Detection and quantification of biogenic amines in cephalopod using dansyl chloride pre-column derivatization-HPLC and their production.

The accurate detection of biogenic amines (BAs) is an important means of ensuring the quality and safety of cephalopod seafood products. In this study, the pre-column derivatization of high-performance liquid chromatography (HPLC) was optimized using dansyl chloride (Dns-Cl) to detect BAs in octopus, cuttlefish, and squid. The reasons for the formation of BAs were investigated by assessing their decarboxylase activity and the rates of decomposition. The findings demonstrated that using Dns-Cl to optimize pre-column derivatization enabled the separation of nine different BAs. The detection limits ranged from 0.07 to 0.25 mg/L, and the results exhibited a high level of linearity (R2 ≥ 0.997). The decarboxylase activity and biodegradation rate positively correlated with the formation of BAs at temperatures below 0°C. Notably, the decarboxylase activity of octopus, cuttlefish, and squid exhibited a significant increase with prolonged storage time, and formyltransferase and carbamate kinase may be the key decarboxylase in cephalopod products. These findings serve as a valuable reference for further investigations into the mechanisms behind BAs production and the development of control technologies for BAs in cephalopod products. This study has successfully demonstrated the effectiveness of the Dns-Cl pre-column derivatization-HPLC method in accurately and efficiently detecting BAs in octopus, cuttlefish, and squid. Moreover, it highlights the influence of decarboxylase content and biodegradation rate on the formation of BAs. Importantly, this method can serve as a reference for detecting BAs in various seafood products.

Multimaterial Printing for Cephalopod-Inspired Light-Responsive Artificial Chromatophores.

Cephalopods use chromatophores distributed on their soft skin to change skin color and its pattern. Each chromatophore consists of a central sac containing pigment granules and radial muscles surrounding the sac. The contraction of the radial muscle causes the central sac to expand in area, making the color of the pigment more visible. With the chromatophores actuating individually, cephalopods can create extremely complex skin color patterns, which they utilize for exquisite functions including camouflage and communication. Inspired by this mechanism, we present an artificial chromatophore that can modulate its color pattern in response to light. Multimaterial projection microstereolithography is used to integrate three functional components including a photoactive hydrogel composite with polydopamine nanoparticles (PDA-NPs), acrylic acid hydrogel, and poly(ethylene glycol) diacrylate. In order to generate light-driven actuation of the artificial chromatophore, the photothermal effect of the PDA-NPs, light-responsive deformation of the photoactive hydrogel composite, and the produced mechanical stresses are studied. Mechanical properties and interfacial bonding strengths between different materials are also investigated to ensure structural integrity during actuation. We demonstrate pattern modulation of the light-responsive artificial chromatophores (LACs) with the projection of different light patterns. The LAC may suggest a new concept for various engineering applications such as the camouflage interface, biophotonic device, and flexible display.

Biomimetic Colorants and Coatings Designed with Cephalopod-Inspired Nanocomposites.

Brilliant and dynamic colors in nature have stimulated the design of dyes and pigments with broad applications ranging from electronic displays to apparel. Inspired by the nanostructured pigment granules present in cephalopod chromatophore organs, we describe the design and fabrication of biohybrid colorants containing the cephalopod-specific pigment, xanthommatin (Xa), encased within silica-based nanostructures. We employed a biomimetic approach to encapsulate Xa with amine-terminated polyamidoamine (PAMAM) dendrimer templates, which helped stabilize the pigment during encapsulation. Depending on the concentration of Xa used in the reaction, the resultant biohybrid nanomaterials generated a range of neutral colors of differing hues. When applied as coatings, these colorants can be triggered to change color from yellow/gold to red in the presence of a chemical reducing agent, as we leverage the natural redox-dependent color change of Xa. Altogether, these capabilities demonstrated the ability to process biochromes like Xa as nanomaterials that can be applied as coatings with a tunable and dynamic range.

Sulfated N-acetylglucosamino-glucuronopyranosyl-arabinopyranan from seafood Amphioctopus neglectus attenuates angiotensin-II prompted cardiac hypertrophy.

