Argentine squid (Illex argentinus): A source of mycosporine-like amino acids with antioxidant properties.

Here we report on the occurrence of mycosporine-like amino acids (MAAs) in the Argentine shortfin squid, Illex argentinus, the second fishery resource mostly exploited in the Argentinean continental shelf. The total content of four MAAs was evaluated by reverse-phase-HPLC in different tissues (eyes, skin, liver, and gonads). Also, the antioxidant activity of crude extracts was assessed by in-vitro determinations: 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), Folin-Ciocalteu, and ferrous ion-chelating capacity assays. The content of MAAs was found to be almost ten times higher in female gonads than in other tissues (11,89 ± 0,56 mg/g dry weight). Extracts from skin, female gonads and eyes, exhibit higher antioxidant activity than the reference compounds ascorbic acid and TROLOX. Overall, Argentine squid waste is a promising potential source of MAAs with antioxidant and UV photoprotective properties, which could bear interest in food, cosmetic and pharmaceutical industries, thus encouraging maximal and sustainable use of fishing resources.

Tuning the morphology to enhance the catalytic activity of α-Ag2WO4 through V-doping.

Here, we present the synthesis of a highly efficient V-doped α-Ag2WO4 catalyst for the oxidation of sulfides to sulfones, exhibiting a high degree of tolerance towards various sensitive functional groups. Remarkably, the catalysts with 0.01% V-doping content exhibited outstanding selectivity towards the oxidation process. Scavenger experiments indicated the direct involvement of electron-hole (e-/h+) pairs, hydroxyl radical (˙OH), and singlet oxygen (1O2) in the catalytic mechanism. Based on the experimental and theoretical results, the higher activity of the V-doped α-Ag2WO4 samples was associated with the preferential formation of the (100) surface in the catalyst morphology.

Toxicity and sublethal effects of lead (Pb) intake on honey bees (Apis mellifera).

Heavy metal pollution is becoming a worldwide problem affecting pollinators. The massive use of lead (Pb), the most harmful metal for the biosphere, in industries has increased the risk for honey bees. Pb exerts toxicity on living organisms inducing mainly oxidative stress. We assessed the toxicity and sublethal effects of Pb ingestion on protein content, catalase (CAT) activity, fat content and fatty acid (FA) profile of honey bee workers (Apis mellifera L.) under different nutritional conditions during chronic exposure tests. The LD50 was 15.13 ± 6.11 µg Pb2+/bee, similar to other reports. A single oral sublethal dose of 15 µg of Pb2+ affected the survival of bees fed with sugary food for ten days after Pb ingestion while supplementing the diet with bee bread improved Pb tolerance. The highest protein content was found in bees fed with the sugar paste and bee bread diet without Pb. CAT activity tended to decrease in bees of Pb groups independently of diet. Fat content was not affected by the diet type received by bees or Pb ingestion, but the FAs profile varied according to the nutritional quality of the diet. The results highlight that a single sublethal dose of Pb negatively affected the body proteins of bees despite the nutritional condition but did not disturb the FAs profile of workers. Nutrition plays an important role in preventing Pb-induced toxicity in honey bees.

Carotenoids from Haloarchaea: Extraction, Fractionation, and Characterization.

Carotenoids are bioactive molecules known to promote human health. Many extreme halophilic archaea synthesize carotenoids, mainly represented by C50 bacterioruberin (BR) and its derivatives. BR has a potent antioxidant capacity, even higher than that of ß-carotene, thus, there is an increasing interest to advance the study of its biological properties as well as to extend its current applications. Here, we describe a procedure to extract and characterize carotenoids (enriched in BR) from haloarchaea using a "hyperpigmented" genetically modified strain of Haloferax volcanii.

Photoprotection Effects of Red Seaweed Meal (Grateloupia cf. Turuturu) as Feed Ingredient in Prawn Artemesia Longinaris.

