Natural bio-waste-derived 3D N/O self-doped heteroatom honeycomb-like porous carbon with tuned huge surface area for high-performance supercapacitor.

Supercapacitor electrodes (SCs) of carbon-based materials with flexible structures and morphologies have demonstrated excellent electrical conductivity and chemical stability. Herein, a clean and cost-effective method for producing a 3D self-doped honeycomb-like carbonaceous material with KOH activation from bio-waste oyster shells (BWOSs) is described. A remarkable performance was achieved by the excellent hierarchical structured carbon (HSC-750), which has a large surface area and a reasonably high packing density. The enhanced BWOSs-derived HSC-750 shows an ultrahigh specific capacitance of 525 F/g at 0.5 A g-1 in 3 M KOH electrolyte, as well as high specific surface area (2377 m2 g-1), pore volume (1.35 cm3 g-1), nitrogen (4.70%), and oxygen (10.58%) doping contents. The SCs also exhibit exceptional cyclic stability, maintaining 98.5% of their capacitance after 10,000 charge/discharge cycles. The two-electrode approach provides a super high energy density of 28 Wh kg-1 at a power density of 250 W kg-1 in an alkaline solution, with remarkable cyclability after 10,000 cycles. The study demonstrates the innovative HSC synthesis from BWOSs precursor and cost-effective fabrication of 3D N/O self-doped heteroatom HSC for flexible energy storage.

Effect of non-enzymatic browning on oysters during hot air drying process: Color and chemical changes and insights into mechanisms.

Hot air drying (HAD) is an extensive method used on oysters and it causes the most intuitive change, a color change. However, the mechanism of color change remains unclear. This study showed that oysters underwent browning during the HAD process. The colorimetric parameter L* decreased while a* and b* increased, all of which were well described by the first-order color kinetic model. Mechanistically, the HDA process induced the oxidative browning of phenols and the generation of Maillard reaction products (5-hydroxymethylfurfural and hydrophilic pyrrole). Meanwhile, the HAD process caused lipid oxidation, leading to the reduction of phosphatidylethanolamine and the generation of reactive carbonyl compounds (aldehydes and α-dicarbonyl compounds). Moreover, the accumulation of hydrophobic pyrroles, a lipid-induced Maillard-like reaction product, was observed. These results suggest that, in addition to phenolic oxidation, sugar- and amino acid-mediated non-enzymatic browning reactions, lipid-mediated Maillard-like reactions play important roles in oyster darkening during the HAD process.

Contamination by microplastics in oysters shows a widespread but patchy occurrence in a subtropical estuarine system.

Microplastics (MPs) have been widely documented in marine biota, with a notable presence in bivalve species. This study examines microplastic (MP) contamination in oysters across a subtropical estuarine system, revealing widespread and highly variable levels of contamination. Our results indicate a general trend of higher contamination in areas with greater anthropogenic impact, and unexpectedly high values in remote Marine Protected Areas, suggesting alternative sources of MPs. We observed a 94.31 % frequency of occurrence and an average contamination level of 8.16 ± 6.39 MP.ind-1, 1.06 ± 1.28 MP.g-1ww, and 7.54 ± 6.55 MP.g-1dw. Transparent fibers, predominantly composed of polyester and polyethylene from likely textile origins, were the most common. The findings underscore the significance of MP pollution in marine environments, even in protected zones. For enhanced spatial assessment and consistent data comparison, we recommend that future studies include MP quantities in terms of dry weight (MP.g-1dw) and biometric data such as size and weight.

Adsorption properties of Pb(II) and Cd(II) in acid mine drainage by oyster shell loaded lignite composite in different morphologies.