Angiotensin converting enzyme (ACE) is a multifunctional enzyme involved in translation of angiotensin-I (AngI) to vasoconstrictor angiotensin-II (AngII). A sulfated N-acetylglucosamino-glucuronopyranosyl-arabinopyranan characterized as poly-[(2-methoxy-ß-arabinopyranosyl)-(1 â†’ 3)-(ß-glucurono)-(1 â†’ 4)-(2-acetamido-2-deoxy-3,6-di-O-sulfonato-ß-glucopyranose)] was purified and reported first time from the edible portion of Amphioctopus neglectus and evaluated for various pharmacological properties. The polysaccharide exhibited potential ACE attenuation property (IC50 0.11 mg mL-1), whereas molecular docking simulations displayed its efficient binding at the ACE active site with lesser inhibitory constant (Ki) of 17.36 nM and binding energy (-10.59 kcal mol-1). The in-vitro analysis showed that the studied polysacharide attenuated AngII prompted cardiac hypertrophy at 50 µg mL-1 in the cardiomyoblast cells, whereas 48% reduction in cellular surface area with extended viability could be correlated with anti-hypertrophic properties of the studied polysaccharide. The sulfated N-acetylglucosamino-glucuronopyranosyl-arabinopyranan purified from A. neglectus could function as a prospective functional lead against the pathophysiological conditions leading to hypertension.

Bioactive fatty acids in seafood from Ionian Sea and relation to dietary recommendations.

The objective of the present study was to determine lipid content, fatty acid composition and the recommended daily portion of 13 fish species, nine bivalves, six crustacean, three echinoderm and three cephalopod species, from the Mediterranean Sea (Southern Italy). Fatty acids profile varied significantly among species (p < .05); polyunsaturated fatty acids represented an important proportion, with docosahexaenoic and eicosapentaenoic acids in the highest amount. A high n3/n6 ratio was found in all species (from 1.0 in body wall of Holothuria polii and H. tubulosa to 10.9 in Mytilus galloprovincialis). The lipid nutritional quality indices (atherogenic index, thrombogenicity index and hypocholesterolaemic/hypercholesterolaemic fatty acid ratio) showed crustaceans Parapaeneus longirostris, Plesionika martia, Melicertus kerathurus, Nephrops norvegicus, as likely to be more beneficial for the consumer health. This paper will be of practical value from a health perspective for populations who consume seafood and a powerful marketing tool for farmers.

Assessment of Tetrabromobisphenol and Hexabromocyclododecanes exposure and risk characterization using occurrence data in foods.

Tetrabromobisphenol A (TBBPA) and Hexabromocyclododecanes (HBCDs) are two of the most used BFRs and they have cumulated in the environment. TBBPA and HBCDs in food were determined and their risks were assessed. The analytical method used was validated in different food categories, and the performance parameters were acceptable based on the criteria of AOAC. Fish and cephalopods were contaminated with TBBPA higher than other foods, and fish contained higher levels of HBCDs than other foods. α-HBCD was the predominant diastereomer in fish and meat and had strong correlations with HBCDs in fish and cephalopods. HBCDs accumulated easier than TBBPA in food. People were exposed to TBBPA from 0.125 ng kg-1 b.w. day-1 to 0.284 ng kg-1 b.w. day-1 and HBCDs from 0.353 ng kg-1 b.w. day-1 to 1.006 ng kg-1 b.w. day-1 via food and air. Food mainly contributed to exposure to TBBPA and HBCDs and vegetables were the main contributors for exposure to TBBPA and HBCDs in food. MOEs for the whole population were over 100, and the risks of exposure to TBBPA and HBCDs from food and the environment were of low concern to public health.

Marine waste to a functional biomaterial: Green facile synthesis of modified-ß-chitin from Uroteuthis duvauceli pens (gladius).

Chitin is the second most abundant biomass on earth but exploited the least. In this study, wastes from Uroteuthis duvauceli was utilized to extract 38.79 ±â€¯1.38% dry weight of ß-chitin using a new combination of decolorization, demineralization, and deproteinization processes. ß-chitin was then derivatized with acrylamide in an efficient and green aqueous 8 wt% NaOH/4 wt% urea solvent via one-pot etherification. The success of carbamoylethyl ether of chitin and carboxyethyl chitin synthesis was confirmed by FTIR, 1H NMR, 13C NMR, XRD, SEM, TGA, and DSC. The synthesized acrylamide-modified ß-chitin derivatives were shown to exhibit water solubility and lower decomposition temperatures, which are primarily due to the disruption of the crystalline structure of ß-chitin upon its dissolution and modification. In this era of climate change, this desirable strategy of harnessing ß-chitin from wastes and converting it to value-added products is highly sought to mitigate the continuing ecological and economical imbalance brought about by marine-food wastes. To the best of our knowledge, this novel contribution is the first to report biorefinery of squid pens from this particular species and functionalizing it with acrylamide in a facile manner, thus, offering greater potential for future development to biocompatible chitin-based biomaterials intended for industrial, pharmaceutical and biomedical applications.

