Although conversion of low value but high-volume lignin by-product to its usable form is one of the determinant factors for building an economically feasible integrated lignocellulose biorefinery, it has been challenged by its structural complexity and inhomogeneity. We and others have shown that uniform lignin nanoparticles can be produced from a wide range of technical lignins, despite the varied lignocellulosic biomass and the pretreatment methods/conditions applied. This value-added nanostructure lignin enriched with multifunctional groups can be a promising versatile material platform for various downstream utilizations especially in the emerging nanocomposite fields. Inspired by the story of successful production and application of nanocellulose biopolymer, two types of uniform lignin nanoparticles (LNPs) were prepared through self-assembling of deep eutectic solvent (DES) and ethanol-organosolv extracted technical lignins derived from a two-stage fractionation pretreatment approach, respectively. Both LPNs exhibited sphere morphology with unique core–shell nanostructure, where the DES–LNPs showed a more uniform particle size distribution. When incorporated into the traditional polymeric matrix such as poly(vinyl alcohol), these LPN products displayed great potential to formulate a transparent nanocomposite film with additional UV-shielding efficacy (reached ~80% at 400 nm with 4 wt% of LNPs) and antioxidant functionalities (reached ~160 μm mol Trolox g−1 with 4 wt% of LNPs). At the same time, the abundant phenolic hydroxyl groups on the shell of LNPs also provided good interfacial adhesion with PVA matrix through the formation of hydrogen bonding network, which further improved the mechanical and thermal performances of the fabricated LNPs/PVA nanocomposite films. Both LNPs are excellent candidates for producing multifunctional polymer nanocomposites using facile technical route. The prepared transparent and flexible LNPs/PVA composite films with high UV-shielding efficacy, antioxidant activity, and biocompatibility are promising in the advanced packaging field, which potentially provides an additional high-value lignin product stream to the lignocellulose biorefinery. This study could open the door for the production and application of novel LNPs in the nascent bioeconomy.

Current single-stage delignification-pretreatment technologies to overcome lignocellulosic biomass recalcitrance are usually achieved at the expense of compromising the recovery of the polysaccharide components, particularly the hemicellulose fraction. One way to enhance overall sugar recovery is to tailor an efficient two-stage pretreatment that can pre-extract the more labile hemicellulose component before subjecting the cellulose-rich residual material to a second-stage delignification process. Previous work had shown that a mild steam pretreatment could recover >65% of the hemicellulose from poplar while limiting the acid-catalysed condensation of lignin. This potentially allowed for subsequent lignin extraction using various lignin solvents to produce a more accessible cellulosic substrate. A two-stage approach using steam and/or solvent pretreatment was assessed for its ability to separate hemicellulose and lignin from poplar wood chips while providing a cellulose-rich fraction that could be readily hydrolysed by cellulase enzymes. An initial steam-pretreatment stage was performed over a range of temperatures (160–200 °C) using an equivalent severity factor of 3.6. A higher steam temperature of 190 °C applied over a shorter residence time of 10 min effectively solubilized and recovered 75% of the hemicellulose while enhancing the ability of various solvents [deep eutectic solvent (DES), ethanol organosolv, soda/anthraquinone (soda/AQ) or a hydrotrope] to extract lignin in a second stage. When the second-stage treatments were compared, the mild DES treatment (lactic acid and betaine) at 130 °C, removed comparable amounts of lignin with higher selectivity than did the soda/AQ and organosolv pretreatments at 170 °C. However, the cellulose-rich substrates obtained after the second-stage organosolv and soda/AQ pretreatments showed the highest cellulose accessibility, as measured by the Simon’s staining technique. They were also the most susceptible to subsequent enzymatic hydrolysis. The second-stage pretreatments varied in their ability to solubilize and extract the lignin component of steam-pretreated poplar while enhancing the enzymatic hydrolysis of the resulting cellulose-rich residual fractions. Although DES extraction was more selective in extracting lignin from the steam-pretreated substrates, the organosolv and soda/AQ post treatments disrupted the cellulose structure to a greater extent while enhancing the ease of enzymatic hydrolysis.

Although recent work has shown natural lignin products are promising to fabricate various polymer based functional composites, high-value applications were challenged by their structural complexity and inhomogeneity. This work specially assessed the potential of four technical lignins for cellulose based functional films production. These four technical lignins were obtained by emerging pretreatment systems, i.e., lactic acid-betaine deep eutectic solvent (DES), ethanol organosolv, soda/anthraquinone (Soda/AQ) and the sodium salicylate hydrotrope, and their phenolic substructures were comparatively identified by prevalent ³¹P NMR technique. The influence of lignin chemical structure on the antioxidant potential and UV-shielding performance of the prepared cellulose/technical lignin composite films were assessed. Results showed severe organosolv and soda/AQ pretreatment produced technical lignins with higher total phenolic hydroxyl groups (3.37 and 3.23 mmol g-1 respectively), which also exhibited higher antioxidant activities. The composite films could effectively block the ultraviolet lights especially for UVB region (ultraviolet B, 280–315 nm) at only 5 wt.% lignin content. The contribution of lignin phenolic substructures to both antioxidant activity and UV-shielding property from high to low was syringyl > guaiacyl > p-hydroxyphenyl phenolic hydroxyl groups. This work provided some useful information that could facilitate upstream lignin extraction or downstream value-added applications.

Construction of sustainable composite biofilms from natural biopolymers are greatly promising for advanced packaging applications due to their biodegradable, biocompatible, and renewable properties. In this work, sustainable advanced food packaging films are developed by incorporating lignin nanoparticles (LNPs) as green nanofillers to starch films. This seamless combination of bio-nanofiller with biopolymer matrix is enabled by the uniform size of nanofillers and the strong interfacial hydrogen bonding. As a result, the as-prepared biocomposites exhibit enhanced mechanical properties, thermal stability, and antioxidant activity. Moreover, they also present outstanding ultraviolet (UV) irradiation shielding performance. As a proof of concept in the application of food packaging, we evaluate the effect of composite films on delaying oxidative deterioration of soybean oil. The results indicate our composite film could significantly decrease peroxide value (POV), saponification value (SV), and acid value (AV) to delay oxidation of soybean oil during storage. Overall, this work provides a simple and effective method for the preparation of starch-based films with enhanced antioxidant and barrier properties for advanced food packaging applications.