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19 July 2022

Zostera marina L.: Supercritical CO2-Extraction and Mass Spectrometric Characterization of Chemical Constituents Recovered from Seagrass

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1
N.I. Vavilov All-Russian Institute of Plant Genetic Resources, B. Morskaya 42-44, 190000 Saint-Petersburg, Russia
2
Department of Bioeconomy and Food Security, Far Eastern Federal University, Sukhanova 8, 690950 Vladivostok, Russia
3
Laboratory of Supercritical Fluid Research and Application in Agrobiotechnology, Tomsk State University, Lenin Str. 36, 634050 Tomsk, Russia
4
Siberian Federal Scientific Centre of Agrobiotechnology, Centralnaya, Presidium, 633501 Krasnoobsk, Russia
Separations2022, 9(7), 182;https://doi.org/10.3390/separations9070182
This article belongs to the Special Issue Metabolite Identification via Liquid Chromatography-Mass Spectrometry
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Abstract

Three types of Zostera marina L. collection were extracted using the supercritical CO2-extraction method. For the purposes of supercritical CO2-extraction, old seagrass ejection on the surf edge, fresh seagrass ejection on the surf edge and seagrass collected in water were used. Several experimental conditions were investigated in the pressure range 50–350 bar, with the used volume of co-solvent ethanol in the amount of 1% in the liquid phase at a temperature in the range of 31–70 °C. The most effective extraction conditions are: pressure 250 Bar and temperature 60 °C for Z. marina collected in sea water. Z. marina contain various phenolic compounds and sulfated polyphenols with valuable biological activity. Tandem mass-spectrometry (HPLC-ESI–ion trap) was applied to detect target analytes. 77 different biologically active components have been identified in Z. marina supercritical CO2-extracts. 38 polyphenols were identified for the first time in Z. marina.

1. Introduction

Zostera marina L. is a perennial marine herbaceous plant, genus Zostera, family Zosteraceae. Zostera lives mainly in the coastal waters of the northern hemisphere, it grows in the Azov, Black, Caspian, White and Far Eastern seas (Figure 1). For the most part, the plant lives in shallow water or at a depth of 1–4 m (sometimes 10 m), mainly on soft sandy or muddy bottoms in the calm waters of bays and bays. In the 30s of the last century, Zostera began to die, the reason for this was a special type of animal–the labyrinthula [1]. During the epidemic, Zostera disappeared from the coasts of North America, the Atlantic and Southern Europe and still does not grow in these places.
Figure 1. (A)—Zostera marina L. (Peter the Great Gulf, Primorsky Krai, Russia); (B)—Reproductive shoot of Z. marina L.
Zostera has a branched root system, forms underwater meadows, sometimes with a very high herbage up to 100 cm high. Plants bloom and pollinate under water, pollen is carried by streams of water. In order to survive in harsh conditions that are not intended for the life of higher plants, that is, in salty sea water, the plant has acquired a number of biochemical features that determines its adaptation to a specific habitat. The plant produces a special pectin, which has no analogues in other plants. Firstly, it was isolated in 1940 by the Russian scientist V.I. Miroshnikov, who named it zosterin. Zosterin from a chemical point of view is a polysaccharide of pectin nature. It is a highly active polyanionic adsorbent, which, passing through the gastrointestinal tract, binds and removes heavy metal ions, bile acids, pathogenic microorganisms, etc. from the body [2].
Interested in the unique nature of zosterin, Yu. S. Ovodov engaged in serious research, the result of which showed that these pectins are among the most complex in structure of objects of natural origin, and this unique feature gives them a high adsorption capacity. Because of this, a pectin called zosterin has found extensive use in medicine [3].
The pectin from Zostera marina has unique features that distinguish it from the glycans of other land plants. Numerous studies have shown that zosterin has a more complex structure than land plant pectins. Although it, like other pectins, has a linear backbone of rhamnogalacturonan and a branched region, however, the latter is a much more complex configuration. Another “block” is attached to it–xylogalacturonan (chains consisting of rings of galacturonic acid and xylose). Xylogalacturonans were found earlier in pectins of some terrestrial plants (for example, in mountain pine pollen). However, in zosterin, this fragment has additional branches that increase the volume of macromolecules.
The use of zosterin as a dietary supplement has an antiulcer effect, normalizes the function of the gastrointestinal tract, enhances the feeling of satiety, thereby facilitating the tolerance of low-calorie diets. An important property of pectin is its ability to reduce blood cholesterol, which provides an anti-sclerotic effect. Features of the metabolism of pectins allow the use of zosterin in diabetes mellitus as an auxiliary antidiabetic agent. Of exceptional interest are experimental data on the antitumor properties of zosterin and its ability to prolong life, i.e., act as a potential geroprotector. The observed effects indicate the multifunctional nature of the impact of this pectin on the body [4,5]. The therapeutic effect of rosmarinic acid, luteolin and its sulfated derivatives-these are one of the most active components of Z. marina–are considered in detail in experimental studies in diseases associated with impaired carbohydrate and lipid metabolism [6].
In this research, supercritical CO2-extraction of three samples of Z. marina was used to obtain an effective amount of polyphenolic substances: old storm seagrass waste, fresh storm seagrass waste, and seagrass collected in water. We used a tandem mass spectrometry to carry out a phytochemical study involving a detailed metabolomic analysis of Z. marina. Eelgrass was collected during expedition work near Vityaz Bay, Primorsky Krai, Russia (N 42°36′10″ E 131°10′55″), during the period from 10 to 20 August 2021.

