Boosting Supercapacitor Efficiency with Amorphous Biomass-Derived C@TiO2 Composites.

Carbon materials are readily available and are essential in energy storage. One of the routes used to enhance their surface area and activity is the decoration of carbons with semiconductors, such as amorphous TiO2, for application in energy storage devices. This work reports the preparation of amorphous TiO2 nanopowders, which were obtained through the anodization of titanium in ethaline media. The obtained amorphous TiO2 was used to obtain TiO2-decorated carbon (obtained through the carbonization of glycogen precursor from mussel cooking wastewater, under N2 atmosphere) composites through three different methods: electrochemical in-situ attachment of TiO2 nanopowders to the carbon matrix using ultrasounds and sonication in ethaline. Commercial TiO2 was used as the comparison material. Morphology, composition, and structure analysis were performed, followed by the electrochemical analysis in ethaline electrolyte. The in-situ attachment of amorphous TiO2 to the carbon matrix shows the most promising electrochemical performance of 956 F g-1 at 1 A g-1 for the three-electrode cell setup, with 100%  and 98% capacitance retention after 1000 and 10000 cycles. On a two-electrode symmetric solid-state electrolyte cell, the gravimetric capacitance is 1251 F g-1, at 1 A g-1, with 90% and 78% capacitance retention after 1000 and 10000 cycles, respectively.

Optimal and sustainable production of tailored fish protein hydrolysates from tuna canning wastes and discarded blue whiting: Effect of protein molecular weight on chemical and bioactive properties.

Thousands tons of discards of blue whiting (BW) and tuna heads (YT) by-products are generated each year in Europe. BW is the species most discarded by European fishing fleet and, in some canning factories, YT are processed for the retrieval of oil rich in omega-3, but producing a huge amount of solid remains and effluents disposal as wastes. The development of optimal and sustainable processes for both substrates is mandatory in order to reach clean solutions under the circular economy precepts. This work focused on the mathematical optimization of the production of tailored fish protein hydrolysates (FPH), from blue whiting and tuna residues, in terms of controlling average molecular weights (Mw) of proteins. For the modeling of the protein depolymerization time-course, a pseudo-mechanistic model was used, which combined a reaction mechanistic equation affected, in the kinetic parameters, by two non-lineal equations (a first-order kinetic and like-Weibull formulae). In all situations, experimental data were accurately simulated by that model achieving R2 values higher than 0.96. The validity of the experimental conditions obtained from modeling were confirmed performing productions of FPH at scale of 5 L-reactor, without pH-control in most of cases, at the different ranges of Mw selected (1-2 kDa, 2-5 kDa and 5-10 kDa). The results showed that FPH from BW with lower Mw led to a remarkable yield of production (12 % w/w of substrate), largest protein contents (77 % w/w of BW hydrolysate), greatest in vitro digestibility (>95 %), highest essential amino acid presence (43 %) and the best antioxidant (DPPH = 62 %) and antihypertensive (IC50-ACE = 80 mg/L) properties. Our results prove that the proposed procedure to produce sustainable FPH, with specific Mw characterisitics, could be extended to other fish waste substrates. Tailored FPH may have the potential to serve as valuable ingredients for functional foods and high-quality aquaculture feed.

Renewable Carbon Materials as Electrodes for High-Performance Supercapacitors: From Marine Biowaste to High Specific Surface Area Porous Biocarbons.

