Several standard in vitro assays were performed in order to determine the potential antioxidant capabilities of purified aqueous extracts of the mycosporine-like amino acids (MAAs), porphyra-334 plus shinorine (P-334 + SH), isolated from the red alga Porphyra rosengurttii, asterina-330 plus palythine (AS-330 + PNE), from the red alga Gelidium corneum, shinorine (SH), from the red alga Ahnfeltiopsis devoniensis, and mycosporine -glycine (MGly), isolated from the marine lichen Lichina pygmaea. The scavenging potential of hydrosoluble radicals (ABTS + decolorization method), the antioxidant activity in lipid medium (β-carotene/ linoleate bleaching method) and the scavenging capacity of superoxide radicals (pyrogallol autooxidation assay) were evaluated. In terms of scavenging of hydrosoluble radicals, the antioxidant activity of all MAAs studied was dose-dependent and it increased with the alkalinity of the medium (pH 6 to 8.5). M-Gly presented the highest activity in all pH tested; at pH 8.5 its IC 50 was 8-fold that of L-ascorbic acid (L-ASC) followed by AS-330 + PNE while P-334 + SH and SH showed scarce activity of scavenging of hydrosoluble free radicals. AS-330 + PNE showed high activity for inhibition of β-carotene oxidation relative to vitamin E and superoxide radical scavenging whilst the activity of P-334 +SH and SH were moderate. According to these results, the potential of MAAs in photoprotection can be considered high due to a double function: (1) UV chemical screening with high efficiency for UVB and UVA regions of the solar spectrum, and (2) their antioxidant capacity.

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The safety and stability of synthetic UV-filters and the procedures for evaluating the photoprotective capability of commercial sunscreens are under continuous review. The influence of pH and temperature stressors on the stability of certain Mycosporine-like amino acids (MAAs) isolated at high purity levels was examined. MAAs were highly stable at room temperature during 24 h at pH 4.5–8.5. At 50 °C, MAAs showed instability at pH 10.5 while at 85 °C, progressive disappearances were observed for MAAs through the studied pH range. In alkaline conditions, their degradation was much faster. Mycosporine-serinol and porphyra-334 (+shinorine) were the most stable MAAs under the conditions tested. They were included in four cosmetically stable topical sunscreens, of which the Sun Protection Factor (SPF) and other Biological Effective Protection Factors (BEPFs) were calculated. The formulation containing these MAAs showed similar SPF and UVB-BEPFs values as those of the reference sunscreen, composed of synthetic UV absorbing filters in similar percentages, while UVA-BEPFs values were slightly lower. Current in vitro data strongly suggest that MAAs, as natural and safe UV-absorbing and antioxidant compounds, have high potential for protection against the diverse harmful effects of solar UV radiation. In addition, novel complementary in vitro tests for evaluation of commercial sunscreens efficacy are proposed.

Mycosporine-like amino acids (MAAs) have gained considerable attention as highly active photoprotective candidates for human sunscreens. However, more studies are necessary to evaluate the extraction efficiencies of these metabolites in cosmetic compatible solvents, as well as, their subsequent HPLC analysis. In the present study, MAA extraction using distilled water and 20% aqueous methanol in four Rhodophyta was investigated. Different re-dissolution solvents and a C8 and C18 columns were tested for the HPLC analysis. Porphyra-334, shinorine, palythine, palythine-serine, asterina-330, and palythinol were identified by HPLC/ESI-MS. The separation of these MAAs were improved employing the C8-column, and using methanol as re-dissolution solvent. Regarding total MAAs concentrations, no differences between the two solvents were found. The highest MAA amounts were observed injecting them directly in the HPLC. According to these results, distilled water could be an excellent extraction solvent for MAAs. Nevertheless, the re-dissolution in pure methanol after dryness would be the best option for the qualitative analysis of the most common MAAs in these red algae. Our results entail important implications regarding the use of red macroalgae as promising candidates as environment-friendly sources of natural sunscreens. coefficients (ε = 28,100-50,000 L·mol −1 ·cm −1 ). They are secondary metabolites capable of absorbing UV radiation with the maximum absorbance between 310 and 365 nm [15][16][17]. MAAs have a general structure that consist of cyclohexenone or cyclohexenimine chromophores conjugated with one or two amino acids that are responsible of UV absorption [18]. The high photostability of MAAs over a wide range of temperature and pH, together with their antioxidant properties, make them promising metabolites in the biotechnology industry. These compounds are recognized as strong UV-absorbing molecules that can be used as an active ingredient in sun-care cosmetic products, therefore could be a potential supplement of chemical filters just used in sunscreens, also due to the fact that they could satisfy consumers who want the incorporation of natural ingredients. Additionally, MAAs could be effective against actinic erythema, but can also protect the humans against other biological effects such as immune suppression or photo-oxidative damage [11,[19][20][21][22][23][24][25]. So, MAAs are promising functional ingredients used for novel cosmeceuticals (cosmetic products with health benefits). In fact, MAAs have already been commercialized as Helioguard®365. This cosmetic reagent contains the MAAs, shinorine and porphyra-334, extracted from the red alga Porphyra umbilicalis and has been successfully commercialized as a natural and safe sunscreen compound. Nowadays, the MAA extraction protocols differ in type of solvents, temperature, and extraction times. The MAA extraction efficiencies and concentrations are affected by these conditions [26][27][28][29]. A variety of extraction and separation methods for MAAs have been...