Reconfigurable soft body trajectories using unidirectionally stretchable composite laminae.

Compliant, continuum structures allow living creatures to perform complex tasks inaccessible to artificial rigid systems. Although advancements in hyper-elastic materials have spurred the development of synthetic soft structures (i.e., artificial muscles), these structures have yet to match the precise control and diversity of motions witnessed in living creatures. Cephalopods tentacles, for example, can undergo multiple trajectories using muscular hydrostat, a structure consisting of aggregated laminae of unidirectional muscle fibers. Here, we present a self-adhesive composite lamina inspired by the structural morphology of the muscular hydrostat, which adheres to any volumetrically expanding soft body to govern its motion trajectory. The composite lamina is stretchable only in one direction due to inextensible continuous fibers unidirectionally embedded within its hyper-elastic matrix. We showcase reconfiguration of inflation trajectories of two- and three-dimensional soft bodies by simply adhering laminae to their surfaces.

Mercury and Po-210 in mollusc species in the island of Gökçeada in the north-eastern Aegean Sea: Bioaccumulation and risk assessment for human consumers.

Among the radioactive pollutants 210Po is the most substantial one in terms of seafood safety due to its efficient accumulation in marine animals and high irradiation of its alpha emission. Mercury is a highly toxic metal for both marine organisms and human beings. Biomagnification of MeHg (methylmercury) through marine food chains has made Hg concern of ecotoxicology and seafood safety. In the current study, the bioaccumulation of 210Po and THg (total mercury) were determined in 20 mollusc species, including 8 bivalves, 7 gastropods and 5 cephalopods collected from the island of Gökçeada in the north-eastern Aegean Sea. The highest accumulation of 210Po and Hg was seen in bivalves and cephalopods, respectively. Elevated Hg concentrations in all body parts (arms, mantle and viscera) were observed in octopus' species. The results of this study suggests that filter feeder bivalves and gastropods have a capacity to concentrate 210Po in their bodies, whereas predator gastropods and cephalopods have a capacity to concentrate Hg in their bodies. 7.0 kg (3.2-14.2) bivalve flesh intake is adequate due to 210Po ingestion in the studied region to reach 1 mSv which is the annual committed effective dose. Octopus consumption of 705 g in a week alone is needed to reach Provisional Tolerable Weekly Intake (PTWI) of mercury, 5 µg kg-1 body weight. Due to very low non-fish seafood consumption in Turkey there is no risk of Hg intake and alpha radiation of 210Po above the limit values through mollusc consumption.

Ecological pressures and the contrasting scaling of metabolism and body shape in coexisting taxa: cephalopods versus teleost fish.

Metabolic rates are fundamental to many biological processes, and commonly scale with body size with an exponent ( bR) between 2/3 and 1 for reasons still debated. According to the 'metabolic-level boundaries hypothesis', bR depends on the metabolic level ( LR). We test this prediction and show that across cephalopod species intraspecific bR correlates positively with not only LR but also the scaling of body surface area with body mass. Cephalopod species with high LR maintain near constant mass-specific metabolic rates, growth and probably inner-mantle surface area for exchange of respiratory gases or wastes throughout their lives. By contrast, teleost fish show a negative correlation between bR and LR. We hypothesize that this striking taxonomic difference arises because both resource supply and demand scale differently in fish and cephalopods, as a result of contrasting mortality and energetic pressures, likely related to different locomotion costs and predation pressure. Cephalopods with high LR exhibit relatively steep scaling of growth, locomotion, and resource-exchange surface area, made possible by body-shape shifting. We suggest that differences in lifestyle, growth and body shape with changing water depth may be useful for predicting contrasting metabolic scaling for coexisting animals of similar sizes. This article is part of the theme issue 'Physiological diversity, biodiversity patterns and global climate change: testing key hypotheses involving temperature and oxygen'.

Correlation between Fatty Acid Profile and Anti-Inflammatory Activity in Common Australian Seafood by-Products.

