Highly Transparent, Strong, and Flexible Films with Modified Cellulose Nanofiber Bearing UV Shielding Property.

This work investigates multifunctional composite films synthesized with cellulose nanofibers (CNFs) and poly(vinyl alcohol) (PVA). First, TEMPO-oxidized CNFs were modified in the heterogeneous phase with benzophenone, diisocyanate, and epoxidized soybean oil via esterification reactions. A thorough characterization was carried out via elemental analysis as well as FT-IR and X-ray photoelectron spectroscopies and solid-state NMR. Following, the surface-modified CNFs were combined with PVA to endow composite films with UV-absorbing capabilities while increasing their thermomechanical strength and maintaining a high light transmittance. Compared to neat PVF films, the tensile strength, Young modulus, and elongation of the films underwent dramatic increases upon addition of the reinforcing phase (maximum values of ∼96 MPa, ∼ 714 MPa, and ∼350%, respectively). A high UV blocking performance, especially in the UVB region, was observed for the introduced multifunctional PVA films at CNF loadings below 5 wt %. The trade-off between modified nanofibril function as interfacial reinforcement and aggregation leads to an optimum loading. The results indicate promising applications, for example, in active packaging.

Preparation and characterization of cellulose nanofibril/chitosan aerogels with high-adsorbability and sensitive indication for indoor free formaldehyde.

The toxic volatile organic compounds (VOCs), especially formaldehyde (FA), released from decoration materials pose a great threat to human health. In this study, formaldehyde adsorption performance of the specially formulated nanocellulose/chitosan aerogel (CNFCA) was investigated in simulated atmosphere. The physicochemical property of the composite aerogel was characterized, which had a large specific surface area (153.67 m2/g), a rough surface and an ultra-thin and porous structure. The composite aerogel showed excellent adsorption capacity for the formaldehyde, its theoretical maximum adsorption capacity was as high as 83.89 mg/g, and the adsorption process was more in accordance with the pseudo-second-order kinetics. The chromogenic reaction between the 4-amino-3-benzo-5-mercapto-1,2,4-triazolium (AHMT) and CNFCA was found that the color of the composite aerogel was depended on the free formaldehyde concentration. Based on this phenomenon, a colorimetric card was proposed and built to detection the formaldehyde in the atmosphere. Moreover, the adsorption mechanism research was found that the CNFCA with a multilayer structure belonged to physicochemical complex adsorption.

Efficient Fast Fractionation of Biomass Using a Diol-Based Deep Eutectic Solvent for Facilitating Enzymatic Hydrolysis and Obtaining High-Quality Lignin.

Current DES pretreatment is often performed under relatively severe conditions with high temperature, long time, and high DES usage. This work studied a short-time diol DES (deep eutectic solvent) pretreatment under mild conditions to fractionate the bamboo, facilitate enzymatic hydrolysis, and obtain high-quality lignin. At an optimized condition of 130 °C for only 10 min, lignin and xylan removal reached 61.34 % and 84.15 %, with residual glucan showing a ~90 % enzymatic hydrolysis yield. Equally important, the dissolved lignin could be readily recovered with 97.51 % yield, exhibiting 96.65 % ß-O-4 preservation. The fractionation and lignin protection mechanisms were unveiled by XRD, FTIR, cellulose-DP, 2D HSQC NMR, 31P NMR and GPC analysis. This study highlighted that short-time fractionation of bamboo can be achieved by a diol-based DES which is an ideal strategy to upgrade the lignocellulose biomass for high enzymatic hydrolysis yields and high-quality lignin stream.

Selective degradation of hemicellulose and lignin for improving enzymolysis efficiency via pretreatment using deep eutectic solvents.

Deep eutectic solvents (DESs) with different acidity and alkalinity were applied for biomass pretreatment, and the conditions were optimized by response surface methodology. The results showed that lactic acid/betaine hydrochloride had the optimal pretreatment efficiency, where the removal rates of hemicellulose and lignin came up to 89% and 73%, and the enzymolysis efficiency was as high as 92%. Furthermore, eight types of chloride salts with different valence states were introduced into the DESs as the third component. The chloride salts could improve the pretreatment efficiency and positively correlated with the metal valence state. Specifically, AlCl3 was significantly superior in improving the pretreatment efficiency, where the enzymolysis efficiency reached 96% due to the destruction of crystalline region and the esterification of partial cellulose. Therefore, it is proposed that adding highly valent metal salts to acidic DESs has higher pretreatment and enzymatic efficiency.

A novel mineral-acid free biphasic deep eutectic solvent/γ-valerolactone system for furfural production and boosting the enzymatic hydrolysis of lignocellulosic biomass.