A new idea to alleviate environmental pollution is the development of low-cost adsorbents using natural minerals and fishery wastes to treat high concentrations of heavy metal pollutants in acid mine drainage (AMD). Adsorbent morphology, adsorptive and regenerative capacity, and application potential are limiting factors for their large-scale use. Oyster shells capable of releasing alkalinity were loaded on the surface of lignite to develop two composite adsorbents with different morphologies (powdery and globular) for the treatment of AMD containing Pb(II) and Cd(II). The results show that the ability of the adsorbent to treat AMD is closely related to its morphologies. The pseudo-second-order kinetic model and the Langmuir model are suitable to describe the adsorption process of OS-M(P), and the maximum adsorption saturation capacities of Pb(II) and Cd(II) are 332.6219 mg/g and 318.9854 mg/g, respectively. The pseudo-second-order kinetic model and the Freundlich model are suitable to describe the adsorption process of OS-M(G). A synergistic result of electrostatic adsorption, neutralization precipitation, ion exchange and complex reaction is achieved in the removal of Pb(II) and Cd(II) by two morphologies of adsorbents. The regeneration times (5 times) and recovery rate (75.75%) of OS-M(G) are higher than those of OS-M(P) (3 times) and recovery rate (20%). The ability of OS-M(G) to treat actual AMD wastewater is still better than that of OS-M(P). OS-M(G) can be used as a promising environmentally friendly adsorbent for the long-term remediation of AMD. This study provides a comprehensive picture of resource management and reuse opportunities for natural mineral and fishery wastes.

Effect of baking on the structure and bioavailability of protein-binding zinc from oyster (Crassoetrea hongkongensis).

To compare the bioavailability of protein-binding zinc, we investigated the impact of baking on the structure of zinc-binding proteins. The results showed that zinc-binding proteins enriched in zinc with relative molecular weights distributed at 6 kDa and 3 kDa. Protein-binding zinc is predisposed to separate from proteins' interiors and converge on proteins' surface after being baked, and its structure tends to be crystalline. Especially -COO, -C-O, and -C-N played vital roles in the sites of zinc-binding proteins. However, baking did not affect protein-binding zinc's bioavailability which was superior to that of ZnSO4 and C12H22O14Zn. They were digested in the intestine, zinc-binding complexes that were easily transported and uptaken by Caco-2 cells, with transport and uptake rates as high as 62.15% and 15.85%. Consequently, baking can alter the conformation of zinc-binding proteins without any impact on protein-binding zinc's bioavailability which is superior to that of ZnSO4 and C12H22O14Zn.

Reactivity and bioconcentration of stable cesium in a hyperturbid fluvial-estuarine continuum: A combination of field observations and geochemical modeling.

Effective, post-accidental management needs an accurate understanding of the biogeochemical behavior of radionuclides in surface environments at a regional scale. Studies on stable isotopes (element homologs) can improve this knowledge. This work focuses on the biogeochemical behavior of stable cesium (Cs) along a major European fluvial-estuarine system, the Gironde Estuary (SW France). We present results obtained from (i) a long-term monitoring (2014-2017) of dissolved (Csd) and particulate (Csp) Cs concentrations at five sites along the freshwater continuum of the Garonne watershed, (ii) Csd and Csp concentrations during four oceanographic campaigns at contrasting hydrological conditions along longitudinal profiles of the estuarine system, (iii) a 24 h cycle of Csp at the estuary mouth, and (iv) a historical trend of Cs bioconcentration in wild oysters at the estuary mouth (RNO/ROCCH, 1984-2017). In addition, we model the partitioning of Cs within the estuarine environment for clay mineral interactions via PhreeqC. At fluvial sites, we observe a geogenic dependence of the Csp and a seasonal variability of Csd, with a downstream increase of the solid-liquid partitioning (log10 Kd values from 3.64 to 6.75 L kg-1) for suspended particulate matter (SPM) < 200 mg L-1. Along the estuarine salinity gradients, Cs shows a non-conservative behavior where fresh SPM (defined as Cs-depleted particles recently put in contact with Csd) act as a Cs sink during both flood and low discharge (drought) conditions. This sorption behavior was explained by the geochemical model, highlighting the relevance of ionic strength, water and SPM residence times. However, at high salinities, the overall log10 Kd value decreases from 6.02 to 5.20 for SPM ∼300-350 mg L-1 due to the Csd oceanic endmember. Despite wild oysters showing low bioconcentration factors (∼1220 L kg-1) at the estuary mouth, they are sensitive organisms to Cs fluxes.

Landscape and risk assessment of microplastic contamination in farmed oysters and seawater along the coastline of China.