Waste, in particular, biowaste, can be a valuable source of novel carbon materials. Renewable carbon materials, such as biomass-derived carbons, have gained significant attention recently as potential electrode materials for various electrochemical devices, including batteries and supercapacitors. The importance of renewable carbon materials as electrodes can be attributed to their sustainability, low cost, high purity, high surface area, and tailored properties. Fish waste recovered from the fish processing industry can be used for energy applications and prioritizing the circular economy principles. Herein, a method is proposed to prepare a high surface area biocarbon from glycogen extracted from mussel cooking wastewater. The biocarbon materials were characterized using a Brunauer-Emmett-Teller surface area analyzer to determine the specific surface area and pore size and by scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman analysis, attenuated total reflectance Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The electrochemical characterization was performed using a three-electrode system, utilizing a choline chloride-based deep eutectic solvent (DES) as an eco-friendly and sustainable electrolyte. Optimal time and temperature allowed the preparation of glycogen-based carbon materials, with a specific surface area of 1526 m2 g-1, a pore volume of 0.38 cm3 g-1, and an associated specific capacitance of 657 F g-1 at a current density of 1 A g-1, at 30 °C. The optimal material was scaled up to a two-electrode supercapacitor using a DES-based solid-state electrolyte (SSE@DES). This prototype delivered a maximum capacitance of 703 F g-1 at a 1 A g-1 of current density, showing 75% capacitance retention over 1000 cycles, delivering the highest energy density of 0.335 W h kg-1 and power density of 1341 W kg-1. Marine waste can be a sustainable source for producing nanoporous carbon materials to be incorporated as electrode materials in energy storage devices.

Valorisation of pork by-products to obtain antioxidant and antihypertensive peptides.

The porcine liver could be used for the extraction of zinc-protoporphyrin (ZnPP) as a natural red meat pigment. During the autolysis process, porcine liver homogenates was incubated at pH 4.8 and 45 °C under anaerobic conditions to obtain insoluble ZnPP. After incubation, the homogenates were readjusted at pH 4.8, and at pH 7.5 before being centrifuged at 5500 × g for 20 min at 4 °C and the resulting supernatant were compared with the obtained at pH 4.8 at the beginning of the incubation. The molecular weight distributions of the porcine liver fractions at both pHs were very similar, however, eight essential amino acids were more abundant in fractions obtained at pH 4.8. Regarding the ORAC assay, porcine liver protein fraction at pH 4.8 showed the highest antioxidant capacity but antihypertensive inhibition was similar for both pHs. Peptides with strong bioactivity potential from aldehyde dehydrogenase, lactoylglutathione lyase, SEC14-like protein 3 and others were identified. The findings have demonstrated the potential of the porcine liver to extract natural pigments and bioactive peptides.

Chitins from Seafood Waste as Sustainable Porous Carbon Precursors for the Development of Eco-Friendly Supercapacitors.

Carbon materials derived from marine waste have been drawing attention for supercapacitor applications. In this work, chitins from squid and prawn marine wastes were used as carbon precursors for further application as electrodes for energy storage devices. Chitins were obtained through a deproteinization method based on enzymatic hydrolysis as an alternative to chemical hydrolysis as commonly presented in the literature. The obtained porous carbons were characterized using a BET surface area analyzer to determine the specific surface area and pore size, as well as scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), Raman spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), to characterize their morphology, composition, and structure. The electrochemical characterization was performed using a glassy carbon (GC) electrode modified with marine waste-based porous carbons as the working electrode through cyclic voltammetry and galvanostatic charge/discharge using ethaline, a choline chloride-based deep eutectic solvent (DES), as an eco-friendly and sustainable electrolyte. Squid and prawn chitin-based carbons presented a surface area of 149.3 m2 g-1 and 85.0 m2 g-1, pore volume of 0.053 cm3 g-1 and 0.029 cm3 g-1, and an associated specific capacitance of 20 and 15 F g-1 at 1 A g-1, respectively. Preliminary studies were performed to understand the effect of -OH groups on the chitin-based carbon surface with DES as an electrolyte, as well as the effect of aqueous electrolytes (1 mol L-1 sulphuric acid (H2SO4) and 1 mol L-1 potassium hydroxide (KOH)) on the capacitance and retention of the half-cell set up. It is provided, for the first time, the use of chitin-based carbon materials obtained through a one-step carbonization process combined with an eco-friendly DES electrolyte for potential application in energy storage devices.

Assessment of the Antibiofilm Performance of Chitosan-Based Surfaces in Marine Environments.

