Nontargeted Screening for Flavonoids in Salicornia Plant by Reversed-Phase Liquid Chromatography-Electrospray Orbitrap Data-Dependent MS2/MS3.

The Salicornia genus has great potential in agrifood industries because of its nutritional benefits related to its high content of antioxidant compounds, including flavonoids. A nontargeted method based on reversed-phase liquid chromatography-electrospray orbitrap data-dependent MS2/MS3 and the fragment ion search (FISh) strategy was developed to screen flavonoids in Salicornia plants. An extensive study of fragmentation of a set of flavonoid standards allowed for the definition of 15 characteristic fragment ions for flagging flavonoids in the plant matrix. The nontargeted analysis was applied to Salicornia europaea species and allowed for the annotation of 25 candidate flavonoids, including 14 that had not been reported previously. Structural prediction of two unreported flavonoids and their isomeric forms was based on an advanced data processing method using an in silico approach and in-house databases compiling flavonoid-specific chemical substitution. Finally, the method developed allowed for the optimization of extraction yields of flavonoids from the plant matrix.

Speciation of metals in indigenous plants growing in post-mining areas: Dihydroxynicotianamine identified as the most abundant Cu and Zn ligand in Hypericum laricifolium.

Ag, As, Cu, Pb and Zn were found to be the principal metallic contaminants of a post-mining area of Peru (Hualgayoc, Cajamarca). Study of metal distribution amongst roots, stems, and leaves of four indigenous hypertolerant plant species, Arenaria digyna, Puya sp., Hypericum laricifolium, Nicotiana thyrsiflora indicated significant translocation of Zn (0.6 < TF ≤ 10.0) and Cu (0.4 < TF ≤ 6.5) into aerial plant organs and substantial water-extractable fraction (20-60%) of these metals, except for A. digyna (root and stems). A study of the metal speciation by ultrahigh-performance size-exclusion (fast-SEC) and hydrophilic ion interaction (HILIC) liquid chromatography with dual ICP (inductively coupled plasma) and electrospray (ESI) Orbitrap MS detection revealed the presence of nicotianamine and deoxymugineic acid copper and zinc complexes in roots, stem and leaves of N. thyrsiflora and Puya sp., and nicotianamine alone in A. digyna. A previously unreported compound, dihydroxy-nicotianamine was identified as the most abundant Cu and Zn ligand in H. laricifolium. The presence of arsenobetaine and an arsenosugar was confirmed by ESI MS. Ag and Pb were hardly translocated to leaves and were found as high molecular species; one of the Pb-containing species co-eluted in fast-SEC-ICP MS with rhamnogalacturonan-II-Pb complex commonly found in in the walls of plants.

Valorization of the Red Algae Gelidium sesquipedale by Extracting a Broad Spectrum of Minor Compounds Using Green Approaches.

Until now, the red algae Gelidium sesquipedale has been primarily exploited for agar production, leaving an undervalued biomass. In this work, the use of eco-friendly approaches employing ultrasound-assisted extraction (UAE) and green solvents was investigated to valorize the algal minor compounds. The green methods used herein showed an attractive alternative to efficiently extract a broad spectrum of bioactive compounds in short extraction times (15 to 30 min vs. 8 h of the conventional method). Using the best UAE conditions, red seaweed extracts were characterized in terms of total phenolics (189.3 ± 11.7 mg GAE/100 g dw), flavonoids (310.7 ± 9.7 mg QE/100 g dw), mycosporine-like amino acids (MAAs) (Σ MAAs = 1271 mg/100 g dw), and phycobiliproteins (72.4 ± 0.5 mg/100 g dw). Additionally, produced algal extracts exhibited interesting antioxidant and anti-enzymatic activities for potential applications in medical and/or cosmetic products. Thus, this study provides the basis to reach a superior valorization of algal biomass by using alternative methods to extract biologically active compounds following eco-friendly approaches. Moreover, the strategies developed not only open new possibilities for the commercial use of Gelidium sesquipedale, but also for the valorization of different algae species since the techniques established can be easily adapted.

Untargeted Analysis for Mycosporines and Mycosporine-Like Amino Acids by Hydrophilic Interaction Liquid Chromatography (HILIC)-Electrospray Orbitrap MS2/MS3.

Mycosporines and mycosporine-like amino acids have been described as natural sunscreens and antioxidant compounds presenting a great potential for health and cosmetic applications. Herein, an untargeted screening approach for mycosporines and mycosporine-like amino acids (MAAs) was developed by the coupling of zwitterionic hydrophilic interaction liquid chromatography (HILIC) with multistage electrospray mass spectrometry MS2/MS3 using an Orbitrap analyzer and fragment ion search (FISh). This method was applied to study the mycosporine and MAA contents of five algae extracted using a 50% methanol solution and sonication. Candidate-MAAs were detected by mining eight characteristic fragment ions in their HILIC data-dependent MS2 mass spectrum. Their exact masses were measured with 3 ppm mass accuracy and their structures were elucidated on the basis of the MS3/MS4 mass spectra. The method developed was validated with a targeted analysis using an extract of Gymnogongrus devoniensis which confirmed the detection of 14 MAAs reported in the literature. In addition, 23 previously unreported MAAs were detected and the structures could be assigned for seven of them. The developed method was applied to the analysis of four algae: Gelidium sesquipedale, Halopithys incurva, Porphyra rosengurtii and Cystoseira tamariscifolia allowing the detection of MAAs, including some reported here for the first time.