2. Results and Discussion

Three samples of Z. marina were subjected to a detailed research: 1. old Z. marina ejection on the surf edge, 2. fresh Z. marina ejection on the surf edge, 3. Z. marina collected in the water. All three Z. marina samples were subjected to supercritical CO2-extraction under different extraction conditions. The applied supercritical pressures ranged from 50 to 350 bar, and the extraction temperature ranged from 31 to 70 °C. The co-solvent EtOH was used in an amount of 1 % of the total amount of solvent. Used different extraction conditions for different seagrass samples showed the best result for bagging in water (Extraction conditions: pressure 250 bar and temperature 60 °C). The total yield of biologically active substances under these extraction conditions was 4.2 mg per 100 mg of supercritical CO2-extract. The quantitative ratio of the extract of biologically active substances obtained by the method of supercritical extraction was achieved by evaporating the CO2 -extract and calculating the ratio of the mass of the extracted plant matrix to the dry mass of the obtained extract. Below are 3D graphs of supercritical extraction of an old Z. marina release (Figure 2); fresh release of Z. marina (Figure 3); Z. marina bagging in water (Figure 4). The structural identification of each compound was carried out on the basis of their accurate mass and MS/MS fragmentation by HPLC–ESI–ion trap– MS/MS. A total of 77 compounds were characterized in three extracts of Z. marina based on their accurate MS and fragment ions by searching online databases and the references.
Figure 2. 3D–graph data of supercritical CO2-extraction. Total yield of biologically active substances from extracts of Z. marina (old seagrass ejection on the surf edge).
Figure 3. 3D–graph data of supercritical CO2-extraction. Total yield of biologically active substances from extracts of Z. marina (fresh seagrass ejection on the surf edge).
Figure 4. 3D–graph data of supercritical CO2-extraction. Total yield of biologically active substances from extracts of Z. marina (Seagrass collected in water).
There were identified 77 compounds (53 compounds from polyphenol group and 24 compounds from other chemical groups). All the identified polyphenols and other compounds along with molecular formulas, and MS/MS data for Z. marina are summarized in Table A1 (Appendix A). For the first time, 38 polyphenols were identified in this plant. There are polyphenols: flavonols Kaempferol, Kaempferide, Herbacetin, Dihydroquercetin, Myricetin, Kaempferol 7-sulfate, Isorhamnetin 3-sulfate, Kaempferol-7-O-α-L-rhamnoside, Aromadendrin 7-O-rhamnoside, Quercitrin, Astragalin, Kaempferol 3-(6’’-malonylglucoside), Herbacetin-3-O-glucoside-7-O-xylo/ara; flavones Dihydroxy-dimethoxy(iso)flavone, Cirsimaritin, Cirsiliol, Jaceosidin, 5,6,4’-Trihydroxy-7,8-dimetoxyflavone, Syringetin, etc.
Figure 5, Figure 6, Figure 7, Figure 8, Figure 9, Figure 10, Figure 11 and Figure 12 shows examples of the decoding spectra (collision-induced dissociation (CID) spectrum) of the ion chromatogram obtained using tandem mass spectrometry. The CID spectrum in positive ion modes of flavan-3-ol (epi)Afzelechin from Z. marina is shown in Figure 5.
Figure 5. CID spectrum of (epi)Afzelechin from Z. marina, m/z 275.01.
Figure 6. CID spectrum of Luteolin 7–sulfate from Z. marina, m/z 366.82.
Figure 7. CID spectrum of Apigenin 7–sulfate from Z. marina, m/z 348.95.
Figure 8. CID spectrum of Pelargonidin 3-O-glucoside acid from Z. marina, m/z 432.55.
Figure 9. CID spectrum of Pelargonidin-3-O-(6-O-malonyl-beta-D-glucoside) acid from Z. marina, m/z 518.85.
Figure 10. CID spectrum of Kaempferol 7–sulfate from Z. marina, m/z 364.87.
Figure 11. CID spectrum of Sagerinic acid from Z. marina, m/z 718.84.
Figure 12. CID spectrum of Umbelliferone from Z. marina, m/z 163.03.