The failure of hemicellulose valorization in a deep eutectic solvent (DES) pretreatment has become a bottleneck that challenges its further development. To address this issue, this study developed a DES/GVL (γ-valerolactone) biphasic system for effective hemicellulose-furfural conversion, enhanced cellulose saccharification and lignin isolation. The results indicated that the biphasic system could significantly improve the lignin removal (as high as 89.1%), 86.0% higher than the monophasic DES, accompanied by âˆ¼100% hemicellulose degradation. Notably, the GVL in the biphasic solvent restricted the condensation of hemicellulose degradation products, which as a result generated large amount of furfural in the pretreatment liquid with a yield of 68.6%. With the removal of hemicellulose and lignin, cellulose enzymatic hydrolysis yield was boosted and reached near 100%. This study highlighted that the novel DES/GVL is capable of fractionating the biomass and benefiting their individual utilization, which could provide a new biorefinery configuration for a DES pretreatment.

Alkali-facilitated deep eutectic solvent for effective bamboo saccharification.

Herein, a Na2S promoted deep eutectic solvent (DES) was established to reduce the natural recalcitrance of moso bamboo (MB) and improve the subsequent enzymatic saccharification. It was found that the addition of Na2S (Choline chloride/Ethylene glycol/Na2S) dramatically promoted the deconstructions of lignin with highest removal of 74.67 %, but at the same time preserved glucan and hemicellulose to the maximum extent. With the fractionation, the enzymatic saccharification yield of pretreated MB can reach 100 % under the pretreatment condition of 140 °C, and lignin could be readily recovered with a high yield of 81.47 %. The proposed DES is superior to normal alkaline DES in terms of the higher lignin removal and recovery yield, carbohydrate preservation and enzymatic digestibility, which indicated Na2S as a novel and powerful reinforcer enhancing the DES fractionation efficiency.

The bamboo delignification saturation point in alkaline hydrogen peroxide pretreatment and its association with enzymatic hydrolysis.

A delignification saturation point (DSP) was observed for bamboo alkaline hydrogen peroxide pretreatment (AHP). Lignin removal was increased from 52.23% to ∼70% when increasing H2O2 dosage from 0% to 2% at the optimum pH, but it cannot be further reinforced as increasing the H2O2. With partial lignin preserved, the glucan hydrolysis yield was found to have a ceiling of ∼80%. This study indicated a strong association between enzymatic digestibility and lignin removal. Anatomical analysis by fluorescence microscope and confocal Raman microscope revealed that the undegradable lignin was mainly existing in the cell corner of sclerenchyma fibers, causing the DSP in the bamboo AHP. Finally, the residual lignin in pretreated bamboo was characterized with GPC, HSQC NMR, and 31P NMR, which revealed the nature of DSP. This study could help to understand the lignin modification during the AHP and further contribute to the establishment of a chemical-saving biorefinery.

Assessing the availability of two bamboo species for fermentable sugars by alkaline hydrogen peroxide pretreatment.

This study comprehensively investigated two bamboo species (i.e. Neosinocalamus affinis and Phyllostachys edulis) in terms of their cell wall ultrastructure, chemical compositions, enzymatic saccharification, and lignin structure before and after alkaline hydrogen peroxide pretreatment (AHP). During AHP, Neosinocalamus affinis (NAB) had higher delignification than Phyllostachys edulis (PEB), and thus showed better enzymatic digestibility (93.05% vs 53.57% for glucan). The fundamental chemical behavior of the bamboo lignins was analyzed by fluorescence microscope (FM), confocal Raman microscope (CRM), molecular weight analysis, and 2D HSQC-NMR. Results indicated that the PEB has thicker cell wall and more concentrated lignin in its compound middle lamella and cell corner middle lamella than NAB. Moreover, PEB lignin contains more G units (S/G of 0.95), in evident contrast to that of NAB lignin (S/G of 1.30), which favor the formation of C-C linkages, thus impeding its degradation during the AHP.

Utilization of guaiacol-based deep eutectic solvent for achieving a sustainable biorefinery.

This study proposed a renewable deep eutectic solvent (DES) pretreatment using lignin-derived guaiacol as the hydrogen bond donor. The DES showed excellent biomass fractionation efficiency after the incorporation of trace AlCl3 as the reinforcer, which removed 79.1 % lignin while preserving more than 90 % glucan. The pretreated bamboo exhibited 96.2 % glucan enzymatic hydrolysis yield at only 110 °C. The physicochemical properties of the pretreated solids were comprehensively investigated to explain how the DES fractionation overcame the biomass recalcitrance. The regenerated lignin from the DES pretreatment was also analyzed, which revealed that lignin ß-O-4 bond was significantly cleaved. This guaiacol-based DES could greatly contribute to establish a closed-loop biorefinery sequence with high lignin fractionation efficiency and great solvent recyclability.