The aim of this research was to determine the effects of adding red seaweed meal rich in ultraviolet radiation absorbing compounds (UACs) to the diet of juvenile prawn Artemesia longinaris and its possible protective effects under stress by ultraviolet radiation (UVR). Three experimental diets were prepared: control diet (D) and two diets supplemented with red seaweed Grateloupia cf. turuturu meal at two inclusion levels (D1: 1 g/100 g; D2: 2 g/100 g). Three experiments were carried out: a) 45-day feeding, b) digestibility, and c) radiation exposure experiment. After the 45-day feeding experiment, no significant differences were found in growth and survival. Accumulation of UACs was detected only in animals fed D1 and D2, and concentration was significantly higher in animals fed D2, with concentrations (12.58 ± 3.50 OD g-1 ) and (3.17 ± 0.4 OD g-1 ) after 45-day feeding and after 7-day UVR exposure, respectively. After 7 days of exposure to different light treatments, significant differences were recorded inradical scavenging activities. In all UVR treatments, rapid signal decay was recorded in the first 5 min of reaction. The red seaweed Grateloupia cf. turuturumeal constitutes an interesting source of photoprotective compounds as an additive in the diet of A. longinaris.

Sensitized photo-oxidation of gadusol species mediated by singlet oxygen.

Gadusols are efficient nature UV sunscreens with antioxidant capacity. The kinetics of the quenching reactions of singlet oxygen O2(1∆g) by gadusol species was evaluated in aqueous solution as well as in the presence of direct charged micelles. Time-resolved phosphorescence detection of O2(1∆g) indicated that gadusolate, the main species under biological pH, is a more efficient quencher than the enol form with a rate constant of ca. 1.3 × 108 L mol-1 s-1. The deactivation proceeds via a collisional mechanism with clear dominance of chemical pathways, according to the rates of gadusol and oxygen consumptions, and typical photooxidation quantum yields of ca. 7%. The relative contributions of the chemical and physical quenching steps were not affected by the presence of anionic or cationic micelles emulating simple pseudo-biological environments. The products of the photo-oxidative quenching support a type II mechanism initiated by the addition of O2(1∆g) to the C-C double bond of gadusolate. These results point to the relevance of considering the role of sacrifice antioxidant along with the UV-screening function for gadusol, particularly in the context of potential biotechnological applications of this natural molecule.

Photochemistry and Photophysics of Shinorine Dimethyl Ester.

The photostability and photophysical properties of the dimethyl ester of the mycosporine-like amino acid shinorine have been experimentally evaluated in aqueous solution and in the presence of direct micelles prepared with a cationic or an anionic detergent, respectively. In comparison with shinorine, the ester molecule increases the photostability, the fluorescence quantum yield and the fluorescence lifetime in water as well as in the micellar solutions. The effects are more pronounced in sodium dodecyl sulfate solutions and suggest that the electrostatic attractions with the micellar interface contribute to limit the movement of the molecules and influence the relative rate of their deactivation channels. However, the predominance of the nonradiative decay is maintained together with the UV photoprotective ability of this atypical mycosporine species.

Anthelminthic activity of glibenclamide on secondary cystic echinococcosis in mice.

Cystic echinococcosis (CE) is a worldwide parasitic zoonosis caused by the larval stage of Echinococcus granulosus. Current chemotherapy against this disease is based on the administration of benzimidazoles (BZMs). However, BZM treatment has a low cure rate and causes several side effects. Therefore, new treatment options are needed. The antidiabetic drug glibenclamide (Glb) is a second-generation sulfonylurea receptor inhibitor that has been shown to be active against protozoan parasites. Hence, we assessed the in vitro and in vivo pharmacological effects of Glb against the larval stage of E. granulosus. The in vitro activity was concentration dependent on both protoscoleces and metacestodes. Moreover, Glb combined with the minimum effective concentration of albendazole sulfoxide (ABZSO) was demonstrated to have a greater effect on metacestodes in comparison with each drug alone. Likewise, there was a reduction in the cyst weight after oral administration of Glb to infected mice (5 mg/kg of body weight administered daily for a period of 8 weeks). However, in contrast to in vitro assays, no differences in effectiveness were found between Glb + albendazole (ABZ) combined treatment and Glb monotherapy. Our results also revealed mitochondrial membrane depolarization and an increase in intracellular Ca2+ levels in Glb-treated protoscoleces. In addition, the intracystic drug accumulation and our bioinformatic analysis using the available E. granulosus genome suggest the presence of genes encoding sulfonylurea transporters in the parasite. Our data clearly demonstrated an anti-echinococcal effect of Glb on E. granulosus larval stage. Further studies are needed in order to thoroughly investigate the mechanism involved in the therapeutic response of the parasite to this sulfonylurea.

Electrochemical characterization of the marine antioxidant gadusol.

