Extraction of Fatty Acids and Phenolics from Mastocarpus stellatus Using Pressurized Green Solvents

Polyunsaturated fatty acids are well known for their protective properties in relation to different skin diseases. Although seaweeds possess a low lipid fraction, they could act as an alternative renewable source of polyunsaturated fatty acids whenever other valuable seaweed components are also valorized. In this study, a biorefinery process using Mastocarpus stellatus as a model seaweed was proposed. The process started with the supercritical carbon dioxide extraction of the lipid and phenolic fractions. The influence of pressure during extraction with pure supercritical CO2 was studied while operating at a selected temperature and solvent flow rate. Kinetic data obtained during the ethanol-modified supercritical CO2 extraction were fitted to the spline model. Sequential processing was proposed with (i) pure CO2 to obtain a product with 30% PUFA content and ω-3:ω-6 ratio 1:1, (ii) ethanol-modified CO2 to extract phenolics, and (iii) microwave-assisted subcritical water extraction operating under previously optimized conditions for the extraction of phenolics, carrageenan and protein fractions. The composition of the supercritical extracts showed potential for use in both dietary and topical applications in skin care products. The remaining solids are suitable for the extraction of other valuable fractions.

Red Seaweeds as a Source of Nutrients and Bioactive Compounds: Optimization of the Extraction

The present work aimed to determine the nutritional composition (ash, protein, fat, carbohydrate content and energy value), phenolic compounds, pigments and organic acids content of three typical red algae from the Northwest of Spain: Chondrus crispus, Mastocarpus stellatus, and Gigartina pistillata; as well as their antioxidant and antimicrobial activities. Furthermore, the present work compared two extraction techniques: conventional heat assisted extraction (HAE) and high pressure assisted extraction (HPAE) to maximize the yield and the concentration of target compounds. Different independent variables were considered for the response study. Time (t) and percentage of ethanol of the solvent (S) were chosen for both techniques and temperature (T) and pressure (P) were used for HAE and HPAE, respectively. The experiments were designed following a response surface methodology (RSM) approach. The obtained results showed a similar nutritional composition between algae samples: low-fat content and high content of proteins, carbohydrates and energy. All tested algae showed good antioxidant and antimicrobial properties. Finally, HEA demonstrated to be the most efficient extraction technique. This study confirms the potential of red algae to be part of the human diet as a source of non-animal protein, due to its nutritional content, phenolic profile, pigments concentration and bioactive properties, which proves that HAE is the optimum technique for the extraction maximization.

Antiproliferative and Antioxidant Activities and Mycosporine-Like Amino Acid Profiles of Wild-Harvested and Cultivated Edible Canadian Marine Red Macroalgae

Antiproliferative and antioxidant activities and mycosporine-like amino acid (MAA) profiles of methanol extracts from edible wild-harvested (Chondrus crispus, Mastocarpus stellatus, Palmaria palmata) and cultivated (C. crispus) marine red macroalgae were studied herein. Palythine, asterina-330, shinorine, palythinol, porphyra-334 and usujirene MAAs were identified in the macroalgal extracts by LC/MS/MS. Extract reducing activity rankings were (p < 0.001): wild P. palmata > cultivated C. crispus = wild M. stellatus > wild low-UV C. crispus > wild high-UV C. crispus; whereas oxygen radical absorbance capacities were (p < 0.001): wild M. stellatus > wild P. palmata > cultivated C. crispus > wild low-UV C. crispus > wild high-UV C. crispus. Extracts were antiproliferative against HeLa and U-937 cells (p < 0.001) from 0.125–4 mg/mL, 24 h. Wild P. palmata and cultivated C. crispus extracts increased (p < 0.001) HeLa caspase-3/7 activities and the proportion of cells arrested at Sub G1 (apoptotic) compared to wild-harvested C. crispus and M. stellatus extracts. HeLa cells incubated with wild P. palmata and cultivated C. crispus extracts also exhibited morphological changes characteristic of apoptosis (shrinkage, rounding). Thus, extracts rich in low-polarity usujirene and polar palythine and asterina-330 MAAs were antiproliferative as inducers of apoptosis in HeLa cells.

Antiproliferative and Antioxidant Activities and Mycosporine-Like Amino Acid Profiles of Wild-Harvested and Cultivated Edible Canadian Marine Red Macroalgae