Marine biofouling is a natural process often associated with biofilm formation on submerged surfaces, creating a massive economic and ecological burden. Although several antifouling paints have been used to prevent biofouling, growing ecological concerns emphasize the need to develop new and environmentally friendly antifouling approaches such as bio-based coatings. Chitosan (CS) is a natural polymer that has been widely used due to its outstanding biological properties, including non-toxicity and antimicrobial activity. This work aims to produce and characterize poly (lactic acid) (PLA)-CS surfaces with CS of different molecular weight (Mw) at different concentrations for application in marine paints. Loligo opalescens pens, a waste from the fishery industry, were used as a CS source. The antimicrobial activity of the CS and CS-functionalized surfaces was assessed against Cobetia marina, a model proteobacterium for marine biofouling. Results demonstrate that CS targets the bacterial cell membrane, and PLA-CS surfaces were able to reduce the number of culturable cells up to 68% compared to control, with this activity dependent on CS Mw. The antifouling performance was corroborated by Optical Coherence Tomography since PLA-CS surfaces reduced the biofilm thickness by up to 36%, as well as the percentage and size of biofilm empty spaces. Overall, CS coatings showed to be a promising approach to reducing biofouling in marine environments mimicked in this work, contributing to the valorization of fishing waste and encouraging further research on this topic.

Hyaluronan Brush-like Copolymers Promote CD44 Declustering in Breast Cancer Cells.

We report on the synthesis of hyaluronan (HA) brush-like copolymers and their application as antagonists of tumorigenic CD44-HA interactions. HA (4.8 kDa, ca. 24 saccharides) was grafted on 2-hydrohyethyl methacrylate (HEMA) by end-on oxime ligation. The obtained copolymers were compared with low and high molecular weight HA in terms of hydrolysis kinetics in the presence of hyaluronidase (isothermal titration calorimetry) and interactions with CD44 (surface plasmon resonance). The results evidenced that the high molecular weight HA and HA-g-HEMA have a much higher affinity to CD44 than low molecular weight HA. Additionally, slower enzymatic degradation was observed for the copolymer, making it an excellent candidate for active targeting of tumorigenic CD44-HA interactions. We, therefore, investigated the effect of the copolymer on cancer cell lines with different expression of CD44 and observed an efficient declustering of CD44 that is usually associated with reduction of metastasis and drug resistance.

Ionogels Derived from Fluorinated Ionic Liquids to Enhance Aqueous Drug Solubility for Local Drug Administration.

Gelatin is a popular biopolymer for biomedical applications due to its harmless impact with a negligible inflammatory response in the host organism. Gelatin interacts with soluble molecules in aqueous media as ionic counterparts such as ionic liquids (ILs) to be used as cosolvents to generate the so-called Ionogels. The perfluorinated IL (FIL), 1-ethyl-3-methylpyridinium perfluorobutanesulfonate, has been selected as co-hydrosolvent for fish gelatin due to its low cytotoxicity and hydrophobicity aprotic polar structure to improve the drug aqueous solubility. A series of FIL/water emulsions with different FIL content and their corresponding shark gelatin/FIL Ionogel has been designed to enhance the drug solubility whilst retaining the mechanical structure and their nanostructure was probed by simultaneous SAXS/WAXS, FTIR and Raman spectroscopy, DSC and rheological experiments. Likewise, the FIL assisted the solubility of the antitumoural Doxorubicin whilst retaining the performing mechanical properties of the drug delivery system network for the drug storage as well as the local administration by a syringe. In addition, the different controlled release mechanisms of two different antitumoral such as Doxorubicin and Mithramycin from two different Ionogels formulations were compared to previous gelatin hydrogels which proved the key structure correlation required to attain specific therapeutic dosages.

Multifunctional PLA/Gelatin Bionanocomposites for Tailored Drug Delivery Systems.

