Marine macroalgae represent a rich source of bioactive compounds that can be implemented in various food, cosmetic, and pharmaceutical products for health improvement. It has been proven that these bioactive compounds, such as polyphenols, polysaccharides, carotenoids, and ω-3 fatty acids possess bioactivity. For the extraction of these compounds, modern methods (Supercritical Fluid Extraction (SFE), Subcritical Water Extraction (SWE), Ultrasound-Assisted Extraction (UAE), and Microwave-Assisted Extraction (MAE)) have been used due to their advantages over the conventional methods. The process parameters of each method must be optimized for obtaining the extracts with the targeted bioactive compounds. In distinction from the existing reviews, the present review provides novelty with respect to: (a) presenting systematically the selected process parameters of SFE (temperature, time, pressure, use of co-solvents), SWE (temperature, time, pressure, solid-solvent ratio), UAE (temperature, time, frequency, power, solid-solvent ratio), and MAE (temperature, time, frequency, power, solvent type) applied for the extractions of marine macroalgae; (b) reporting the major groups or individual compounds extracted with their biological activities (if determined); and, (c) updating available references.

The orange peel (Citrus sinensis L.) from the variety Washington Navel was extracted by supercritical CO₂ (SC-CO₂) at different parameters. The extracts were analyzed by gas chromatography-mass spectrometry (GC-MS) and high-performance liquid chromatography (HPLC). Limonene predominance was found (up to 89%). The principal oxygenated monoterpenes were linalool, α-terpineol, decanal, and (E)-citral. Ultrasound-assisted extraction was performed on the remaining solid residue (after SC-CO₂extraction) to obtain the extracts rich in hesperidin. The influence of different extraction parameters on hesperidin content (3.3–23.0 µg/mL) was determined. The prediction performance in optimizing the extraction yield of dominant compounds was studied by response surface methodology and artificial neural network.

The endemic brown macroalga Fucus virsoides J. Agardh from the Adriatic Sea was in the focus of the present research. The volatiles of fresh (FrFv) and air-dried (DrFv) samples of F. virsoides obtained by headspace solid-phase microextraction (HS-SPME) and hydrodistillation (HD) were analyzed by gas chromatography equipped with flame ionization detector and mass spectrometry (GC-FID/MS). The major HS-FrFv compound was pentadecane (61.90–71.55%) followed by pentadec-1-ene (11.00–7.98%). In HS-DrFv, pentadec-1-ene was not present, and few lower aliphatic compounds appeared, as well as benzaldehyde and benzyl alcohol. In HD-FrFv, particularly abundant were alkenes (such as pentadec-1-ene (19.32%), or (E)-pentadec-7-ene (8.35%)). In HD-DrFv, more oxidation products were present (e.g., carbonyl compounds such as tridecanal (18.51%)). The fatty acids profile of freeze-dried sample (FdFv) after conversion to methyl esters was determined by GC-FID, and oleic acid was dominant (42.28%), followed by arachidonic acid (15.00%). High-performance liquid chromatography-high-resolution mass spectrometry with electrospray ionization (HPLC-ESI-HRMS) was used for the screening of less polar fractions (F3 and F4) of F. virsoides. Mono- and diglycerides of stearic, palmitic, oleic, and arachidonic acids were found. Terpenoids and steroids comprised the compounds C₂₀H₃₀₍₃₂₎O₂ and C₂₉H₄₈O₍₂₎. Among carotenoids, fucoxanthin was identified. Chlorophyll derivatives were also found (C₅₅H₇₄₍₇₂₎N₄O_(5-7)), dominated by pheophytin a. The antioxidant activity of the fractions was investigated by in vitro assays (oxygen radical absorbance capacity (ORAC), reduction of radical cation (ABTS•⁺), 2,2-diphenyl-1-picryl-hydrazyl-hydrate (DPPH) assay, and ferric reducing antioxidant power (FRAP)) and by in vivo zebrafish model (along with fish embryotoxicity). In vitro experiments proved good radical scavenging abilities of F3 and F4 fractions, which were additionally supported by the protective effect against hydrogen peroxide-induced oxidative stress in zebrafish embryos.