The electrochemical properties of gadusol, a metabolite extracted from fish roes, were determined for the first time by cyclic- and square-wave voltammetries on a glassy carbon electrode in buffered aqueous solutions. The aims of the work were characterization of the redox behavior and assessment of the mechanism underlying the antioxidant capacity of the compound. Anodic waves with peak potentials of 710 +/- 5 mV and 601 +/- 9 mV vs. Ag/AgCl were obtained for gadusol and its anion gadusolate, respectively. The voltammograms point to the irreversible nature of the oxidation process and reveal better antioxidant properties for the compound under physiological pH, with a moderate reductive power, but improved stability under atmospheric oxidation in comparison with other natural antioxidants such as ascorbic acid. The presence of direct ionic micelles prepared with sodium dodecyl-sulfate or cetyl-trimethyl-ammonium chloride yielded no significant differences regarding homogeneous medium in the cyclic voltammetry of gadusolate. The results provide evidence of the electron transfer mechanism for the quenching reaction of standard-reactive species by gadusolate and support it as a promising candidate to be tested as an antioxidant additive to food, cosmetic and pharmaceutical formulas. The direct analysis of the metabolite in biological systems and natural extracts by electrochemical methods is also envisaged.

Photophysics and reductive quenching reactivity of gadusol in solution.

The photostability and photophysics of gadusol in aqueous solution has been studied. The photodecomposition quantum yields (ca. 4 × 10(-2) and 1 × 10(-4) at acidic and neutral pH, respectively) confirm the high photostability of the metabolite, independently of the presence of oxygen, under physiological conditions. The nature of the electronic transition of gadusol has been assigned as π→π* on the basis of the solvatochromic shifts of the UV absorption spectrum and the time-dependent density functional theory calculation of the vertical transition energies. The results from the photoacoustic calorimetry point to the rapid non-radiative decay as the dominant relaxation pathway of the excited species at pH 7, which is consistent with the proposed UV-sunscreening role of the molecule in the early atmosphere. Laser flash photolysis experiments probed that the ground state of the enolate form (gadusolate) undergoes electron transfer reactions with some triplet sensitizers in water or methanol solution. A rate constant of 2 × 10(8) M(-1) s(-1) has been determined for the quenching of rose bengal triplet state in water at pH 7. This reductive quenching reactivity may be considered as one of the underlying mechanisms that support the antioxidant capacity of gadusol in biological environments.

UVB photoprotective role of mycosporines in yeast: photostability and antioxidant activity of mycosporine-glutaminol-glucoside.

Several yeast species are able to synthesize and accumulate UV-radiation-absorbing mycosporine metabolites that are of unclear physiological function. In this work we analyzed the relationship between mycosporine-glutaminol glucoside (MGG) production, cell survival after UVB irradiation, and formation of cyclobutane pyrimidine dimers (CPDs). We also assessed the photostability and singlet oxygen quenching activity of MGG. A set of nine isolates of the basidiomycetous yeast Cryptococcus steppossus cultured in both dark and light conditions was used for the studies. Survival of the UVB-irradiated isolates and MGG concentration had a linear relationship when the concentration was over 2.5 mg g(-1). CPD accumulation and MGG accumulation were inversely related. MGG in aqueous solution was photostable with a photodecomposition quantum yield of 1.16 × 10(-5). MGG quenching of singlet oxygen was also observed, and the rate constant for the process in D(2)O was 5.9 × 10(7) M(-1) s(-1). Our results support the idea that MGG plays an important role as a UVB photoprotective metabolite in yeasts by protecting against direct damage on DNA and probably against indirect damage by singlet oxygen quenching.

Experimental study of the excited-state properties and photostability of the mycosporine-like amino acid palythine in aqueous solution.

Characterization of the excited states of the mycosporine-like amino acid palythine (lambda(max) = 320 nm) in aqueous solutions was achieved experimentally. The low value for the photodegradation quantum yield, (1.2 +/- 0.2) x 10(-5), confirms that palythine is highly photostable in air saturated-aqueous solutions. Laser flash photolysis of acetone in the presence of palythine allowed for the observation of a transient spectrum which is consistent with the triplet-triplet absorption of palythine. Kinetic treatment of the transient signals yields a lifetime of the triplet state of ca. 9 micros and a triplet energy around 330 kJ mol(-1). The photoacoustic calorimetry results are consistent with non-radiative decay as the major fate of excited palythine. A comparison of the photodegradation quantum yields and photophysical properties of palythine with those previously determined for the other mycosporine-like amino acids, shinorine and porphyra-334, suggests that geometrical isomerization around the C=N bond may contribute to the rapid deactivation of this group of molecules.