The disposal of food waste is a current and pressing issue, urging novel solutions to implement sustainable waste management practices. Fish leftovers and their processing byproducts represent a significant portion of the original fish, and their disposal has a high environmental and economic impact. The utilization of waste as raw materials for the production of different classes of biofuels and high-value chemicals, a concept known as “biorefinery”, is gaining interest in a vision of circular economy and zero waste policies. In this context, an interesting route of valorization is the extraction of omega-3 fatty acids (ω-3 FAs) for nutraceutical application. These fatty acids, such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) have received attention over the last decades due to their beneficial effects on human health. Their sustainable production is a key process for matching the increased market demand while reducing the pressure on marine ecosystems and lowering the impact of waste production. The high resale value of the products makes this waste a powerful tool that simultaneously protects the environment and benefits the global economy. This review aims to provide a complete overview of the sustainable exploitation of fish waste to recover ω-3 FAs for food supplement applications, covering composition, storage, and processing of the raw material.

Recent advances in the chemistry of melanins have begun to disclose a number of important structure-property-function relationships of crucial relevance to the biological role of human pigments, including skin (photo) protection and UV-susceptibility. Even slight variations in the monomer composition of black eumelanins and red pheomelanins have been shown to determine significant differences in light absorption, antioxidant, paramagnetic and redox behavior, particle morphology, surface properties, metal chelation and resistance to photo-oxidative wear-and-tear. These variations are primarily governed by the extent of decarboxylation at critical branching points of the eumelanin and pheomelanin pathways, namely the rearrangement of dopachrome to 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA), and the rearrangement of 5-S-cysteinyldopa o-quinoneimine to 1,4-benzothiazine (BTZ) and its 3-carboxylic acid (BTZCA). In eumelanins, the DHICA-to-DHI ratio markedly affects the overall antioxidant and paramagnetic properties of the resulting pigments. In particular, a higher content in DHICA decreases visible light absorption and paramagnetic response relative to DHI-based melanins, but markedly enhances antioxidant properties. In pheomelanins, likewise, BTZCA-related units, prevalently formed in the presence of zinc ions, appear to confer pronounced visible and ultraviolet A (UVA) absorption features, accounting for light-dependent reactive oxygen species (ROS) production, whereas non-carboxylated benzothiazine intermediates seem to be more effective in inducing ROS production by redox cycling mechanisms in the dark. The possible biological and functional significance of carboxyl retention in the eumelanin and pheomelanin pathways is discussed.

Eumelanins, the chief photoprotective pigments in man and mammals, owe their black color to an unusual broadband absorption spectrum whose origin is still a conundrum. Excitonic effects from the interplay of geometric order and disorder in 5,6-dihydroxyindole (DHI)-based oligomeric/polymeric structures play a central role, however the contributions of structural (scaffold-controlled) and redox (π-electron-controlled) disorder have remained uncharted. Herein, we report an integrated experimental-theoretical entry to eumelanin chromophore dynamics based on poly(vinyl alcohol)-controlled polymerization of a large set of 5,6-dihydroxyindoles and related dimers. The results a) uncover the impact of the structural scaffold on eumelanin optical properties, disproving the widespread assumption of a universal monotonic chromophore; b) delineate eumelanin chromophore buildup as a three-step dynamic process involving the rapid generation of oxidized oligomers, termed melanochromes (phase I), followed by a slow oxidant-independent band broadening (phase II) leading eventually to scattering (phase III); c) point to a slow reorganization-stabilization of melanochromes via intermolecular redox interactions as the main determinant of visible broadband absorption.

Pheomelanin has been implicated in the increased susceptibility to UV-induced melanoma for people with light skin and red hair. Recent studies identified a UV-independent pathway to melanoma carcinogenesis and implicated pheomelanin’s pro-oxidant properties that act through the generation of reactive oxygen species and/or the depletion of cellular antioxidants. Here, we applied an electrochemically-based reverse engineering methodology to compare the redox properties of human hair pheomelanin with model synthetic pigments and natural eumelanin. This methodology exposes the insoluble melanin samples to complex potential (voltage) inputs and measures output response characteristics to assess redox activities. The results demonstrate that both eumelanin and pheomelanin are redox-active, they can rapidly (sec-min) and repeatedly redox-cycle between oxidized and reduced states and pheomelanin possesses a more oxidative redox potential. This study suggests that pheomelanin’s redox-based pro-oxidant activity may contribute to sustaining a chronic oxidative stress condition through a redox-buffering mechanism.

Herein the antioxidant and food stabilizing properties of a PNS hydroalcoholic extract (PNSE) are reported. Chemical degradation of PNSE demonstrated the presence of condensed tannins as the main phenolic components. PNSE showed remarkable antioxidant properties in the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay (EC50= 0.004 mg/mL). PNSE was initially tested as an inhibitor of mushroom tyrosinase, exhibiting a quite low IC50 value (0.055 mg/mL) against the enzyme diphenolase activity, suggesting its use in enzymatic browning inhibition. The anthocyanin stabilization properties were evaluated under accelerated aging conditions of both pure pigments and commercial fruit juices, and PNSE was found to be effective at concentrations (0.05 mg/mL) at which well-known stabilizers such as chlorogenic and ferulic acids proved to fail. PNSE also performed well in the stabilization of spray dried anthocyanins for use as food colorant, increasing the half life of blackberry anthocyanins up to 20%. In order to explore the possibility of using PNSE as a functional additive for active packaging, polylactic acid (PLA) films containing PNSE were prepared by solvent-casting and no substantial alteration of the mechanical properties was found on addition of the extract up to 10% w/w. The films showed remarkable antioxidant properties (DDPH reduction >60% with a 3% w/w loading, at a dose of 1 mg/mL in the DPPH solution) and delayed the onset of browning of apple smoothies (ca. 30% inhibition with a 10% w/w loading). These results highlight the exploitation of PNS as a low-cost polyphenol source for food industry applications.