Facilitating enzymatic hydrolysis with a novel guaiacol-based deep eutectic solvent pretreatment.

Herein, we established a novel deep eutectic solvent (DES) using lignin-derived guaiacol as hydrogen bond donor (HBD). The sole ChCl/guaiacol system was found to be inefficient for the fractionation of wheat straw (WS), while the incorporation of trace AlCl3 significantly facilitated the degradation of hemicellulose and lignin, resulting in a complete enzymatic digestibility of the pretreated WS. Further, this study revealed that the DES-degraded lignin was readily precipitated during the washing process, and thus hindered the enzymatic hydrolysis of poplar and bamboo (with hydrolysis yield of 42.03% and 71.67%, respectively). Alkali washing offers a possible approach to remove the precipitated lignin, after which a near 100% hydrolysis yield was also obtained for poplar and bamboo.

VS2 and its doped composition: Catalytic depolymerization of alkali lignin for increased bio-oil production.

VS2 spheres and VS2 sheets with doped compositions (Mo, Ag and graphite) were successfully prepared by one-step hydrothermal method and characterized by different techniques including X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption isotherms. Catalysts were applied for the depolymerization of alkali lignin. VS2 spheres exhibited lower yield of degraded lignin and bio-oil than those with VS2 sheets and VS2 flowers heated to 250 °C and held for 1.5 h with 2.0 MPa H2. The catalytic depolymerization performance was markedly affected by the dopant in the VS2 sheets, with the highest degraded lignin yield of 81.22%, achieved over 5 wt% Ag-VS2 at 290 °C under 2.0 MPa H2 for 1.5 h, yielding 61.23% bio-oil. The VS2-based catalysts show excellent selectivity in the interruption of the lignin structure and target production of bio-oil. The bio-oil showed that the relevant contents of a phenolic-type compound changes significantly according to the dopant in the VS2 catalyst.

Size-Controlled and Super Long-Term Stable Lignin Nanospheres through a Facile Self-Assembly Strategy from Kraft Lignin.

In diverse fields, much attention has been concentrated on the preparation of lignin nanospheres with various structures. Here we report a facile self-assembly strategy for preparing super long-term stable hollow and solid nanospheres based on lignin fractionation. We found that different lignins obtained at different pHs during fractionation can form nanospheres with different particle sizes and structures. The self-assembled and formation mechanisms of the nanospheres were surveyed by dynamic light scattering (DLS), elemental analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The analysis results showed that the phenolic hydroxyl groups and the intermolecular π-π interaction play a decisive effect in the formation of nanospheres. This study can not only facilitate the advance of lignin-based nanotechnologies but also provide a broad prospect for the use of black liquor.

Synergistic enhancement of nanocellulose foam with dual in situ mineralization and crosslinking reaction.

Cellulose nanocrystals (CNCs) foams have recently gained research interests because they are renewable, abundant, biodegradable and exhibit high surface area. However, the application of CNCs-based foams is still challenging, which is attributed to its lack of effective entanglements between the CNCs particles, thus lowering foam properties. In this study, a synergistic enhancement strategy was proposed, based on the in situ mineralization with hydroxyapatite (HAP) layer onto the CNCs surface, followed by a chemical crosslinking reaction. The physical and chemical structures of the composites were analyzed with SEM, STEM, XRD, FTIR, and TGA. By controlling the amount of coated HAP and the crosslinker, it is possible to manufacture a series of CNCs-based foams that are lightweight (50-75 mg/cm3), highly porous (~90%) with high water absorption (>1300%) and outstanding mechanical strength properties (as high as 1.37 MPa). Moreover, our study further indicated that these CNCs/HAP materials could increase the proliferation of rat osteoblast cells. The method developed in this study presents a novel approach to design improved networked CNCs foam, which has the potential to be used in thermal-retardant material, wastewater treatment, tissue engineering, and personal care applications.

Maximizing enzymatic hydrolysis efficiency of bamboo with a mild ethanol-assistant alkaline peroxide pretreatment.

To overcome the delignification saturation point in traditional alkaline hydrogen peroxide pretreatment (AHP), a powerful modified AHP delignification methodology was established by introducing ethanol into the system. The pretreatment caused significant lignin removal of bamboo at elevated pretreatment temperature with the highest lignin removal reaching 80.0% at 100 °C, higher than that (74.9% lignin removal) in pretreatment without the ethanol assistance. In addition, a certain amount of carbohydrates was also solubilized during the process whose recovery was 83.3% (glucan) and 67.6% (hemicellulose), respectively. The pretreated solid exhibited excellent enzymatic digestibility, with hydrolysis yields of ~100% and 95.7% for glucan and xylan, respectively. Our studies further indicate that this delignification methodology is versatile for hardwood and herbaceous plants, but does not perform well on softwood.