[M+H]+ ion produced two fragment ions with m/z 245.02 and m/z 175.03 (Figure 5). The fragment ion with m/z 245.02 produced one characteristic daughter ion with m/z 175.01. It was identified in the references in extract from Cassia granidis [7]; Cassia abbreviata [8]; A. cordifolia; F. glaucescens; F. herrerae [9]. It should be noted separately that the presence of many sulfated polyphenols was found in the supercritical extracts of Z. marina. For example, these are the following chemical compounds: Luteolin 7-sulfate; Diosmetin 7-sulfate, Kaempferol 7-sulfate, Isorhamnetin 3-sulfate, Apigenin7-sulfate, Chrysoeriol 7-sulfate, Luteolin 7,3′-disulfate, (2S)-Naringenin 4′-O-sulfate. The CID spectrum in positive ion modes of flavone Luteolin 7-sulfate from Z. marina is shown in Figure 6.
[M+H]+ ion produced one fragment ion with m/z 286.89 (Figure 6). The fragment ion with m/z 286.89 produced two characteristic daughter ions with m/z 152.96, and m/z 286.85. It was identified in the bibliography in extracts from Z. marina [10,11]. The CID spectrum in negative ion modes of flavone Apigenin 7-sulfate from Z. marina is shown in Figure 7.
[M–H]− ion produced one fragment ion with m/z 268.96 (Figure 7). The fragment ion with m/z 268.96 produced two characteristic daughter ions with m/z 225.01 and m/z 268.93. The fragment ion with m/z 225.01 formed one daughter ion with m/z 197.01. It was identified in the bibliography in extracts from G. linguiforme [9]; Z. marina [11]; sulphates [12]. We also want to separately note the first identification of the presence of a large class of anthocyanins in Z. marina: Pelargonidin 3-O-glucoside; Cyanidin 3-O-glucoside; Pelargonidin 3-O-(6-O-malonyl-beta-D-glucoside); Cyanidin 3-(6”-malonylglucoside). All these anthocyanins were identified firstly in Z. marina. The CID spectrum in positive ion modes of anthocyanin Pelargonidin 3-O-glucoside from Z. marina is shown in Figure 8.
[M+H]+ ion produced one fragment ion with m/z 270.90. (Figure 8). The fragment ion with m/z 270.90 formed five daughter ions with m/z 152.88, m/z 224.93, m/z 202.95, m/z 162.85, and m/z 118.96. It was identified in the bibliography in extract from Rubus ulmifolius [13]; Strawberry [14]; Vigna unguiculata [15].
The CID spectrum in positive ion modes of anthocyanin Pelargonidin 3-O-(6-O-malonyl-beta-D-glucoside) from Z. marina is shown in Figure 9. [M+H]+ ion produced two fragment ions with m/z 270.91, and m/z 432.81 (Figure 9). The fragment ion with m/z 270.91 formed two daughter ions with m/z 153.00, m/z 224.93. It was identified in the bibliography in extract from Strawberry [14], Wheat [16].
The CID spectrum in negative ion modes of flavonol Kaempferol 7-sulfate from Z. marina is shown in Figure 10. [M–H]– ion produced one fragment ion with m/z 284.92 (Figure 10). The fragment ion with m/z 284.92 formed four daughter ions with m/z 266.90, m/z 256.96, m/z 238.98, and m/z 213.03. It was identified in the bibliography in extract from F. pulverulenta Frankeniaceae [12].
The CID spectrum in negative ion modes of phenolic acid Sagerinic acid from Z. marina is shown in Figure 11. [M–H]– ion produced two fragment ions with m/z 358.92 and m/z 197.02 (Figure 11). The fragment ion with m/z 358.92 formed two daughter ions with m/z 179.08, m/z 161.03. It was identified in the bibliography in extract from Mentha [17]; Lamiaceae spp. [18]; Lepechinia [19].
The CID spectrum in positive ion mode of hydroxycoumarin Umbelliferone from Z. marina is shown in Figure 12. [M+H]+ ion produced one fragment ion with m/z 144.99 (Figure 12). The fragment ion with m/z 144.99 produced one characteristic daughter ion with m/z 117.08 It was identified in the bibliography in extracts from F. glaucescens [9]; Sanguisorba officinalis [20]; Actinidia chinensis [21].
Separately, it should be noted that a detailed analysis of the presence of polyphenols and biologically active substances from other chemical groups showed the highest number of compounds in the seagrass collected in water and fresh release on the shore than in the old release on the shore. The ratio was 31 and 30 versus 26 for polyphenols, respectively (Table 1).
Table 1. Identified polyphenols by tandem mass-spectrometry in three samples: eelgrass collected in water; fresh eelgrass ejection on the surf edge; old eelgrass ejection on the surf edge.
Thus, it can be stated that as a result of the most detailed study by tandem mass spectrometry, new data on the content of biologically active substances in Z. marina have been obtained.

