Yellow discoloration of the liposome system of cuttlefish (Sepia pharaonis) as influenced by lipid oxidation

Lipid oxidation, discoloration, loss of amine groups and pyrrolization of the liposome systems of cuttlefish (Sepia pharaonis) in the presence of FeCl₃ and ascorbic acid were studied. Thiobarbituric acid-reactive substances (TBARS) and the b^∗-value of cuttlefish liposomes increased with a coincidental decrease in amine groups when the incubation temperatures (0, 4, 25, and 37 °C) and incubation times (0–24 h) were increased (p < 0.05). As lipid oxidation and yellow pigment formation in the cuttlefish liposome proceeded, a loss of amine groups and pyrrolization were also detected. The effects of FeCl₃ and ascorbic acid, at different concentrations, on TBARS production, b^∗-value, loss of amine groups and pyrrolization of cuttlefish liposome were also investigated. Both FeCl₃ and ascorbic acid showed prooxidative effects in cuttlefish liposome in a concentration-dependent manner. Sodium chloride (0–2%) reduced TBARS, b^∗-values and pyrrole compounds. These results suggest a positive correlation between lipid oxidation and the development of yellow pigments in cuttlefish phospholipids.     

Effect of different treatments on the quality of cuttlefish (Sepia officinalis L.) viscera

The effects of different preservation times (cuttlefish auction), transformation factory treatments, different times of frozen storage at −20 °C and various defrosting temperatures were investigated with respect to the chemical changes of the viscera of cuttlefish (Sepia officinalis). During auction storage, pH and TCA (trichloroacetic acid)-soluble protein concentration decreased, whereas intracellular (cathepsins, total acid proteases and acid phosphatases) and extracellular (amylase, chymotrypsin, trypsin and total alkaline proteases) enzymatic activities increased. In cuttlefish transformation factories, pH value and TCA-soluble protein concentration increased. In transformation factory conditions, lipase and amylase levels varied, while other assayed enzymes were stable. Moreover, during transformation factory treatment, the molecular weight of proteins/peptides decreased and the oil composition evolution reflected hydrolysis of cuttlefish viscera. Thus, cuttlefish viscera fatty acid composition differed between fresh viscera and factory viscera. Despite changes in the fatty acid chain composition during factory transformation, the percentage of poly-unsaturated fatty acids remained high. Frozen storage implied major changes in viscera quality such as an increase in pH and a decrease in the quantity of high molecular weight protein. Moreover, the higher the defrosting temperature, the higher was the pH. During storage at −20 °C the quantities of proteins, carbohydrates and lipids decreased slightly.     

Seasonal changes of fatty acids of cuttlefish Sepia officinalis L. (Mollusca: Cephalopoda) in the north eastern Mediterranean sea

The total lipids and seasonal variations in the fatty acids of the mantle of cuttlefish (Sepia officinalis) captured in the north eastern Mediterranean were investigated and the mantle was found to be a good source of polyunsaturated fatty acids (ω3 PUFAs, in particular). In all seasons, the major fatty acids in the cuttlefish mantle were observed to be palmitic acid (16:0), stearic acid (18:0), eicosapentaenoic acid (EPA, 20:5ω3) and docosahexaenoic acid (DHA, 22:6ω3). A comparison of the saturated fatty acid (29.5–36.8%), monounsaturated fatty acids (7.81–9.84%) and polyunsaturated fatty acids (43.7–49.6%) of the cuttlefish mantle revealed that polyunsaturated fatty acids (PUFA) constituted the highest proportion. The levels of DHA in the cuttlefish mantle in autumn, winter, spring and summer were 27.6%, 28.5%, 29.5% and 23.9%, while those of EPA were 16.8%, 15.4%, 14.7% and 13.9%, respectively.     

Extraction and functional properties of gelatin from the skin of cuttlefish (Sepia officinalis) using smooth hound crude acid protease-aided process

The characteristics and functional properties of gelatin from skin cuttlefish (Sepia officinalis) were investigated and compared to those of halal bovine gelatin (HBG). The gelatin extraction efficiency was improved by an acid-swelling process in the presence of smooth hound crude acid protease extract (SHCAP). The yields of gelatins from cuttlefish skin after 48 h with acid and with crude acid protease (15 units/g alkaline-treated skin) were 2.21% and 7.84%, respectively. The gelatin from skin cuttlefish had high protein (91.35%) but low fat (0.28%) contents. Compared to HBG, the cuttlefish-skin gelatin (CSG) has different amino acids composition than halal bovine gelatin. CSG contained slightly low hydroxyproline and proline (180‰) than HBG (219‰), whereas the content of serine was higher (49‰ versus 29‰). The gel strength of the gelatin gel from CSG (181 g) was lower than that of HBG (259 g) (p < 0.05) possibly due to lower hydroxyproline content. Cuttlefish-skin gelatin exhibited a similar emulsifying activity but greater emulsifying and foam stability than the halal bovine gelatin (p < 0.05). Foam formation ability, foam stability and water-holding capacity of CSG were slightly lower than those of the HBG, but fat-binding capacity was higher in the cuttlefish gelatin.     

