Synthesis of Silver Nanoparticles and Detection of Glucose via Chemical Reduction with Nanocellulose as Carrier and Stabilizer.

The application of silver nanoparticles (AgNPs) in antibacterial materials, glucose detection, etc., is of broad interest for researchers around the world. Nanocellulose with many excellent properties can be used as a carrier and stabilizer to assist in the synthesis of AgNPs. In this study, cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs) were used to assist in the synthesis of AgNPs under the reduction of glucose and detection of glucose concentration under different conditions. Transmission electron microscopy (TEM) analysis showed that the AgNPs in the nanocellulose-AgNPs (NC-AgNPs) system were roughly spherical and randomly distributed on the nanocellulose. In the whole reaction system, when the concentration of nanocellulose is 0.11 mg/mL, the concentration of silver ammonia solution is 0.6 mM, and the mixing time is 2.5 h, according to the UV-Vis analysis, the absorbance of CNF-AgNPs at 425 nm exhibited a good linear relationship (R2 = 0.9945) with the glucose concentration range (5-50 µM), while the absorbance of CNC-AgNPs at 420 nm showed a good linear relationship (R2 = 0.9956) with the glucose concentration range (5-35 µM). The synthesis of NC-AgNPs can be further developed into a sensor with higher sensitivity and higher stability for detecting glucose concentration and a material with antibacterial effects.

Switchable Deep Eutectic Solvents for Lignin Dissolution and Regeneration.

Deep eutectic solvents (DESs) are promising for lignin dissolution and extraction. However, they usually possess high polarity and are difficult to recycle. To overcome this drawback, a variety of switchable ionic liquids (SILs) composed of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and alcohols was synthesized and screened. According to the thermodynamic modeling suggestions, the selected DBU-HexOH SIL was coupled with hydrogen-bond donors to form switchable-DES (SDES) systems with moderated viscosity, conductivity, and pH while maintaining switchability. The SDESs produced a well-improved lignin and lignin model compound solubility compared with those of SILs; charging CO2 into SDES (SDESCO2) caused a further increase in solubility. The solubility (25 °C) of syringic acid, ferulic acid, and milled wood lignin in SDESCO2 reached 230.57, 452.17, and 279.12 mg/g, respectively. Such SDES-dissolved lignin can be regenerated using acetone as an anti-solvent. The SDES-regenerated lignin exhibited a well-preserved structure with no noticeable chemical modifications. Furthermore, the SDESCO2 lignin possessed a higher molecular weight (Mw = 10,340 g/mol; Mn = 7672 g/mol), improved uniformity (polydispersity index = 1.35), and a higher guaiacyl lignin unit content compared with the original milled wood lignin. The SDES system proposed in the present work could benefit the fractionation of lignin compounds and facilitate downstream industrial processes.

Strength Enhancement of Regenerated Cellulose Fibers by Adjustment of Hydrogen Bond Distribution in Ionic Liquid.

To improve the physical strength of regenerated cellulose fibers, cellulose dissolution was analyzed with a conductor-like screening model for real solvents in which 1-allyl-3-methylimidazolium chloride (AMIMCl) worked only as a hydrogen bond acceptor while dissolving the cellulose. This process could be promoted by the addition of urea, glycerol, and choline chloride. The dissolution and regeneration of cellulose was achieved through dry-jet and wet-spinning. The results demonstrated that the addition of hydrogen bond donors and acceptors either on their own or in combination can enhance the tensile strength, but their effects on the crystallinity of the regenerated fibers were quite limited. Compared with the regenerated fibers without any additives, the tensile strength was improved from 54.43 MPa to 139.62 MPa after introducing the choline chloride and glycerol, while related the crystallinity was only changed from 60.06% to 62.97%. By contrast, a more compact structure and fewer pores on the fiber surface were identified in samples with additives along with well-preserved cellulose frameworks. Besides, it should be noted that an optimization in the overall thermal stability was obtained in samples with additives. The significant effect of regenerated cellulose with the addition of glycerol was attributed to the reduction of cellulose damage by slowing down the dissolution and cross-linking in the cellulose viscose. The enhancement of the physical strength of regenerated cellulose fiber can be realized by the appropriate adjustment of the hydrogen bond distribution in the ionic liquid system with additives.