3. Materials and Methods

3.1. Materials

Phytomass of Z. marina was collected during expedition work near Vityaz Bay, Primorsky Krai, Russia (N 42°36′10″ E 131°10′55″), during the period from 10 to 20 August 2021. All samples were morphologically authenticated according to the current standard of Pharmacopoeia of the Eurasian Economic Union [22].

3.2. Chemicals and Reagents

HPLC-grade acetonitrile was purchased from Fisher Scientific (Southborough, UK), MS-grade formic acid was from Sigma-Aldrich (Steinheim, Germany). Ultra-pure water was prepared from a SIEMENS ULTRA clear (SIEMENS water technologies, Munich, Germany), and all other chemicals were analytical grade.

3.3. SC-CO2 Extraction

SC-CO2 extraction was performed using the SFE-500 system (Thar SCF Waters, Milford, CT, USA) supercritical pressure extraction apparatus. System options include: Co-solvent pump (Thar Waters P-50 High Pressure Pump), for extracting polar samples. CO2 flow meter (Siemens, Germany), to measure the amount of CO2 being supplied to the system, multiple extraction vessels, to extract different sample sizes or to increase the throughput of the system. Flow rate was 10–25 mL/min for liquid CO2 and 1.00 mL/min for EtOH. Extraction samples of 20 g Z. marina were used. The extraction time was counted after reaching the working pressure and equilibrium flow, and it was 60–90 min for each sample.

3.4. Liquid Chromatography

HPLC was performed using Shimadzu LC-20 Prominence HPLC (Shimadzu, Japan) was used, equipped with an UV-sensor and a Shodex ODP-40 4E reverse phase column to perform the separation of multicomponent mixtures. The gradient elution program was as follows: 0.01–4 min, 100% C2H3N; 4–60 min, 100–25% C2H3N; 60–75 min, 25–0% C2H3N; control washing 75–120 min 0% C2H3N. The entire HPLC analysis was performed using a UV-VIS detector SPD-20A (Shimadzu, Japan) at wavelengths of 230 and 330 nm, at 17 °C provided with column oven CTO-20A (Shimadzu, Japan) with an injection volume of 20 μL.