Low-temperature synthesis of nanometric apatite from biogenic sources

Nanosized calcium deficient carbonated apatite was synthesized from three different natural resources, namely chicken eggshells (calcite), cuttlefish bones (aragonite) and mussel shells (aragonite/calcite). The calcium precursors were ball-milled in (NH₄)₂HPO₄ or H₃PO₄ – containing aqueous medium for different times and then dried at temperatures ranging from 20 °C to 150 °C. The formation of hydroxyapatite (HA) is shown to be strongly affected by such treatment, the amount of synthesized HA increasing with temperature. Aragonite from cuttlebones and the aragonitic fraction of mussels is found to be transformed more easily with respect to the calcite from eggshells. The reaction is also favored by an acidic milling media with respect to basic one. The feasibility of the synthesis process at nearly room temperature described in the present work has interesting potentialities in the retention of the organic portions of the original biological resource in the produced nanometric inorganic compound.     

Chemical Composition of Inks of Diverse Marine Molluscs Suggests Convergent Chemical Defenses

Some marine molluscs, notably sea hares, cuttlefish, squid, and octopus, release ink when attacked by predators. The sea hare Aplysia californica releases secretions from the ink gland and opaline gland that protect individuals from injury or death from predatory spiny lobsters through a combination of mechanisms that include chemical deterrence, sensory disruption, and phagomimicry. The latter two mechanisms are facilitated by millimolar concentrations of free amino acids (FAA) in sea hare ink and opaline, which stimulate the chemosensory systems of predators, ultimately leading to escape by sea hares. We hypothesize that other inking molluscs use sensory disruption and/or phagomimicry as a chemical defense. To investigate this, we examined concentrations of 21 FAA and ammonium in the defensive secretions of nine species of inking molluscs: three sea hares (Aplysia californica, Aplysia dactylomela, Aplysia juliana) and six cephalopods (cuttlefish: Sepia officinalis; squid: Loligo pealei, Lolliguncula brevis, Dosidicus gigas; octopus: Octopus vulgaris, Octopus bimaculoides). We found millimolar levels of total FAA and ammonium in these secretions, and the FAA in highest concentration were taurine, aspartic acid, glutamic acid, alanine, and lysine. Crustaceans and fish, which are major predators of these molluscs, have specific receptor systems for these FAA. Our chemical analysis supports the hypothesis that inking molluscs have the potential to use sensory disruption and/or phagomimicry as a chemical defense.     

Properties of film from cuttlefish (Sepia pharaonis) skin gelatin incorporated with cinnamon,clove and star anise extracts

Properties of film from cuttlefish (Sepia pharaonis) ventral skin gelatin without and with partial hydrolysis (1.2% degree of hydrolysis) incorporated with 1% ethanolic extract of cinnamon (CME), clove (CLE) and star anise (SAE) were determined. Films with different herb extracts (without and with oxidation) had higher tensile strength (TS) but lower elongation at break (EAB), compared with the control film (without addition of herb extracts) (p < 0.05). Lower water vapor permeability (WVP) and L^∗-value but higher b^∗- and ΔE^∗-values were observed when the extracts were incorporated (p < 0.05). Electrophoretic study revealed that cross-linking was pronounced in films containing different herb extracts. Oxidized extracts yielded films with higher TS and WVP than those without oxidized herb extracts (p < 0.05). Generally, similar properties were noticeable for films from gelatin with and without partial hydrolysis. Nevertheless, higher mechanical properties were obtained for the latter. FTIR spectra indicated that protein–polyphenol interactions were involved in the film. Thermo-gravimetric analysis revealed that films incorporated with SAE or SAE with oxidation (OSAE) exhibited lower heat susceptibility and weight loss in the temperature range of 50–600 °C, compared with control film. Films with SAE and OSAE had smoother surface for gelatin without hydrolysis; however, coarser surface was observed in film from gelatin with partial hydrolysis. Thus, the incorporation of different herb extracts directly affected the properties of film from cuttlefish skin gelatin with and without hydrolysis.     

