Marennine, promising blue pigments from a widespread Haslea diatom species complex.

In diatoms, the main photosynthetic pigments are chlorophylls a and c, fucoxanthin, diadinoxanthin and diatoxanthin. The marine pennate diatom Haslea ostrearia has long been known for producing, in addition to these generic pigments, a water-soluble blue pigment, marennine. This pigment, responsible for the greening of oysters in western France, presents different biological activities: allelopathic, antioxidant, antibacterial, antiviral, and growth-inhibiting. A method to extract and purify marennine has been developed, but its chemical structure could hitherto not be resolved. For decades, H. ostrearia was the only organism known to produce marennine, and can be found worldwide. Our knowledge about H. ostrearia-like diatom biodiversity has recently been extended with the discovery of several new species of blue diatoms, the recently described H. karadagensis, H. silbo sp. inedit. and H. provincialis sp. inedit. These blue diatoms produce different marennine-like pigments, which belong to the same chemical family and present similar biological activities. Aside from being a potential source of natural blue pigments, H. ostrearia-like diatoms thus present a commercial potential for aquaculture, cosmetics, food and health industries.

Complex metabolic interactions between benzo(a)pyrene and tributyltin in presence of dichlorodiphenyltrichloroethane in South American catfish Rhamdia quelen.

In an attempt to explore complex metabolic interactions between toxicants present in polluted freshwater, hepatic metabolism of benzo(a)pyrene (BaP) and tributyltin (TBT) in fish was investigated when these compounds were administrated alone, mixed together and along with dichlorodiphenyltrichloroethane (DDT). Ten Rhamdia quelen per group were treated with a single intra-peritoneal (IP) dose (5-day experiment) or three successive doses (15-day experiment) either containing BaP (0.3; 3 or 30mgkg(-1)) or TBT (0.03; 0.3 or 3mgkg(-1)) or a combination of BaP+TBT, BaP+DDT, TBT+DDT and BaP+TBT+DDT under their respective lower doses, with DDT dose kept at 0.03mgkg(-1). Tetrahydroxy-benzo(a)pyrene (BaP-tetrol-I), and dibutyltin (DBT) and monobutyltin (MBT) were analyzed to assess BaP and TBT hepatic metabolism, respectively. A significant difference in BaP-tetrol-I concentration was observed in liver and bile between the lowest and the highest doses of BaP in both 5 and 15-day experiments. In the 15-day experiment, the presence of TBT with BaP reduced the amount of BaP-tetrol-I in bile compared to the BaP alone. The time of exposure and the number of doses affected BaP-tetrol-I concentration in the bile of fish exposed to BaP 0.3mgkg(-1) and BaP+DDT. TBT and its metabolites concentrations showed a dose-dependent increase in the liver in both experiments and in the bile in the 5-day experiment. TBT at its lowest dose was completely metabolized into DBT and MBT in the liver in the 15-day experiment. No TBT metabolites were detected in the bile of fish exposed to the mixtures in the 5-day experiment, except for a small MBT amount found in BaP+TBT+DDT. This study strengthens the hypothesis of a metabolic interaction between BaP and TBT in fish and suggests DDT as an important third player when present in the mixture.

Spatial distribution and speciation of mercury in a recovering deepwater redfish (Sebastes mentella) population from St. Lawrence Estuary and Gulf, Canada.

Mercury (Hg) pollution poses a significant threat to the environment, particularly in the form of methylmercury (MeHg). However, little is known about the distribution and influencing factors of Hg in deep-sea (>200m) fish, which is crucial for assessing potential health risks to fish and humans. In Canada, the deepwater redfish (Sebastes mentella) has been designated as an endangered species. After a 25-year fishing moratorium, the redfish population in the St. Lawrence Estuary and Gulf is recovering, and resuming of commercial fishing and human consumption are expected. This study aimed to investigate the distribution of MeHg and total Hg (THg) in the muscle of redfish, as well as the factors influencing its distribution, and to assess the potential human health risks associated with redfish consumption. The redfish samples (n = 123) were collected by Fisheries and Oceans Canada in 2019. The concentrations of THg and MeHg in redfish muscle were determined to be 93.3 ± 183 ng/g (mean ± SD, wet weight) and 78.2 ± 149 ng/g, respectively. Large redfish (>30 cm) accumulated 20 to 30 times more Hg than small redfish (17-30 cm). Small redfish from the Estuary-Western Gulf had higher levels of MeHg and THg than those from the Laurentian Channel and the Northeast Gulf, but the Hg availability to redfish among the three areas were similar. Significant predictors of MeHg concentrations in redfish muscle were determined to be fish length, muscle moisture, δ15N, and N%. MeHg consumption by the general population with an average fish consumption rate is not anticipated to have adverse effects. This study establishes a baseline for future Hg monitoring in the deep water environments in this region. Further research is required to elucidate the cause-effect relationships between various environmental/biological parameters and Hg accumulation in deep-sea biota.

Regioselective pivaloylation of N-phthaloylchitosan: a promising soluble intermediate for chitosan chemistry.

A simple and efficient pivaloylation of primary alcohols was realized on N-phthaloylchitosan that was regioselectively and entirely protected. The selectivity of this mild esterification was demonstrated by comparison with (1)H NMR chemical shifts of H-1 and H-3 of complete 3,6-O-dipivaloylated derivatives. The selective hydrazinolysis of N-phthaloyl groups in the presence of pivaloyl ester was achieved in ethanol/water. High molecular weight 6-O-pivaloylchitosan, purified by ultrafiltration, with solubility in organic solvents was obtained. The selective introduction of a phosphorus moiety in O-3 using chlorodiphenylphosphine has led to 3-O-diphenylphosphinito-N-phthaloyl-6-O-pivaloylchitosan with a ds of 0.97 from energy dispersive X-ray spectroscopy, which demonstrates the potential applications of O-6 pivaloyl protection. The pivaloylation of O-6 alcohols can enhance the solubility of some chitosan derivatives and therefore contributes to the development of applications involving chitosan through regioselective modifications of alcohol and amino groups.