Antiproliferative and antioxidant activities and mycosporine-like amino acid (MAA) profiles of methanol extracts from edible wild-harvested (Chondrus crispus, Mastocarpus stellatus, Palmaria palmata) and cultivated (C. crispus) marine red macroalgae were studied herein. Palythine, asterina-330, shinorine, palythinol, porphyra-334 and usujirene MAAs were identified in the macroalgal extracts by LC/MS/MS. Extract reducing activity rankings were (p < 0.001): wild P. palmata > cultivated C. crispus = wild M. stellatus > wild low-UV C. crispus > wild high-UV C. crispus; whereas oxygen radical absorbance capacities were (p < 0.001): wild M. stellatus > wild P. palmata > cultivated C. crispus > wild low-UV C. crispus > wild high-UV C. crispus. Extracts were antiproliferative against HeLa and U-937 cells (p < 0.001) from 0.125–4 mg/mL, 24 h. Wild P. palmata and cultivated C. crispus extracts increased (p < 0.001) HeLa caspase-3/7 activities and the proportion of cells arrested at Sub G1 (apoptotic) compared to wild-harvested C. crispus and M. stellatus extracts. HeLa cells incubated with wild P. palmata and cultivated C. crispus extracts also exhibited morphological changes characteristic of apoptosis (shrinkage, rounding). Thus, extracts rich in low-polarity usujirene and polar palythine and asterina-330 MAAs were antiproliferative as inducers of apoptosis in HeLa cells.

Ultrasound-Assisted Water Extraction of Mastocarpus stellatus Carrageenan with Adequate Mechanical and Antiproliferative Properties

Ultrasound-assisted water extraction was optimized to recover gelling biopolymers and antioxidant compounds from Mastocarpus stellatus. A set of experiments following a Box–Behnken design was proposed to study the influence of extraction time, solid liquid ratio, and ultrasound amplitude on the yield, sulfate content, and thermo-rheological properties (viscoelasticity and gelling temperature) of the carrageenan fraction, as well as the composition (protein and phenolic content) and antiradical capacity of the soluble extracts. Operating at 80 °C and 80 kHz, the models predicted a compromise optimum extraction conditions at ~35 min, solid liquid ratio of ~2 g/100 g, and ultrasound amplitude of ~79%. Under these conditions, 40.3% carrageenan yield was attained and this product presented 46% sulfate and good mechanical properties, a viscoelastic modulus of 741.4 Pa, with the lowest gelling temperatures of 39.4 °C. The carrageenans also exhibited promising antiproliferative properties on selected human cancer cellular lines, A-549, A-2780, HeLa 229, and HT-29 with EC50 under 51.9 μg/mL. The dried soluble extract contained 20.4 mg protein/g, 11.3 mg gallic acid eq/g, and the antiradical potency was equivalent to 59 mg Trolox/g.

Formulation and Thermomechanical Characterization of Functional Hydrogels Based on Gluten Free Matrices Enriched with Antioxidant Compounds

Native starch from potatoes and hybrid carrageenans from the red alga Mastocarpus stellatus have been used as gluten-free gelling matrices to obtain functional hydrogels. The enrichment of gelling matrices with antioxidant compounds from natural sources is an increasing market trend. In this context, this work is aimed at the formulation and thermo-rheological characterization of functional hydrogels using potato starch from agro-industrial waste and kappa–iota hybrid carrageenans extracted from the above seaweed, enriched with antioxidant compounds from different agro-industrial products, such as waste coming from the pruning of green tea and two varieties of hops used in the brewing industry. Environmentally friendly technologies such as microwave hydrodiffusion and gravity, microwave-assisted extraction, ultrasounds and autohydrolysis were used for the recovery of antioxidant compounds. The results point out that functional hydrogels based on potato starch and hybrid carrageenans with a wide range of viscoelastic features can be achieved, with the particularity of being suitable for people with celiac disease. The incorporation of selected antioxidant extracts from vegetable by-products involved the drop (about tenfold) of the viscous and elastic properties of the formulated gels. The sequential combination of the above treatments could even further expand the thermo-rheological properties of formulated hydrogels, with potential application in functional foodstuffs and novel gluten-free goods.

Variability and Potential of Seaweeds as Ingredients of Ruminant Diets: An In Vitro Study

This study was designed to analyze the chemical composition and in vitro rumen fermentation of eight seaweed species (Brown: Alaria esculenta, Laminaria digitata, Pelvetia canaliculata, Saccharina latissima; Red: Mastocarpus stellatus, Palmaria palmata and Porphyra sp.; Green: Cladophora rupestris) collected in Norway during spring and autumn. Moreover, the in vitro ruminal fermentation of seventeen diets composed of 1:1 oat hay:concentrate, without (control diet) or including seaweeds was studied. The ash and N contents were greater (p < 0.001) in seaweeds collected during spring than in autumn, but autumn-seaweeds had greater total extractable polyphenols. Nitrogen in red and green seaweeds was greater than 2.20 and in brown seaweeds, it was lower than 1.92 g/kg DM. Degradability after 24 h of fermentation was greater in spring seaweeds than in autumn, with Palmaria palmata showing the greatest value and Pelvetia canaliculata the lowest. Seaweeds differed in their fermentation pattern, and autumn Alaria esculenta, Laminaria digitata, Saccharina latissima and Palmaria palmata were similar to high-starch feeds. The inclusion of seaweeds in the concentrate of a diet up to 200 g/kg concentrate produced only subtle effects on in vitro ruminal fermentation.