Microplastic (MP) pollution poses a significant threat to marine ecosystem and seafood safety. However, comprehensive and comparable assessments of MP profiles and their ecological and health in Chinese farming oysters are lacking. This study utilized laser infrared imaging spectrometer (LDIR) to quantify MPs in oysters and its farming seawater at 18 sites along Chinese coastlines. Results revealed a total of 3492 MPs in farmed oysters and seawater, representing 34 MP types, with 20-100 µm MP fragments being the dominant. Polyurethane (PU) emerged as the predominant MP type in oysters, while polysulfones were more commonly detected in seawater. Notably, oysters from the Bohai Sea exhibited a higher abundance of MPs (13.62 ± 2.02 items/g) and estimated daily microplastic intake (EDI, 2.14 ± 0.26 items/g/kg·bw/day), indicating a greater potential health risk in the area. Meanwhile, seawater from the Yellow Sea displayed a higher level (193.0 ± 110.7 items/L), indicating a greater ecological risk in this region. Given the pervasiveness and abundance of PU and its high correlation with other MP types, we proposed PU as a promising indicator for monitoring and assessing the risk MP pollution in mariculture in China. These findings provide valuable insights into the extent and characteristics of MP pollution in farmed oysters and seawater in China.

Microplastic contamination in filter-feeding oyster Saccostrea cuccullata: Novel insights in a marine ecosystem.

Microplastic (MP) pollution has become a pressing global concern. Oysters are well-known filter feeders who ingest food by filtering microscopic particles suspended in the surrounding water. Along with organic matter, filter-feeding also causes accidental ingestion of MP by oysters. Hence, the aim of the current investigation is to understand the MP contamination in filter-feeding oysters. A total of 500 specimens of oyster Saccostrea cuccullata collected from the intertidal zone of five sampling locations on the Gujarat coast, India. Specimens underwent analysis following established protocols. Each specimen was found to exhibit MP contamination, showing an abundance of 2.72 ± 1.98 MPs/g. A negative relationship was found between shell length and MP abundance. Predominantly, fibers were documented across all study sites. Black, blue, and red-colored MPs with 1-2 mm sizes were most dominant. MP polymer composition was identified as polyethylene terephthalate and polypropylene. Findings provide baseline information on levels of MPs contamination, which can be used to monitor future effects of MP pollution.

Pharmaceutical Residues in Edible Oysters along the Coasts of the East and South China Seas and Associated Health Risks to Humans and Wildlife.

The investigation of pharmaceuticals as emerging contaminants in marine biota has been insufficient. In this study, we examined the presence of 51 pharmaceuticals in edible oysters along the coasts of the East and South China Seas. Only nine pharmaceuticals were detected. The mean concentrations of all measured pharmaceuticals in oysters per site ranged from 0.804 to 15.1 ng g-1 of dry weight, with antihistamines being the most common. Brompheniramine and promethazine were identified in biota samples for the first time. Although no significant health risks to humans were identified through consumption of oysters, 100-1000 times higher health risks were observed for wildlife like water birds, seasnails, and starfishes. Specifically, sea snails that primarily feed on oysters were found to be at risk of exposure to ciprofloxacin, brompheniramine, and promethazine. These high risks could be attributed to the monotonous diet habits and relatively limited food sources of these organisms. Furthermore, taking chirality into consideration, chlorpheniramine in the oysters was enriched by the S-enantiomer, with a relative potency 1.1-1.3 times higher when chlorpheniramine was considered as a racemate. Overall, this study highlights the prevalence of antihistamines in seafood and underscores the importance of studying enantioselectivities of pharmaceuticals in health risk assessments.

Seasonal profile of common pharmaceuticals in edible bivalve molluscs.

Pharmaceuticals are recognised as environmental contaminants of emerging concern (CECs) due to their increasing presence in the aquatic environment, along with high bioactivity linked to their therapeutic use. Therefore, information on environmental levels is urgently required. This study examined the presence of a range of common pharmaceuticals in oysters and mussels intended for human consumption from England and Wales using stable isotope dilution tandem mass spectrometry. A range of compounds were detected in bivalve tissue, with the Selective Serotonin Reuptake Inhibitor antidepressant sertraline being most abundant, reaching a maximum concentration of 22.1 ng/g wet weight shellfish tissue. Levels of all pharmaceuticals showed seasonal and geographical patterns. A dietary risk assessment revealed that the levels of pharmaceuticals identified in bivalve molluscs represent a clear hazard, but not a risk for the consumer. This study highlights the requirement for further monitoring of the presence of pharmaceuticals and other CECs in bivalve molluscs.