Comparison of mixed enzymatic pretreatment and post-treatment for enhancing the cellulose nanofibrillation efficiency.

In this work, lignocellulosic nanofibrils (LCNF) produced from mechanical fibrillation with mixed enzymatic pretreatment or post-treatment were compared and the chemical composition, water retention value (WRV), average-number height and crystallinity for the obtained LCNF were evaluated. Compared to pure mechanical fibrillation, both mixed enzymatic pretreatment and post-treatment could efficiently facilitate cellulose nanofibrillation. Moreover, mixed enzymatic pretreatment was more suitable for LCNF production, resulting in a relatively higher WRV of 909% and smaller average-number height of 15 nm. These discoveries provide new insights into a more efficient biological method for the production and application of cellulose nanomaterials.

Lignocellulosic nanofibrils produced using wheat straw and their pulping solid residue: From agricultural waste to cellulose nanomaterials.

Each year millions of tons of agricultural wastes are produced, however, not well utilized in China. Considering the economic development and environmental protection, the valorization of these wastes is increasingly necessary and important. Here we used p-toluenesulfonic acid hydrolysis followed by mild disk grinding for on-farm valorization of wheat straw (WS) and their pulping solid residue (waste wheat straw, WWS) to produce lignocellulosic nanofibrils (LCNF). Alkaline peroxide post-treatment was further conducted to obtain purified lignocellulosic nanofibrils (P-LCNF) with lower lignin content and thinner diameters. The raw materials and resulting LCNF and P-LCNF were investigated in each process for their chemical component, crystal structure, morphology, and thermal properties. Interestingly, although WS fiber had higher lignin content than WWS fiber, the WS fiber with lower ash content resulted in LCNF and P-LCNF with smaller height and lower thermal stability, but higher crystallinity and higher specific surface area. Higher ash content in WWS fiber protected cellulose and lignin from depolymerization and degradation, respectively, which endowed LCNF and P-LCNF with entangled network structure. Overall, this study indicated that the low-temperature fractionation process on WS and WWS fibers could yield cellulose nanomaterials with potential value-added application and achieve the efficient utilization of agricultural wastes.

Bio-inspired nanocomposite by layer-by-layer coating of chitosan/hyaluronic acid multilayers on a hard nanocellulose-hydroxyapatite matrix.

This study proposed a layer-by-layer technique on the hard CNCs/hydroxyapatite (HAP) matrix using biodegradable and biocompatible chitosan and hyaluronic acid (HA). Inspired by the mineralized collagen in human bone, the CNCs/HAP matrix was synthesized by a facile in situ HAP coating on the CNCs fibers. The chemical and crystalline structure of the CNCs/HAP matrix was investigated with FTIR, XRD, HRTEM, and SAED. The surface of the CNCs/HAP matrix was analyzed by AFM which showed a flat structure with a roughness of 23.12 nm, however, the surface roughness increased to 56.09 nm with the assembly of chitosan and HA. After the LBL assembly, the surface hydrophilicity of the CNCs/HAP films was improved. Moreover, the CNCs/HAP matrix showed enhanced mechanical property than pure CNCs matrix. Although there is compromise in the mechanical property after the LBL assembly, it is anticipated its bioaffinity and biocompatibility will increase with the incoporation of chitosan and HA.

Improving cellulose nanofibrillation of waste wheat straw using the combined methods of prewashing, p-toluenesulfonic acid hydrolysis, disk grinding, and endoglucanase post-treatment.

Here we established a new approach for improving the cellulose nanofibrillation of high ash content waste wheat straw (WWS). The results were comprehensively elucidated from the ash removal, delignification, mechanical fibrillation and endoglucanase post-treatment. When water dosage was increased from 50 to 500 times of the WWS weight, the ash content gradually decreased during prewashing process, which facilitated lignin solubilization in subsequent p-toluenesulfonic acid (p-TsOH) hydrolysis. Approximately 80% of lignin in prewashed WWS could be dissolved during acid hydrolysis to result in a relatively higher crystallinity of 59.1%. Compared with the lignocellulosic nanofibrils (LCNF) directly obtained using acid hydrolysis and disk grinding, prewashing-assisted acid hydrolyzed WWS was fibrillated into LCNF with smaller height of 57.0 nm. Mild endoglucanase post-treatment could further produce less entangled LCNF with thinner diameters. In short, this study presented a promising and green pathway to achieve an efficient utilization of agricultural residue wastes to cellulose nanomaterials.