The Dual Effect of Ionic Liquid Pretreatment on the Eucalyptus Kraft Pulp during Oxygen Delignification Process.

Oxygen delignification presents high efficiency but causes damage to cellulose, therefore leading to an undesired loss in pulp strength. The effect of ionic liquid pretreatment of [BMIM][HSO4] and [TEA][HSO4] on oxygen delignification of the eucalyptus kraft pulp was investigated at 10% IL loading and 10% pulp consistency, after which composition analysis, pulp and fiber characterizations, and the mechanism of lignin degradation were carried out. A possible dual effect of enhancing delignification and protecting fibers from oxidation damage occurred simultaneously. The proposed [TEA][HSO4] pretreatment facilitated lignin removal in oxygen delignification and provided fibers with improved DP, fiber length and width, and curl index, resulting in the enhanced physical strength of pulp. Particularly, its folding endurance improved by 110%. An unusual brightness reduction was identified, followed by detailed characterization on the pulps and extracted lignin with FTIR, UV, XPS, and HSQC. It was proposed that [TEA][HSO4] catalyzed the cleavage of ß-O-4 bonds in lignin during the oxygen delignification, with the formation of Hibbert's ketones and quinonoid compounds. The decomposed lignin dissolved and migrated to the fiber surface, where they facilitated the access of the oxidation agent and protected the fiber framework from oxidation damage. Therefore, it was concluded that ionic liquid pretreatment has a dual effect on oxygen delignification.

High-Strength Regenerated Cellulose Fiber Reinforced with Cellulose Nanofibril and Nanosilica.

In this study, a novel type of high-strength regenerated cellulose composite fiber reinforced with cellulose nanofibrils (CNFs) and nanosilica (nano-SiO2) was prepared. Adding 1% CNF and 1% nano-SiO2 to pulp/AMIMCl improved the tensile strength of the composite cellulose by 47.46%. The surface of the regenerated fiber exhibited a scaly structure with pores, which could be reduced by adding CNF and nano-SiO2, resulting in the enhancement of physical strength of regenerated fibers. The cellulose/AMIMCl mixture with or without the addition of nanomaterials performed as shear thinning fluids, also known as "pseudoplastic" fluids. Increasing the temperature lowered the viscosity. The yield stress and viscosity sequences were as follows: RCF-CNF2 > RCF-CNF2-SiO22 > RCF-SiO22 > RCF > RCF-CNF1-SiO21. Under the same oscillation frequency, G' and G" decreased with the increase of temperature, which indicated a reduction in viscoelasticity. A preferred cellulose/AMIMCl mixture was obtained with the addition of 1% CNF and 1% nano-SiO2, by which the viscosity and shear stress of the adhesive were significantly reduced at 80 °C.

Enhancement of Lignin Extraction of Poplar by Treatment of Deep Eutectic Solvent with Low Halogen Content.

A novel choline-based deep eutectic solvent (DES) with low halogen content-namely choline lactate-lactic acid (CLL)-was synthesized by replacing the chloride anion with lactate anion in choline chloride-lactic acid (CCL). CLL and CCL treatments were conducted at 140 °C for 12 h with hydrogen bond acceptor/hydrogen bond donor =1/10, thereafter composition analysis and characterizations of the lignin extracted by DES treatment (DES lignin) and the solid residue were carried out. The proposed low halogen content DES presented an improved lignin extraction efficiency. The CLL treatment extracted 90.13% of initial lignin from poplar, while CCL extracted 86.02%. In addition, the CLL treatment also provided DES lignin with an improved purity (91.17%), lower molecular weight (Mw/Mn=1805/971 g/mol) and more concentrated distribution (polydispersity index=1.86). The efficient lignin extraction was mainly ascribed to the cleavage of ß-O-4 bonds in lignin macromolecule, especially in the guaiacyl units, thereby breaking them into smaller molecules, facilitating the lignin extraction. The replacement of chloride anion allowed CLL acting as a more efficient DES to interact with lignin macromolecules, thus providing lignin with higher uniformity and suitable molecular weight. The low halogen content DES system proposed in present work could benefit the fractionation of biomass, improve the valorization of lignin compounds and facilitate industrial process in the downstream.