Hazardous impacts of heavy metal pollution on biometric and biochemical composition of pearl oyster Pinctada radiata from five sites along Alexandria coast, with reference to its potential health risk assessment.

This study investigated the effect of heavy metals on the pearl oyster Pinctada radiata from 5 sites along the coast of Alexandria, with focus on its ecological health and potential risks to human consumption. Pollution results showed that Abu-Qir had the highest Cu and Cd values. Montaza and Eastern Harbor had the highest Fe and Pb values, respectively. Statistically, differences in metal concentrations among study sites were significant (p < 0.05). Non-carcinogenic risk (TTHQ) of tested metals and carcinogenic ones of Cd and Pb showed "high risk" on human health by consuming pearl oysters. Morphometric measurements and condition indices were studied to assess growth patterns and health in relation to heavy metals exposure. Key findings showed detectable declines in size and condition index in Eastern Harbor, whereas Abu-Qir recorded the highest values. This condition index performance presented Abu-Qir, Mammora, and Miami as ideal locations for spat collection and oyster rearing, potentially enhancing Egyptian pearl farming. Average values of spatial proximate contents of pearl oyster showed that it was rich in proteins (33.07-58.52%) with low fat content (1.39-1.87%) and carbohydrates (9.72-17.63%). Biochemical composition of pearl oyster demonstrated its high nutritional value which supported its promotion as a functional food for human consumption. The calorie content of pearl oyster was less than 2 Kcal, making this species an alternative source of healthy food to reduce obesity. Regression analysis indicated that Cu, Cd, and Pb had significant effect on 2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity, calories, vitamins, and pigment content of the collected oysters.

Integrated analysis of marine biotoxins and contaminants of emerging concern in bivalve mollusks from Santa Catarina, Brazil.

Santa Catarina is the main producer state of oysters and mussels in Brazil, reaching 98 % of national production. To assure the safety of bivalve mollusks production, control programs of marine biotoxins (MBs) have been continuously performed. Herein, the co-occurrence of MBs and contaminants of emerging concern (CECs) in oyster and mussels from the main production sites of Santa Catarina was reported, covering 178 compounds. Samples of wild and non-cultivated oysters and mussels were also assessed. Chemometric tools were used to evaluate and optimize several sample preparation techniques such as solid-liquid, ultrasound assisted, and pressurized liquid extraction. The optimized protocol was based on ultrasound assisted extraction followed by liquid chromatography coupled to tandem mass spectrometry. The results showed the incidence of several CECs and MBs. In the case of MBs, all results were below the regulatory limits for both cultivated and non-cultivated samples. Wild mollusks have shown a higher number of compounds. Regarding CECs, the more frequent compounds were caffeine, diclofenac, meloxicam, and sertraline. Domoic acid and okadaic acid were the main toxins detected. The results highlighted the need of monitoring for MBs and the potential of oyster and mussels as sentinel organisms to risk analysis of CECs in coastal regions. To the best of our knowledge, this is the first method to describe a simultaneous sample preparation and analysis of CECs and MBs in bivalve mollusks, as well as the first report of meloxicam and florfenicol in mussels and oysters.

Interlaboratory Evaluation of Multiple LC-MS/MS Methods and a Commercial ELISA Method for Determination of Tetrodotoxin in Oysters and Mussels.