A series of bionanocomposites composed of shark gelatin hydrogels and PLA nanoparticles featuring different nanostructures were designed to generate multifunctional drug delivery systems with tailored release rates required for personalized treatment approaches. The global conception of the systems was considered from the desired customization of the drug release while featuring the viscoelastic properties needed for their ease of storage and posterior local administration as well as their biocompatibility and cell growth capability for the successful administration at the biomolecular level. The hydrogel matrix offers the support to develop a direct thermal method to convert the typical kinetic trapped nanostructures afforded by the formulation method whilst avoiding the detrimental nanoparticle agglomeration that diminishes their therapeutic effect. The nanoparticles generated were successfully formulated with two different antitumoral compounds (doxorubicin and dasatinib) possessing different structures to prove the loading versatility of the drug delivery system. The bionanocomposites were characterized by several techniques (SEM, DLS, RAMAN, DSC, SAXS/WAXS and rheology) as well as their reversible sol-gel transition upon thermal treatment that occurs during the drug delivery system preparation and the thermal annealing step. In addition, the local applicability of the drug delivery system was assessed by the so-called "syringe test" to validate both the storage capability and its flow properties at simulated physiological conditions. Finally, the drug release profiles of the doxorubicin from both the PLA nanoparticles or the bionanocomposites were analyzed and correlated to the nanostructure of the drug delivery system.

Characterization of Tuna Gelatin-Based Hydrogels as a Matrix for Drug Delivery.

The skin of yellowfin tuna is one of the fishery industry solid residues with the greatest potential to add extra value to its circular economy that remains yet unexploited. Particularly, the high collagen content of fish skin allows generating gelatin by hydrolysis, which is ideal for forming hydrogels due to its biocompatibility and gelling capability. Hydrogels have been used as drug carriers for local administration due to their mechanical properties and drug loading capacity. Herein, novel tuna gelatin hydrogels were designed as drug vehicles with two structurally different antitumoral model compounds such as Doxorubicin and Crocin to be administrated locally in tissues with complex human anatomies after surgical resection. The characterization by gel permeation chromatography (GPC) of purified gelatin confirmed their heterogeneity composition, exhibiting three major bands that correspond to the ß and α chains along with high molecular weight species. In addition, the Fourier Transform Infrared (FT-IR) spectra of gelatin probed the secondary structure of the gelatin showing the simultaneous existence of α helix, ß sheet, and random coil structures. Morphological studies at different length scales were performed by a multi-technique approach using SAXS/WAXS, AFM and cryo-SEM that revealed the porous network formed by the interaction of gelatin planar aggregates. In addition, the sol-gel transition, as well as the gelation point and the hydrogel strength, were studied using dynamic rheology and differential scanning calorimetry. Likewise, the loading and release profiles followed by UV-visible spectroscopy indicated that the novel gelatin hydrogels improve the drug release of Doxorubicin and Crocin in a sustained fashion, indicating the structure-function importance in the material composition.

Extraction and Characterization of Gelatin from Skin By-Products of Seabream, Seabass and Rainbow Trout Reared in Aquaculture.

The expansion of fish filleting, driven by the increasing demand for convenience food, concomitantly generates a rising amount of skinning by-products. Current trends point to a growing share of aquaculture in fish production, so we have chosen three established aquaculture species to study the properties of gelatin extracted from their skin: rainbow trout, commonly filleted; and seabass and seabream, marketed whole until very recently. In the first case, trout skin yields only 1.6% gelatin accompanied by the lowest gel strength (96 g bloom), while yield for the other two species exceeds 6%, and gel strength reaches 181 and 229 g bloom for seabass and seabream, respectively. These results are in line with the proportion of total imino acids analyzed in the gelatin samples. Molecular weight profiling shows similarities among gelatins, but seabass and seabream gelatins appear more structured, with higher proportion of ß-chains and high molecular weight aggregates, which may influence the rheological properties observed. These results present skin by-products of seabream, and to a minor extent seabass, as suitable raw materials to produce gelatin through valorization processes.

Production and Physicochemical Characterization of Gelatin and Collagen Hydrolysates from Turbot Skin Waste Generated by Aquaculture Activities.

