Enhancing the Radical Scavenging Activity and UV Resistance of Lignin Nanoparticles via Surface Mannich Amination toward a Biobased Antioxidant.

In recent years, lignin specific activities, such as antioxidation and antibacterial and anti-ultraviolet performance, have drawn more and more attention. Nevertheless, the insufficient radical scavenging (antioxidation) activity has become one of the main drawbacks that limits its high-value application. In this study, lignin nanoparticles (LNPs) were prepared via a facile acid treatment strategy. Subsequently, surface amination of LNPs (a-LNPs) was carried out through the Mannich reaction. Specifically, the antioxidant behavior of LNPs and modified LNPs was evaluated by DPPH/DMPO radical scavenging and in vitro HeLa cell reactive oxygen species (ROS) scavenging tests, which demonstrated that the antioxidation activity of a-LNPs was more evident than that of both LNPs and butylated hydroxytoluene (BHT) commercial antioxidant. The mechanism of the radical scavenging ability of aminated LNPs was elucidated and proved to be related to the bond dissociation enthalpy of Ar-O···H, determined by the electron-donating effect of the substituted groups in the ortho-position. Meanwhile, the morphologies, solubilities, and UV-absorbing and antibacterial behavior of LNPs and a-LNPs were also studied, and the results showed that a-LNP sample exhibited higher UV resistance performance than LNPs. We expected that the modified LNPs with high antioxidation activity can serve as a safe and lower-cost biobased antioxidant.

Effect of Cellulose Nanocrystals and Lignin Nanoparticles on Mechanical, Antioxidant and Water Vapour Barrier Properties of Glutaraldehyde Crosslinked PVA Films.

In this work, PVA nanocomposite films containing cellulose nanocrystals (CNC) and different amounts of lignin nanoparticles (LNP), prepared via a facile solvent cast method, were crosslinked by adding glutaraldehyde (GD). The primary objective was to investigate the effects of crosslinker and bio-based nanofillers loading on thermal, mechanical, antioxidant and water barrier behaviour of PVA nanocomposite films for active food packaging. Thermogravimetric analysis showed improved thermal stability, due to the strong interactions between LNP, CNC and PVA in the presence of GD, while Wide-angle X-ray diffraction results confirmed a negative effect on crystallinity, due to enhanced crosslinking interactions between the nanofillers and PVA matrix. Meanwhile, the tensile strength of PVA-2CNC-1LNP increased from 26 for neat PVA to 35.4 MPa, without sacrificing the ductility, which could be explained by a sacrificial hydrogen bond reinforcing mechanism induced by spherical-like LNP. UV irradiation shielding effect was detected for LNP containing PVA films, also migrating ingredients from PVA nanocomposite films induced radical scavenging activity (RSA) in the produced films in presence of LNP. Furthermore, PVA-CNC-LNP films crosslinked by GD showed marked barrier ability to water vapour.

Poly(lactic acid)/lignin films with enhanced toughness and anti-oxidation performance for active food packaging.

In this study, grafting of star-like lignin microparticles (LMP) onto PLA (LMP-g-PLA) was successfully realized by ring open polymerization of l-lactide, initiating from the hydroxyl groups on LMP surface. After that, various amount of LMP-g-PLA were melt blended with neat PLA and ethylene-vinyl acetate-glycidyl methacrylate (NPG) to prepare different PLA composites films, by exploiting the interfacial reactions between epoxy groups of NPG and carboxyl and hydroxyl groups of both LMP-g-PLA and PLA. Mechanical test results show that the addition of LMP-g-PLA made a significant contribution to the toughness of PLA/NPG blend, as the elongation at break increased up to 236% in PLA/NPG/1LMP sample. Although the addition of NPG and LMP-g-PLA hindered the crystallization capacity of PLA, good dispersion of LMP-g-PLA and compatibility between LMP and PLA acted as longer tortuous paths, consequently reducing the water vapor transmission rate. Meanwhile, the UV-Vis spectroscopy results showed that PLA/NPG/LMP films have excellent UV resistance behaviour without sacrificing too much the transparency. Results from overall migration tests and testing of anti-oxidant behaviour demonstrated that PLA films blended with NPG and lignin can be used as competitive materials in active food packaging industry.