BACKGROUND: Given the recent detection of tetrodotoxin (TTX) in bivalve molluscs but the absence of a full collaborative validation study for TTX determination in a large number of shellfish samples, interlaboratory assessment of method performance was required to better understand current capabilities for accurate and reproducible TTX quantitation using chemical and immunoassay methods. OBJECTIVE: The aim was to conduct an interlaboratory study with multiple laboratories, using results to assess method performance and acceptability of different TTX testing methods. METHODS: Homogenous and stable mussel and oyster materials were assessed by participants using a range of published and in-house detection methods to determine mean TTX concentrations. Data were used to calculate recoveries, repeatability, and reproducibility, together with participant acceptability z-scores. RESULTS: Method performance characteristics were good, showing excellent sensitivity, recovery, and repeatability. Acceptable reproducibility was evidenced by HorRat values for all LC-MS/MS and ELISA methods being less than the 2.0 limit of acceptability. Method differences between the LC-MS/MS participants did not result in statistically different results. Method performance characteristics compared well with previously published single-laboratory validated methods and no statistical difference was found in results returned by ELISA in comparison with LC-MS/MS. CONCLUSION: The results from this study demonstrate that current LC-MS/MS methods and ELISA are on the whole capable of sensitive, accurate, and reproducible TTX quantitation in shellfish. Further work is recommended to expand the number of laboratories testing ELISA and to standardize an LC-MS/MS protocol to further improve interlaboratory precision. HIGHLIGHTS: Multiple mass spectrometric methods and a commercial ELISA have been successfully assessed through an interlaboratory study, demonstrating excellent performance.

Effects of curcumin-mediated photodynamic treatment on lipid degradation of oysters during refrigerated storage.

BACKGROUND: Oyster's lipid degradation leads to a decrease in edible and nutritional value. Curcumin-mediated photodynamic treatment (PDT) is an innovative non-thermal technology, although evaluation of the oyster's lipid degradation has been scarce. In the present study, we investigated peroxide value, thiobarbituric acid reactive substance, triacylglycerol and free fatty acids to evaluate the effect of curcumin-mediated PDT on lipid degradation of oysters during refrigerated storage. RESULTS: The results showed that curcumin-mediated PDT could delay oyster's lipid degradation. Next, the activities of enzymes were detected to determine the mechanisms behind the effects of curcumin-mediated PDT. It was revealed that the activities of lipase, phospholipase A2 (PLA2 ), phospholipase C (PLC), phospholipase D (PLD) and lipoxygenase (LOX) were significantly inhibited after curcumin-mediated PDT (P < 0.05). Furthermore, 16 s rRNA analysis established that the relative abundances of Pseudoalteromonas and Psychrilyobacter were reduced by 51.58% and 43.82%, respectively, after curcumin-mediated PDT. CONCLUSION: Curcumin-mediated PDT could delay oyster's lipid degradation by inhibiting the activities of lipase, PLA2 , PLC, PLD and LOX, as well as by changing the oyster's microbial composition, reducing the relative abundance of Pseudoalteromonas and Psychrilyobacter. © 2021 Society of Chemical Industry.

Oyster Hydrolysates Attenuate Muscle Atrophy via Regulating Protein Turnover and Mitochondria Biogenesis in C2C12 Cell and Immobilized Mice.

Sarcopenia, also known as skeletal muscle atrophy, is characterized by significant loss of muscle mass and strength. Oyster (Crassostrea gigas) hydrolysates have anti-cancer, antioxidant, and anti-inflammation properties. However, the anti-sarcopenic effect of oyster hydrolysates remains uninvestigated. Therefore, we prepared two different oyster hydrolysates, namely TGPN and PNY. This study aimed to determine the anti-muscle atrophy efficacy and molecular mechanisms of TGPN and PNY on both C2C12 cell lines and mice. In vitro, the TGPN and PNY recovered the dexamethasone-induced reduction in the myotube diameters. In vivo, TGPN and PNY administration not only improved grip strength and exercise endurance, but also attenuated the loss of muscle mass and muscle fiber cross-sectional area. Mechanistically, TGPN and PNY increased the expression of protein synthesis-related protein levels via phosphoinositide 3-kinase (PI3K)/protein kinase B (Akt)/mammalian target of the rapamycin pathway, and reduced the expression of protein degradation-related protein levels via the PI3K/Akt/forkhead box O pathway. Also, TGPN and PNY stimulated NAD-dependent deacetylase sirtuin-1(SIRT1), peroxisome proliferator-activated receptor gamma coactivator-1 alpha (PGC-1α), nuclear respiratory factor 1,2, mitochondrial transcription factor A, along with mitochondrial DNA content via SIRT1/PGC-1α signaling. These findings suggest oyster hydrolysates could be used as a valuable natural material that inhibits skeletal muscle atrophy via regulating protein turnover and mitochondrial biogenesis.