Rising trends in fish filleting are increasing the amount of processing by-products, such as skins of turbot, a flatfish of high commercial value. In line with circular economy principles, we propose the valorization of turbot skins through a two-step process: initial gelatin extraction described for the first time in turbot, followed by hydrolysis of the remaining solids to produce collagen hydrolysates. We assayed several methods for gelatin extraction, finding differences in gelatin properties depending on chemical treatment and temperature. Of all methods, the application of NaOH, sulfuric, and citric acids at 22 °C results in the highest gel strength (177 g), storage and loss moduli, and gel stability. We found no relation between mechanical properties and content of pyrrolidine amino acids, but the best performing gelatin displays higher structural integrity, with less than 30% of the material below 100 kDa. Collagen hydrolysis was more efficient with papain than alcalase, leading to a greater reduction in Mw of the hydrolysates, which contain a higher proportion of essential amino acids than gelatin and show high in vitro anti-hypertensive activity. These results highlight the suitability of turbot skin by-products as a source of gelatin and the potential of collagen hydrolysates as a functional food and feed ingredient.

Characterization of Gelatin and Hydrolysates from Valorization of Farmed Salmon Skin By-Products.

Salmon processing commonly involves the skinning of fish, generating by-products that need to be handled. Such skin residues may represent valuable raw materials from a valorization perspective, mainly due to their collagen content. With this approach, we propose in the present work the extraction of gelatin from farmed salmon and further valorization of the remaining residue through hydrolysis. Use of different chemical treatments prior to thermal extraction of gelatin results in a consistent yield of around 5%, but considerable differences in rheological properties. As expected from a cold-water species, salmon gelatin produces rather weak gels, ranging from 0 to 98 g Bloom. Nevertheless, the best performing gelatins show considerable structural integrity, assessed by gel permeation chromatography with light scattering detection for the first time on salmon gelatin. Finally, proteolysis of skin residues with Alcalase for 4 h maximizes digestibility and antihypertensive activity of the resulting hydrolysates, accompanied by the sharpest reduction in molecular weight and higher content of essential amino acids. These results indicate the possibility of tuning salmon gelatin properties through changes in chemical treatment conditions, and completing the valorization cycle through production of bioactive and nutritious hydrolysates.

The Effect of Molecular Weight on the Antimicrobial Activity of Chitosan from Loligo opalescens for Food Packaging Applications.

The growing requirement for sustainable processes has boosted the development of biodegradable plastic-based materials incorporating bioactive compounds obtained from waste, adding value to these products. Chitosan (Ch) is a biopolymer that can be obtained by deacetylation of chitin (found abundantly in waste from the fishery industry) and has valuable properties such as biocompatibility, biodegradability, antimicrobial activity, and easy film-forming ability. This study aimed to produce and characterize poly(lactic acid) (PLA) surfaces coated with ß-chitosan and ß-chitooligosaccharides from a Loligo opalescens pen with different molecular weights for application in the food industry. The PLA films with native and depolymerized Ch were functionalized through plasma oxygen treatment followed by dip-coating, and their physicochemical properties were assessed by Fourier-transform infrared spectroscopy, X-ray diffraction, water contact angle, and scanning electron microscopy. Their antimicrobial properties were assessed against Escherichia coli and Pseudomonas putida, where Ch-based surfaces reduced the number of biofilm viable, viable but nonculturable, and culturable cells by up to 73%, 74%, and 87%, respectively, compared to PLA. Biofilm growth inhibition was confirmed by confocal laser scanning microscopy. Results suggest that Ch films of higher molecular weight had higher antibiofilm activity under the food storage conditions mimicked in this work, contributing simultaneously to the reuse of marine waste.

Development of Chitosan-Based Surfaces to Prevent Single- and Dual-Species Biofilms of Staphylococcus aureus and Pseudomonas aeruginosa.

