Quantitative and Qualitative HPLC Analysis of Mycosporine-Like Amino Acids Extracted in Distilled Water for Cosmetical Uses in Four Rhodophyta

Abstract

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...

Efficient Extraction and Antioxidant Capacity of Mycosporine-Like Amino Acids from Red Alga Dulse Palmaria palmata in Japan

“…Sinha et al [ 43 ] reported that shinorine and porphyra-334 were stable at 75 °C for up to 6 h. Coba et al [ 44 ] reported that MAAs were highly stable at room temperature during 24 h at pH 4.5–8.5 at 50 °C. Chaves-Peña et al [ 45 ] reported that the content of MAAs by water extraction and 20% methanol extraction was stable. When we extracted MAAs using methanol only, the content of the MAAs was stable despite of the extraction term ( Table 6 ).…”

Mycosporine-Like Amino Acids (MAAs): Biology, Chemistry and Identification Features

“…Since MAAs are potential compounds to be used as sunscreens in cosmetic products, the extraction protocol must be optimized taking into account their physicochemical and absorption properties and must use environmentally friendly and inexpensive solvents [ 9 , 50 ]. Traditional extraction method is usually performed by a solid/liquid extraction from the raw material and is carried out on fresh or lyophilized samples with different temperature ranges [ 51 , 52 ].…”

Mycosporine-Like Amino Acids from Marine Resource

“…Nishida et al [ 33 ] applied a successive extraction method by using water and then methanol extraction, and spectrophotometric and HPLC analyses revealed that the yield of MAAs by 6 h water extraction was the highest among the tested conditions. Nevertheless, according to Chaves-Peña et al [ 32 ] the re-dissolution in pure methanol after dryness was the best option for the qualitative analysis of the most common MAAs in red algae in contrast to those reported by Karsten et al [ 31 ]. The efficient extraction in water has advantages for the use of MAAs in natural cosmetics since methanol is a reactive that is not allowed in natural cosmetics.…”

“…Consequently, Karsten et al [ 31 ] suggested that methanol should be avoided as a re-dissolution solvent for the HPLC sample preparation. The protocol for extraction and HPLC identification based on the C18 column by Karsten et al [ 31 ] is compared with protocols reported in three papers in this issue [ 32 , 33 , 34 ].…”

“…Chaves-Peña et al [ 32 ], in this issue, compared MAA extraction using distilled water and 20% aqueous methanol in four Rhodophyta. Different re-dissolution solvents and C8 and C18 columns were tested for the HPLC analysis.…”