Biomimetic construction of environmental-tolerant composite hydrogels based on galactomannan for tough, flexible and conductive sensors.

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.

Nature-inspired construction of iridescent CNC/Nano-lignin films for UV resistance and ultra-fast humidity response.

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.

Stretchable and fatigue resistant hydrogels constructed by natural galactomannan for flexible sensing application.

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.

Efficient depolymerization of lignin through microwave-assisted Ru/C catalyst cooperated with metal chloride in methanol/formic acid media.

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.

Valorization of Miscanthus × giganteus by γ-Valerolactone/H2O/FeCl3 system toward efficient conversion of cellulose and hemicelluloses.

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.

Promoting enzymatic hydrolysis of aggregated bamboo crystalline cellulose by fast microwave-assisted dicarboxylic acid deep eutectic solvents pretreatments.

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.

Pretreatment of willow using the alkaline-catalyzed sulfolane/water solution for high-purity and antioxidative lignin production.

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.

Microwave-assisted efficient depolymerization of alkaline lignin in methanol/formic acid media.

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.

Facile isothermal solid acid catalyzed ionic liquid pretreatments to enhance the combined sugars production from Arundo donax Linn.

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.

Unraveling the Structural Modifications in Lignin of Arundo donax Linn. during Acid-Enhanced Ionic Liquid Pretreatment.

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.