Fermented Oyster Extract Attenuated Dexamethasone-Induced Muscle Atrophy by Decreasing Oxidative Stress.

It is well known that oxidative stress induces muscle atrophy, which decreases with the activation of Nrf2/HO-1. Fermented oyster extracts (FO), rich in γ-aminobutyric acid (GABA) and lactate, have shown antioxidative effects. We evaluated whether FO decreased oxidative stress by upregulating Nrf2/HO-1 and whether it decreased NF-κB, leading to decreased IL-6 and TNF-α. Decreased oxidative stress led to the downregulation of Cbl-b ubiquitin ligase, which increased IGF-1 and decreased FoxO3, atrogin1, and Murf1, and eventually decreased muscle atrophy in dexamethasone (Dexa)-induced muscle atrophy animal model. For four weeks, mice were orally administered with FO, GABA, lactate, or GABA+Lactate, and then Dexa was subcutaneously injected for ten days. During Dexa injection period, FO, GABA, lactate, or GABA+Lactate were also administered, and grip strength test and muscle harvesting were performed on the day of the last Dexa injection. We compared the attenuation effect of FO with GABA, lactate, and GABA+lactate treatment. Nrf2 and HO-1 expressions were increased by Dexa but decreased by FO; SOD activity and glutathione levels were decreased by Dexa but increased by FO; NADPH oxidase activity was increased by Dexa but decreased by FO; NF-κB, IL-6, and TNF-α activities were increased by Dexa were decreased by FO; Cbl-b expression was increased by Dexa but restored by FO; IGF-1 expression was decreased by Dexa but increased by FO; FoxO3, Atrogin-1, and MuRF1 expressions were increased by Dexa but decreased by FO. The gastrocnemius thickness and weight were decreased by Dexa but increased by FO. The cross-sectional area of muscle fiber and grip strength were decreased by Dexa but increased by FO. In conclusion, FO decreased Dexa-induced oxidative stress through the upregulation of Nrf2/HO-1. Decreased oxidative stress led to decreased Cbl-b, FoxO3, atrogin1, and MuRF1, which attenuated muscle atrophy.

High Hydrostatic Pressure Treatment of Oysters (Crassostrea gigas)-Impact on Physicochemical Properties, Texture Parameters, and Volatile Flavor Compounds.

High hydrostatic pressure (HHP) treatment is a non-thermal processing technology, which is widely used in the food processing field at present. In this study, the effects of HHP treatment (100~500 MPa for 5 min) on the physicochemical properties, texture parameters, and volatile flavor compounds of oysters were investigated. The results showed that HHP treatment increased the water content while reducing the crude protein and ash content of the oyster. Texture parameters showed that HHP treatment improved the hardness, springiness, chewiness, and cohesiveness of oysters, compared with the control group. In addition, the saturated fatty acid (SFA) content was slightly increased after HHP treatment, while the difference in monounsaturated fatty acid (MUFA) and polyunsaturated fatty acid (PUFA) content was not significant. Furthermore, HHP increased hexenoic aldehyde, 2,4-heptadienal, 1-octene-3-ol, and 2-octen-1-ol and decreased the contents of 3. 6-nadien-1-ol, 3-octanone, and 2-undecanone, suggesting that HHP might inhibit the fishiness of oyster and showed a positive effect on its flavor. Based on the above results, HHP improved the edible qualities such as texture properties and volatile flavor of oysters. This meets the requirements of consumers on the edible quality of seafood and provides new ideas for the development of seafood.

Simultaneous determination of triazine herbicides and their metabolites in shellfish by HPLC-MS/MS combined with Q/E-Orbitrap HRMS.