Implantable medical devices (IMDs) are susceptible to microbial adhesion and biofilm formation, which lead to several clinical complications, including the occurrence of implant-associated infections. Polylactic acid (PLA) and its composites are currently used for the construction of IMDs. In addition, chitosan (CS) is a natural polymer that has been widely used in the medical field due to its antimicrobial and antibiofilm properties, which can be dependent on molecular weight (Mw). The present study aims to evaluate the performance of CS-based surfaces of different Mw to inhibit bacterial biofilm formation. For this purpose, CS-based surfaces were produced by dip-coating and the presence of CS and its derivatives onto PLA films, as well surface homogeneity were confirmed by contact angle measurements, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The antimicrobial activity of the functionalized surfaces was evaluated against single- and dual-species biofilms of Staphylococcus aureus and Pseudomonas aeruginosa. Chitosan-based surfaces were able to inhibit the development of single- and dual-species biofilms by reducing the number of total, viable, culturable, and viable but nonculturable cells up to 79%, 90%, 81%, and 96%, respectively, being their activity dependent on chitosan Mw. The effect of CS-based surfaces on the inhibition of biofilm formation was corroborated by biofilm structure analysis using confocal laser scanning microscopy (CLSM), which revealed a decrease in the biovolume and thickness of the biofilm formed on CS-based surfaces compared to PLA. Overall, these results support the potential of low Mw CS for coating polymeric devices such as IMDs where the two bacteria tested are common colonizers and reduce their biofilm formation.

Characterization of Protein Hydrolysates from Fish Discards and By-Products from the North-West Spain Fishing Fleet as Potential Sources of Bioactive Peptides.

Fish discards and by-products can be transformed into high value-added products such as fish protein hydrolysates (FPH) containing bioactive peptides. Protein hydrolysates were prepared from different parts (whole fish, skin and head) of several discarded species of the North-West Spain fishing fleet using Alcalase. All hydrolysates had moisture and ash contents lower than 10% and 15%, respectively. The fat content of FPH varied between 1.5% and 9.4% and had high protein content (69.8-76.6%). The amino acids profiles of FPH are quite similar and the most abundant amino acids were glutamic and aspartic acids. All FPH exhibited antioxidant activity and those obtained from Atlantic horse mackerel heads presented the highest 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity, reducing power and Cu2+ chelating activity. On the other hand, hydrolysates from gurnard heads showed the highest ABTS radical scavenging activity and Fe2+ chelating activity. In what concerns the α-amylase inhibitory activity, the IC50 values recorded for FPH ranged between 5.70 and 84.37 mg/mL for blue whiting heads and whole Atlantic horse mackerel, respectively. α-Glucosidase inhibitory activity of FPH was relatively low but all FPH had high Angiotensin Converting Enzyme (ACE) inhibitory activity. Considering the biological activities, these FPH are potential natural additives for functional foods or nutraceuticals.

Deciphering Structural Determinants in Chondroitin Sulfate Binding to FGF-2: Paving the Way to Enhanced Predictability of their Biological Functions.

Controlling chondroitin sulfates (CSs) biological functions to exploit their interesting potential biomedical applications requires a comprehensive understanding of how the specific sulfate distribution along the polysaccharide backbone can impact in their biological activities, a still challenging issue. To this aim, herein, we have applied an "holistic approach" recently developed by us to look globally how a specific sulfate distribution within CS disaccharide epitopes can direct the binding of these polysaccharides to growth factors. To do this, we have analyzed several polysaccharides of marine origin and semi-synthetic polysaccharides, the latter to isolate the structure-activity relationships of their rare, and even unnatural, sulfated disaccharide epitopes. SPR studies revealed that all the tested polysaccharides bind to FGF-2 (with exception of CS-8, CS-12 and CS-13) according to a model in which the CSs first form a weak complex with the protein, which is followed by maturation to tight binding with k D ranging affinities from ~ 1.31 µM to 130 µM for the first step and from ~ 3.88 µM to 1.8 nM for the second one. These binding capacities are, interestingly, related with the surface charge of the 3D-structure that is modulated by the particular sulfate distribution within the disaccharide repeating-units.

Isolation and Characterization of Polysaccharides from the Ascidian Styela clava.