Marine organisms are a rich source of biologically active lipids with anti-inflammatory activities. These lipids may be enriched in visceral organs that are waste products from common seafood. Gas chromatography-mass spectrometry and fatty acid methyl ester (FAME) analyses were performed to compare the fatty acid compositions of lipid extracts from some common seafood organisms, including octopus (Octopus tetricus), squid (Sepioteuthis australis), Australian sardine (Sardinops sagax), salmon (Salmo salar) and school prawns (Penaeus plebejus). The lipid extracts were tested for anti-inflammatory activity by assessing their inhibition of nitric oxide (NO) and tumor necrosis factor alpha (TNFα) production in lipopolysaccharide (LPS)-stimulated RAW 264.7 mouse cells. The lipid extract from both the flesh and waste tissue all contained high amounts of polyunsaturated fatty acids (PUFAs) and significantly inhibited NO and TNFα production. Lipid extracts from the cephalopod mollusks S. australis and O. tetricus demonstrated the highest total PUFA content, the highest level of omega 3 (ω-3) PUFAs, and the highest anti-inflammatory activity. However, multivariate analysis indicates the complex mixture of saturated, monounsaturated, and polyunsaturated fatty acids may all influence the anti-inflammatory activity of marine lipid extracts. This study confirms that discarded parts of commonly consumed seafood species provide promising sources for the development of new potential anti-inflammatory nutraceuticals.

Dynamic pigmentary and structural coloration within cephalopod chromatophore organs.

Chromatophore organs in cephalopod skin are known to produce ultra-fast changes in appearance for camouflage and communication. Light-scattering pigment granules within chromatocytes have been presumed to be the sole source of coloration in these complex organs. We report the discovery of structural coloration emanating in precise register with expanded pigmented chromatocytes. Concurrently, using an annotated squid chromatophore proteome together with microscopy, we identify a likely biochemical component of this reflective coloration as reflectin proteins distributed in sheath cells that envelop each chromatocyte. Additionally, within the chromatocytes, where the pigment resides in nanostructured granules, we find the lens protein Ω- crystallin interfacing tightly with pigment molecules. These findings offer fresh perspectives on the intricate biophotonic interplay between pigmentary and structural coloration elements tightly co-located within the same dynamic flexible organ - a feature that may help inspire the development of new classes of engineered materials that change color and pattern.

Comparative Proteomic Analysis of Slime from the Striped Pyjama Squid, Sepioloidea lineolata, and the Southern Bottletail Squid, Sepiadarium austrinum (Cephalopoda: Sepiadariidae).

Sepioloidea lineolata, the striped pyjama squid (family Sepiadariidae), is a small species of benthic bobtail squid distributed along the Southern Indo-Pacific coast of Australia. Like other sepiadariid squids, it is known to secrete large volumes of viscous slime when stressed. In order to identify key proteins involved in the function of sepiadariid slimes, we compared the slime proteome of Sepioloidea lineolata with that of a closely related species, Sepiadarium austrinum. Of the 550 protein groups identified in Sepioloidea lineolata slime, 321 had orthologs in Sepiadarium austrinum, and the abundance of these (iBAQ) was highly correlated between species. Both slimes were dominated by a small number of abundant proteins, and several of these were short secreted proteins with no homologues outside the class Cephalopoda. No mucins were identified within either species' slime, suggesting that it is structurally distinct from mucin polymer-based gels found in many vertebrate and echinoderm secretions. The extent of N-glycosylation in the slime of Sepioloidea lineolata was also studied via glycan cleavage with Peptide: N-glycosidase F (PNGase-F). Although very few (four) proteins showed strong evidence of N-glycosylation, we found that treatment with PNGase-F led to a slight increase in peptide identification rates compared with controls.

From pristine aragonite to blocky calcite: Exceptional preservation and diagenesis of cephalopod nacre in porous Cretaceous limestones.

Aragonite (along with calcite) is one of the most common polymorphs of the crystalline calcium carbonate that forms the skeletal structures of organisms, but it has relatively low preservation potential. Under ambient conditions and in the presence of water, aragonite transforms into calcite, the stable polymorph. Aragonite is also more soluble therefore, in water-permeable siliceous limestones (opokas) that are typical of Upper Cretaceous deposits of Poland and Ukraine, the primary aragonitic skeletons are either entirely dissolved and found as moulds and casts or transformed into secondary calcite, whereas the primary calcitic shells remain well preserved. Contrary to the common notion of the lack of aragonite in such porous carbonate deposits, we show that relics of aragonite can be preserved as a nacreous lining on cephalopod moulds or as thin, lenticular structures entrapped in neomorphic calcite. Based on the observed intermediate steps of aragonite alteration, we propose an extended model of nacre diagenesis. Among the originally aragonitic biota, only nautilids and ammonites have retained relics of pristine skeletons. Such selective preservation of only some aragonitic structures (nacre but not the prismatic aragonitic layers) points to the role of microstructural and biochemical differences between cephalopod shell layers that may set a threshold for the dissolution, dissolution/precipitation or preservation of original biomineral structures.