Triazine herbicides are used extensively in agriculture and aquaculture worldwide because of their broad effectiveness in weed control. However, after they are discharged into the sea, they seriously contaminate aquatic ecosystems and threaten aquatic organisms, especially shellfish. Currently, there are no established methods for the detection and confirmation of triazine herbicides and their metabolites in biological matrixes. Hence, the food safety of aquatic products cannot be accurately evaluated, which creates a technical barrier against international aquatic product trade. In this study, for the first time, a method was developed for the analysis and confirmation of seven triazine herbicides and 13 metabolites in shellfish, based on alkaline acetonitrile extraction and neutral Al2O3 cartridge purification coupled with internal standard calibration. Specifically, quantitative and qualitative analysis was conducted using high-performance liquid chromatography-triple quadrupole mass spectrometry (HPLC-MS/MS), and accurate identification was carried out by quadrupole orbitrap high-resolution mass spectrometry (Q/E Orbitrap HRMS). The results showed that target analytes demonstrated good linearity within the corresponding range (R2 > 0.995). The limit of detection and limit of quantitation of the proposed method were 0.1 and 0.3 µg/kg, respectively. The average recoveries of analytes were between 70.0% and 120% when spiked at three levels with blank oyster (Crassostrea gigas) as the matrix, and the relative standard deviations (RSDs) were all less than 12% (n=6). The proposed method was successfully applied for the detection of triazine herbicide residues in oyster samples during actual breeding, and the presence of DIP, HP, DEHA, and other metabolites in positive samples was confirmed by Q/E Orbitrap HRMS. This method exhibits high accuracy, high sensitivity, and good reproducibility. It has promising application prospects in the field of hazard analysis and the positive identification of aquatic products.

Method performance verification for the combined detection and quantitation of the marine neurotoxins cyclic imines and brevetoxin shellfish metabolites in mussels (Mytilus edulis) and oysters (Crassostrea gigas) by UHPLC-MS/MS.

A single laboratory method performance verification is reported for a rapid sensitive UHPLC-MS/MS method for the quantification of eight cyclic imine and two brevetoxin analogues in two bivalve shellfish matrices: mussel (Mytilus edulis) and Pacific oyster (Crassostrea gigas). Targeted cyclic imine analogues were from the spirolide, gymnodimine and pinnatoxin groups, namely 20-Me-SPX-C, 13-desMe-SPX-C, 13,19-didesMe-SPX-C, GYM-A, 12-Me-GYM, PnTx-E, PnTx-F and PnTx-G. Brevetoxin analogues consisted of the shellfish metabolites BTX-B5 and S-desoxy-BTX-B2. A rapid dispersive extraction was used as well as a fast six-minute UHPLC-MS/MS analysis. Mobile phase prepared using ammonium fluoride and methanol was optimised for both chromatographic separation and MS/MS response to suit all analytes. Method performance verification checks for both matrices were carried out. Matrix influence was acceptable for the majority of analogues with the MS response for all analogues being linear across an appropriate range of concentrations. In terms of limits of detection and quantitation the method was shown to be highly sensitive when compared with other methods. Acceptable recoveries were found with most analogues, with laboratory precision in terms of intra- and inter-batch precision deemed appropriate. The method was applied to environmental shellfish samples with results showing low concentrations of cyclic imines to be present. The method is fast and highly sensitive for the detection and quantification of all targeted analogues, in both mussel and oyster matrices. Consequently, the method has been shown to provide a useful tool for simultaneous monitoring for the presence or future emergence of these two toxin groups in shellfish.

Structure and Immunomodulatory Activity of Glycogen Derived from Honeybee Larvae (Apis mellifera).

Honeybee larvae have been recognized as nutrient-rich food in many countries. Although glycogen, a storage form of glucose in animals, is synthesized in honeybee larvae, there is no information on the structure of glycan and its biological activity. In this study, we successfully extracted glycogen from honeybee larvae using hot water extraction and investigated the structure and biological activity of glycan. It was found that the molecular weight of glycogen from honeybee larvae is higher than that of glycogen from bovine liver and oysters. In addition, treatment of RAW264.7 cells with glycogen from honeybee larvae resulted in a much higher production of tumor necrosis factor (TNF)-α and interleukin (IL)-6 than treatment with glycogen from either bovine liver or oysters. These results suggest that the high molecular weight glycogen from honeybee larvae is a functional food ingredient with immunomodulatory activity.