Styela clava is an edible sea squirt farmed in Korea that has gradually invaded other seas, negatively impacting the ecology and economy of coastal areas. Extracts from S. clava have shown wide bioactivities, and ascidians have the unique capability among animals of biosynthesizing cellulose. Thus, S. clava is a relevant candidate for valorization. Herein, we aimed at surveying and characterizing polysaccharides in both tunic and flesh of this ascidian. To this end, we enzymatically hydrolyzed both tissues, recovering crystalline cellulose from the tunic with high aspect ratios, based on results from microscopy, X-ray diffraction, and infrared spectroscopy analyses. Alkaline hydroalcoholic precipitation was applied to isolate the polysaccharide fraction that was characterized by gel permeation chromatography (with light scattering detection) and NMR. These techniques allowed the identification of glycogen in the flesh with an estimated Mw of 7 MDa. Tunic polysaccharides consisted of two fractions of different Mw. Application of Diffusion-Ordered NMR allowed spectroscopically separating the low-molecular-weight fraction to analyze the major component of an estimated Mw of 40-66 kDa. We identified six different sugar residues, although its complexity prevented the determination of the complete structure and connectivities of the residues. The two more abundant residues were N-acetylated and possibly components of the glycosaminoglycan-like (GAG-like) family, showing the remaining similarities to sulfated galactans. Therefore, Styela clava appears as a source of nanocrystalline cellulose and GAG-like polysaccharides.

Optimal Recovery of Valuable Biomaterials, Chondroitin Sulfate and Bioapatites, from Central Skeleton Wastes of Blue Shark.

The industrial filleting of blue shark (Prionace glauca) led to the generation of a large number of central skeletons of low interest to fishmeal plants handling such wastes. In this context, the present study describes the optimization of the hydrolysis process (pH 8.35, T 58 °C, 1% (v/w) of alcalase and t = 4 h) to produce chondroitin sulfate (CS) together with the recovery of bioapatites. Then, that hydrolysate was chemically treated with an optimal alkaline-hydroalcoholic-saline solution (0.48 M of NaOH, 1.07 volumes of EtOH and 2.5 g/L of NaCl) and finally purified by ultrafiltration-diafiltration (30 kDa) to obtain glycosaminoglycan with a purity of 97% and a productive yield of 2.8% (w/w of skeleton). The size of the biopolymer (CS) was of 58 kDa with prevalence of 6S-GalNAc sulfation (4S/6S ratio of 0.25), 12% of GlcA 2S-GalNAc 6S and 6% of non-sulfated disaccharides. Crude bioapatites were purified by pyrolysis and FT-Raman and XRD techniques confirm the presence of hydroxyapatite [Ca5(PO4)3(OH)], with a molar mass of 502.3 g/mol, embedded in the organic matrix of the skeleton. The mineralized tissues of blue shark are promising marine sources for the extraction of high value biomaterials with clinical application in bone and tissue regeneration and are still completely unexplored.

Optimization of the Enzymatic Protein Hydrolysis of By-Products from Seabream (Sparus aurata) and Seabass (Dicentrarchus labrax), Chemical and Functional Characterization.

Valorization of seabass and seabream by-products is becoming increasingly relevant, as marketing of these species moves from selling whole fish to filleting for convenience products. With this aim, we optimized for the first time the production of fish protein hydrolysates (FPH) by enzymatic hydrolysis from filleting by-products of these commercially relevant aquaculture species, isolating fish oil at the same time. On the whole, both fish yielded similar amounts of protein, but frames and trimmings (FT) were the best source, followed by heads and viscera. In vitro antioxidant and antihypertensive activities showed similar figures for both species, placing FPHs from FT as the most active. Molecular weights ranged from 1381 to 2023 Da, corresponding to the lowest values of FT, in line with the higher hydrolysis degrees observed. All FPHs reached high digestibility (>86%) and displayed an excellent amino acid profile in terms of essential amino acids and flavor, making them suitable as food additives and supplements.