Improvement of functional properties and antioxidant activities of cuttlefish (Sepia officinalis) muscle proteins hydrolyzed by Bacillus mojavensis A21 proteases

Functional properties and antioxidant activities of cuttlefish (Sepia officinalis) muscle protein hydrolysates, with different degrees of hydrolysis (DH from 7.3% to 18.8%), obtained by treatment with Bacillus mojavensis A21 alkaline proteases were investigated. Protein contents for all freeze-dried cuttlefish muscle protein hydrolysates (CMPHs) ranged from 80% to 86%. For the functional properties, hydrolysis by A21 proteases increased (p < 0.05) protein solubility to above 78% over a wide pH range (2.0–11.0). However, the interfacial activities (emulsion activity index, emulsion stability index, foaming capacity and foaming stability) decreased with the increase of the DH. All CMPHs exhibited significant metal chelating activity and DPPH free radical-scavenging activity, and inhibited linoleic acid peroxidation. Antioxidant properties of protein hydrolysates increased with protein hydrolysis and the highest activities were obtained at DH of 16%. The IC₅₀ values for DPPH radical-scavenging and metal chelating activities were found to be 0.52 ± 0.01 mg/ml and 0.67 ± 0.13 mg/ml. The obtained results suggested that functional properties and antioxidant activities of cuttlefish muscle protein hydrolysates were influenced by the degree of hydrolysis.The composition of amino acids of undigested and hydrolyzed proteins was determined. CMPHs have a high percentage of essential amino acids such as arginine, lysine, histidine and leucine. They have a high nutritional value and could be used as supplement to poorly balanced dietary proteins.     

Heteroatom-doped carbon nanospheres derived from cuttlefish ink: A bifunctional electrocatalyst for oxygen reduction and evolution

The development of efficient bifunctional catalysts for both oxygen reduction and oxygen evolution reactions is highly desirable but challenging in energy conversion and storage systems. Here, a simple yet cost-effective strategy is developed to produce heteroatom-doped carbon nanospheres using natural cuttlefish ink as the precursor. For the oxygen reduction reaction, the catalyst exhibits more positive onset-potential and larger diffusion limiting current density compared with benchmark platinum catalyst in alkaline medium. Moreover, the as synthesized catalyst shows low onset-potential for oxygen evolution reaction, indicating its outstanding catalytic activity. The catalyst shows a potential gap of 0.75 V between the oxygen evolution reaction potential at a current density of 10 mA cm^?2 and the oxygen reduction reaction potential at the half-wave potential, outperforming most of other noble metal-free carbon catalysts in the current state of research. The remarkable catalytic performance can be assigned to heteroatoms doping, full exposure of the active sites, large surface area and enrichment of pores for sufficient contact and rapid transportation of the reactants. This study offers a new approach for the synthesis of metal-free carbon nanomaterials from natural resources, and broadens the design for the fabrication of bifunctional oxygen reduction and oxygen evolution catalysts.     

Sensory, microbiological, physical and chemical properties of cuttlefish (Sepia officinalis) and broadtail shortfin squid (Illex coindetii) stored in ice

The objective of this study was to characterize whole raw cuttlefish (Sepia officinalis) and shortfin squid (Illex coindetii) during storage in ice through sensory, microbiological, chemical and physical analyses. The recently developed Quality Index Method (QIM) tables for these species were used for sensory analysis. Shelf-life of whole cuttlefish and shortfin squid were estimated as around 10 and 9 days, respectively, according to QIM, which is shorter than for most species, especially fish. The numbers of microorganisms found in cuttlefish and shortfin squid surfaces until rejection were lower than in fish, which suggest predominance of enzymatic (autolytic) degradation. H₂S-producing bacteria constituted a significant proportion of the spoilage flora. Physical analysis performed using the RT-Freshmeter and the Torrymeter showed these instruments can be applied to cuttlefish and shortfin squid, providing useful complementary information on the rates of change of electrical properties. Free tryptophan and VBN contents significantly changed during the first storage week indicating that low levels of these compounds could be used as indicators of fresh and high quality cuttlefish and broadtail shortfin squid. Urea can be useful as spoilage indicator for cuttlefish, as well as agmatine for broadtail shortfin squid. An overall look into data obtained shows, as expected, that spoilage of these cephalopod species can be considered a different phenomena when compared to fish and is not yet completely clarified.