Ericaria crinita and Ericaria amentacea from the Adriatic Sea (Croatia) were investigated with respect to the presence of less-polar compounds for the first time after fractionation by solid-phase extraction (SPE). The composition of less-polar fractions of freeze-dried E. crinita (FdEc) and E. amentacea (FdEa) were analyzed by high-performance liquid chromatography–high-resolution mass spectrometry with electrospray ionization (UHPLC-ESI-HRMS). The major identified compounds were: amides of higher aliphatic acids (palmitoleamide, linoleamide, palmitamide, oleamide and erucamide) and related compounds, carotenoid (fucoxanthin), chlorophyll derivatives (pheophytin a and b and their derivatives) and higher terpenes (loliolide, isoamijiol with its oxidation product), β-stigmasterol and (3β,6α)-14-methylergosta-8,24(28)-diene-3,6-diol). The toxic effects observed on the less-polar fractions obtained from Ericaria species on zebrafish Danio rerio embryos could be associated with the high abundance of all five detected amides. The antioxidant activity of the fractions was evaluated by means of five independent assays, including the reduction of the radical cation (ABTS), the oxygen radical absorbance capacity (ORAC), ferric-reducing antioxidant power (FRAP), the 2,2-diphenyl-1-picryl-hydrazyl (DPPH) assay and the Folin–Ciocalteu method. A higher antioxidant activity of E. amentacea in comparison to that of the E. crinita fractions was found with IC₅₀ concentrations of 0.072 and 1.177 mg/mL, respectively. The correlation between the activity and the chemical composition revealed that the synergistic effect of different compounds impacted their antioxidant response.

The focus of present study is on Codium bursa collected from the Adriatic Sea. C. bursa volatiles were identified by gas chromatography and mass spectrometry (GC-FID; GC-MS) after headspace solid-phase microextraction (HS-SPME), hydrodistillation (HD), and supercritical CO₂ extraction (SC-CO₂). The headspace composition of dried (HS-D) and fresh (HS-F) C. bursa was remarkably different. Dimethyl sulfide, the major HS-F compound was present in HS-D only as a minor constituent and heptadecane percentage was raised in HS-D. The distillate of fresh C. bursa contained heptadecane and docosane among the major compounds. After air-drying, a significantly different composition of the volatile oil was obtained with (E)-phytol as the predominant compound. It was also found in SC-CO₂ extract of freeze-dried C. bursa (FD-CB) as the major constituent. Loliolide (3.51%) was only identified in SC-CO₂ extract. Fatty acids were determined from FD-CB after derivatisation as methyl esters by GC-FID. The most dominant acids were palmitic (25.4%), oleic (36.5%), linoleic (11.6%), and stearic (9.0%). FD-CB H₂O extract exhibited better antifungal effects against Fusarium spp., while dimethyl sulfoxide (DMSO) extract was better for the inhibition of Penicillium expansum, Aspergillus flavus, and Rhizophus spp. The extracts showed relatively good antifungal activity, especially against P. expansum (for DMSO extract MIC₅₀ was at 50 µg/mL).

The peels of Citrus reticulata Blanco mandarin cultivars of different Croatian varieties (Zorica rana, Chahara, Okitsu, Kuno) were extracted using 15 different choline chloride-based deep eutectic solvents (DESs) at 50 °C for 30 min and with 20% water addition. The extracts were analyzed by high performance liquid chromatography with diode array detection (HPLC-DAD) to determine the most suitable DES for the extraction of hesperidin in the samples. The screening results indicated that choline chloride: acetamide (1:2) provided the most efficient hesperidin extraction (112.14 mg/g of plant), while choline chloride:citric acid (1:1) solvent showed the lowest hesperidin yield (1.44 mg/g of plant). The Box–Behnken design was employed to optimize extraction parameters for each variety of mandarin peel, including extraction time, temperature and water content on hesperidin extraction. The results indicated that hesperidin content in mandarin peels was completely variety-dependent. Being a novel and efficient green media for hesperidin extraction, deep eutectic solvents could also serve as promising solvent systems for the production of extracts rich in bioactive compounds.