An introduction to color-changing systems from the cephalopod protein reflectin.

Cephalopods possess unrivaled camouflage and signaling abilities that are enabled by their sophisticated skin, wherein multiple layers contain chromatophore pigment cells (as part of larger chromatophore organs) and different types of reflective cells called iridocytes and leucophores. The optical functionality of these cells (and thus cephalopod skin) critically relies upon subcellular structures partially composed of unusual structural proteins known as reflectins. Herein, we highlight studies that have investigated reflectins as materials within the context of color-changing coatings. We in turn discuss these proteins' multi-faceted properties, associated challenges, and future potential. Through our presentation of selected case studies, we hope to stimulate additional dialogue and spur further research on photonic technologies based on and inspired by reflectins.

Influence of the submarine volcanic eruption off El Hierro (Canary Islands) on the mesopelagic cephalopod's metal content.

This work investigates whether a submarine volcanic eruption off El Hierro (Canary Islands) in October 2011 influenced the metal contents of two deep water cephalopod species: Abraliopsis morisii and Pyroteuthis margaritifera. This was assessed by comparing metal contents in specimens collected off the island of El Hierro and in the neighbouring islands of La Palma and Tenerife during an experimental deep water fishing trip. The concentration of 20 heavy metals was analyzed in 180 specimens of A. morisii and P. margaritifera collected around the three islands to test for inter-island differences for each species and metal. While both species showed geographical differences in metal concentrations, the main finding was that A. morisii could be a bioindicator species for metals such as Li, Sr and Ca.

Color Richness in Cephalopod Chromatophores Originating from High Refractive Index Biomolecules.

Cephalopods are arguably one of the most photonically sophisticated marine animals, as they can rapidly adapt their dermal color and texture to their surroundings using both structural and pigmentary coloration. Their chromatophore organs facilitate this process, but the molecular mechanism potentiating color change is not well understood. We hypothesize that the pigments, which are localized within nanostructured granules in the chromatophore, enhance the scattering of light within the dermal tissue. To test this, we extracted the phenoxazone-based pigments from the chromatophore and extrapolated their complex refractive index (RI) from experimentally determined real and approximated imaginary portions of the RI. Mie theory was used to calculate the absorbance and scattering cross sections (cm2/particle) across a broad diameter range at λ = 589 nm. We observed that the pigments were more likely to scatter attenuated light than absorb it and that these characteristics may contribute to the color richness of cephalopods.

[Cephalopods as a Source of New Antimicrobial Substances].

Under the conditions of emergence of microbial strains with new properties, including antibiotic resistance, in human and animal populations the search for new antimicrobial substances with improved pharmacological properties and new mechanisms of action from natural objects, in particular from aquatic organisms, is continued. This review presents extensive data on antibacterial, antiviral and antifungal properties of biologically active substances (BAS) of different chemical nature, recovered from representatives of the class of cephalopods (squid, octopus, cuttlefish, nautilus). Analysis of the literature shows that antibacterial activity of some BAS is not inferior, but in some cases is even superior to that of the available antibiotics. The authors note that the review includes the results, mainly of the in vitro studies. Adequate extrapolation of these data to the in vivo conditions is required, that could serve as foundation for development of new generations of medicinal compounds, functional foods and biologically active food supplements.

Biologically Active Substances from Marine Hydrobionts with Antibacterial Activity in Composition of New Wound Dressings.

The data on the experimental study of the efficacy of the gel wound dressings based on chitosan and calcium alginate containing bioactive substances from marine hydrobionts with complex therapeutic action (sulfated polysaccharides from brown algae, hydrolyzed bivalves, peptides from nerve ganglia of cephalopods) are described. The model of thermal burns complicated by Staphylococcus aureus infection was used. Planimetric and bacteriological investigations revealed pronounced wound healing and antibacterial effects of the gel coating. The gel containing sulfated polysaccharides from brown algae showed the highest wound healing activity.