Nanoparticles of Lignins and Saccharides from Fishery Wastes as Sustainable UV-Shielding, Antioxidant, and Antimicrobial Biofillers.

Lignin nanoparticles containing saccharides from fishery wastes were prepared as sustainable biofillers for advanced materials. Organosolv lignin and Kraft lignin were used as polyphenol components in association with chitosan and chitooligosaccharides. The chemophysical and biological activities of lignin/saccharide nanoparticles, such as UV-shielding, antioxidant, and antimicrobial activities, were found to be dependent on both molecular weight and deacetylation degree of saccharides, with the best performance being obtained in the presence of low-molecular-weight and highly deacetylated chitooligosaccharides. In addition, chitooligosaccharides showed a synergistic antioxidant effect with lignins, associated with antimicrobial activity against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive).

Lignin Nanoparticles Deliver Novel Thymine Biomimetic Photo-Adducts with Antimelanoma Activity.

We report here the synthesis of novel thymine biomimetic photo-adducts bearing an alkane spacer between nucleobases and characterized by antimelanoma activity against two mutated cancer cell lines overexpressing human Topoisomerase 1 (TOP1), namely SKMEL28 and RPMI7951. Among them, Dewar Valence photo-adducts showed a selectivity index higher than the corresponding pyrimidine-(6-4)-pyrimidone and cyclobutane counterpart and were characterized by the highest affinity towards TOP1/DNA complex as evaluated by molecular docking analysis. The antimelanoma activity of novel photo-adducts was retained after loading into UV photo-protective lignin nanoparticles as stabilizing agent and efficient drug delivery system. Overall, these results support a combined antimelanoma and UV sunscreen strategy involving the use of photo-protective lignin nanoparticles for the controlled release of thymine dimers on the skin followed by their sacrificial transformation into photo-adducts and successive inhibition of melanoma and alert of cellular UV machinery repair pathways.

Nano-Structured Lignin as Green Antioxidant and UV Shielding Ingredient for Sunscreen Applications.

Green, biocompatible, and biodegradable antioxidants represent a milestone in cosmetic and cosmeceutical applications. Lignin is the most abundant polyphenol in nature, recovered as a low-cost waste from the pulp and paper industry and biorefinery. This polymer is characterized by beneficial physical and chemical properties which are improved at the nanoscale level due to the emergence of antioxidant and UV shielding activities. Here we review the use of lignin nanoparticles in cosmetic and cosmeceutical applications, focusing on sunscreen and antiaging formulations. Advances in the technology for the preparation of lignin nanoparticles are described highlighting structure activity relationships.

Layer-by-Layer Preparation of Microcapsules and Nanocapsules of Mixed Polyphenols with High Antioxidant and UV-Shielding Properties.

Microcapsules and nanocapsules based on the contemporary presence of sulfonate lignin and tannic acid have been prepared by the layer-by-layer procedure, using MnCO3 or organosolv lignin as core templates, and polydiallyldimethylammonium chloride or chitosan as positive charged supporting layers. Nanocapsules and microcapsules of mixed polyphenols showed antioxidant activity, UV-shielding properties, and electrochemical responsiveness, higher than that in homopolymer nanocapsule counterparts and of the native polyphenols, suggesting the presence of synergistic effects between the two components. The presence of UV-visible bathochromic shift suggested the formation of J-aggregates characterized by an orientation of the adjacent phenolic rings parallel to the longitudinal direction of the layer, with a head-to-tail like arrangement. Moreover, nanocapsules of mixed polyphenols showed an aggregation state higher than that observed in references, the specific morphology of their surface being dependent on the structural arrangement of the different components.

Functionalized Tyrosinase-Lignin Nanoparticles as Sustainable Catalysts for the Oxidation of Phenols.

Sustainable catalysts for the oxidation of phenol derivatives under environmentally friendly conditions were prepared by the functionalization of lignin nanoparticles with tyrosinase. Lignin, the most abundant polyphenol in nature, is the main byproduct in the pulp and paper manufacturing industry and biorefinery. Tyrosinase has been immobilized by direct adsorption, encapsulation, and layer-by-layer deposition, with or without glutaraldehyde reticulation. Lignin nanoparticles were found to be stable to the tyrosinase activity. After the enzyme immobilization, they showed a moderate to high catalytic effect in the synthesis of catechol derivatives, with the efficacy of the catalyst being dependent on the specific immobilization procedures.

Laccase-Mediated Enhancement of the Antioxidant Activity of Propolis and Poplar Bud Exudates.

The treatment of propolis and poplar bud exudates with laccase from Trametes versicolor and 2,2,6,6-tetramethyl-1-piperidinyloxy free radical increased the antioxidant activity, as evaluated by the 2,2'-diphenyl picrylhydrazyl (DPPH)- and t-butyl-OOH-induced DNA breakage comet assay analyses. The effect was highest for shorter reaction times. Propolis showed the highest antioxidant activity in the DPPH test, whereas poplar bud exudates were more active in reducing the t-butyl-OOH-induced lesions in the Chinese hamster ovary cell line. Even if the concentration of polyphenols decreased during the oxidation, the formation of low-molecular-weight phenols phloroglucinol 4 (1,3,5-trihydroxy benzene), hydroquinone 5 (1,4-dihydroxy benzene), and catechol 6 (1,2-dihydroxy benzene), characterized by the radical-scavenging activity, can account for the observed increase in the antioxidant activity.