the best set of conditions. RESULTS: The optimized isothermal pretreatment (110 °C, IL for 3 h, Amberlyst for 1 h) resulted in significant enhancement in combined sugars released (58.4 g/100 g raw materials), recovering 85.0 % of the total reducing glycan in the raw biomass. This remarkable improvement could be correlated to cellulose crystallinity reduction, crystalline conversion, and partial removal of the main chemical components caused by the pretreatment. Particularly, solubilization of hemicelluloses and partial depolymerization of cellulose contributed to the synergetic improvement of sugars production in enzymatic hydrolysis and in situ. Irrespective of the generous differences in mass recovery, the highest cellulose digestibility of 90.2 % and sugar released of 43.0 % (based on initial materials) in the pretreatment liquor were obtained. Interestingly, lignin (0.8-6.1 %) and sugars derived lactic acid (4.70-5.94 %) were produced without any notable deleterious effects. CONCLUSIONS: Isothermal [C4mim]Cl-Amberlyst pretreatment was a highly effective, simple, and convenient process that produced high yields of fermentable sugars from recalcitrant biomass by in situ hydrolysis of soluble biomass and enhancement of cellulose digestibility of the regenerated biomass. Relatively high amount of new revenues beyond sugars of this pretreatment could promote the commercial viability.

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Solid acid-enhanced ionic liquid (IL) pretreatment is of paramount importance for boosting the yield of sugars from biomass cost-effectively and environmentally friendly. To unravel the chemical and supramolecular structural changes of lignin after pretreatment, IL-acid lignin (ILAL) and subsequent residual cellulolytic enzyme lignin (RCEL) were isolated from Arundo donax Linn. The structural features were compared with those of the corresponding milled wood lignin (MWL). Results indicated that the pretreatment caused loss of ß-O-4', ß-ß', ß-1' linkages and formation of condensed structures in lignin. A preferential breakdown of G-type lignin may have occurred, evidenced by an increased S/G ratio revealed by 2D HSQC NMR analysis. It was determined that the depolymerization of ß-O-4' linkage, lignin recondensation, and cleavage of ferulate-lignin ether linkages took place. Moreover, a simulation module was first developed to define morphological changes in lignin based on AFM and TEM analyses. Briefly, tree branch like aggregates was destroyed to monodisperse particles.

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