3.5. Mass Spectrometry

MS analysis was performed on an ion trap amaZon SL (BRUKER DALTONIKS, Germany) equipped with an ESI source in negative ion mode. The optimized parameters were obtained as follows: ionization source temperature: 70 °C, gas flow: 4 L/min, nebulizer gas (atomizer): 7.3 psi, capillary voltage: 4500 V, end plate bend voltage: 1500 V, fragmentary: 280 V, collision energy: 60 eV. An ion trap was used in the scan range m/z 100–1.700 for MS and MS/MS. The mass spectra were recorded in negative and positive ion mode. The capture rate was one spectrum/s for MS and two spectrum/s for MS/MS. Data collection was controlled by Hystar Data Analysis 4.1 software (BRUKER DALTONIKS, Bremen, Germany). All experiments were repeated three times. A four-stage ion separation mode (MS/MS mode) was implemented. After a comparison of the m/z values, retention times, and the fragmentation patterns with the MS/MS spectral data retrieved from the cited articles and after a database search (MS2T, MassBank, HMDB), a comprehensive table was compiled of the molecular masses of the analytes isolated from CO2 extracts of Z. marina for ease of annotation (Appendix A (Table A1)).

4. Conclusions

Three types of Zostera marina L. collection were extracted using the supercritical CO2-extraction method. For the purposes of supercritical CO2-extraction, old seagrass ejection on the surf edge, fresh seagrass ejection on the surf edge and seagrass collected in water were used. Several experimental conditions were investigated in the pressure range 50–350 bar, with the used volume of co-solvent ethanol in the amount of 1 % in the liquid phase at a temperature in the range of 31–70 °C. The most effective extraction conditions are: pressure 250 Bar and temperature 60 °C for Z. marina collected in sea water. Z. marina contain various phenolic compounds and sulfated polyphenols with valuable biological activity. Tandem mass-spectrometry (HPLC-ESI–ion trap) was applied to detect target analytes. High-accuracy mass spectrometric data were recorded on an ion trap amaZon SL BRUKER DALTONIKS equipped with an ESI source in the mode of negative and positive ions. The four-stage ion separation mode was implemented. 77 different biologically active components have been identified in Z. marina supercritical CO2-extracts. 38 polyphenols were identified for the first time in Z. marina.
These data could support future research for the production of a variety of pharmaceutical products containing extracts of Z. marina. The richness of various biologically active compounds, including compounds of polyphenol group, amino acids, carotenoids, Omega- fatty acids, sterols, triterpenoids, iridoids, etc., provides great opportunities for the design of new nutritional and dietary supplements based on extracts from this genus Zostera.

Author Contributions

Conceptualization, L.A.T. and M.P.R.; methodology, L.A.T., A.M.Z. and M.P.R.; software, M.P.R.; validation, L.A.T., M.P.R. and K.G.; formal analysis, M.P.R. and A.M.Z.; investigation, L.A.T. and A.B.P.; resources, K.G. and L.A.T.; data curation, V.D.S.; writing—original draft preparation—M.P.R. and A.M.Z.; writing—review and editing A.M.Z. and K.G.; visualization, M.P.R. and A.M.Z.; supervision, K.G.; project administration, A.M.Z., K.G. and L.A.T. All authors have read and agreed to the published version of the manuscript.

Funding

This research was carried out with financial support of the Ministry of Education and Science of the Russian Federation within the framework of the implementation of a complex project for the creation of high-tech production provided by the Decree of the Russian Federation Government dated 9 April 2010 № 218. The project is entitled “Development of industrial technology and organization in the Far Eastern Federal District of the high-tech production of feed Vitamin A of increased stability and bioavailability”, agreement No. 075-11-2021-065, 25 June 2021.

Institutional Review Board Statement

Not applicable.

Data Availability Statement

All data are available from the corresponding author upon request.

Acknowledgments

Research work according to “Development of industrial technology and organization in the Far Eastern Federal District of the high-tech production of feed Vitamin A of increased stability and bioavailability”, agreement No. 075-11-2021-065, 25 June 2021.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

Table A1. Compounds identified from the CO2-extracts of Zostera marina in positive and negative ionization modes by HPLC-ion trap-MS/MS.
Table A1. Compounds identified from the CO2-extracts of Zostera marina in positive and negative ionization modes by HPLC-ion trap-MS/MS.
№Class of CompoundsIdentified CompoundsFormulaMassMolecular ion [M-H]-Molecular ion [M+H]+2 fragmentation MS/MS 3 Fragmentation MS/MS 4 Fragmentation MS/MS References
POLYPHENOLS
1FlavonolKaempferol [3,5,7-Trihydroxy-2-(4-hydro- xyphenyl)-4H-chromen-4-one] *C15H10O6286.24 287258; 241; 187; 137229; 213; 153203; 132Rhus coriaria [23]; Andean blueberry [24]; Potato leaves [25]; Impatients glandulifera Royle [26]; Rapeseed petals [27]; Rh. sichotense [28]
2FlavonolKaempferide [4’-O-Methylkaempferol] *C16H12O6300.2629 301286258229; 201; 153Spondias purpurea [29]; Ocimum [30]; Alpinia officinarum [31]; Brazilian propolis [32]
3FlavonolHerbacetin [3,5,7,8-Tetrahydroxy-2-(4-hydro- xyphenyl)-4H-chromen-4-one] *C15H10O7302.2357 303275; 202; 185; 157175; 157 Ocimum [30]; Rhodiola rosea [33]
4FlavonolDihydroquercetin [Taxifolin; Taxifoliol] *C15H12O7304.25303 285267; 241; 215; 135171Andean blueberry [24]; millet grains [34]; Camellia kucha [35]; Rosa rugosa [36]
5FlavonolMyricetin [3,5,7-Trihydroxy-2-(3,4,5-Trihydroxyphenyl)-4H-Chromen-4-One] *C15H10O8318.2351 319289; 261; 239; 219; 191; 173261; 243; 214; 191; 173; 159233; 215; 191; 161; 143Sanguisorba officinalis [20]; Andean blueberry [24]; millet grains [34]; Rosa rugosa [36]; Vaccinium macrocarpon [37]
6FlavonolKaempferol 7-sulphate *C15H10O9S366.2995365 285241; 199; 151197; 171; 143F. pulverulenta Frankeniaceae [12]
7FlavonolIsorhamnetin 3-sulphate *C16H10O10S394.3096393 313298269Senecio galicus Asteraceae; Polygonium hydropiper Polygoniaceae [12]
8FlavonolKaempferol-7-O-α-L-rhamnoside *C21H20O10432.3775431 257227; 157215; 145Rhodiola crenulata [38]; Rhodiola sachalinensis [39]
9FlavonolAromadendrin 7-O-rhamnoside *C21H22O10434.3934433 259; 229227; 199; 157215; 199Eucalyptus [40]
10FlavonolQuercitrin [Quercetin 3-L- rhamnoside; Quercetrin] *C21H20O11448.3769 449303; 203203185Rhus coriaria [23]; Camellia kucha [35]; Vaccinium macrocarpon [37,41]; Propolis [42]
11FlavonolAstragalin [Kaempferol 3-O-glucoside; Kaempferol-3-Beta-Monoglucoside; Astragaline] *C21H20O11448.3769 449287; 367153; 240 Actinidia chinensis [21]; Rapeseed petals [27]; Spondias purpurea [29]; Camellia kucha [35]; Lonicera japonicum [43]
12FlavonolKaempferol 3-(6’’-malonylglucoside) *C24H22O14534.4231 535449; 287263; 219; 153 A. cordifolia [9]; Impatients glandulifera Royle [26]; Mexican lupine species [44]
13FlavonolHerbacetin-3-O-glucoside-7-O-xylo/ara *C26H28O16596.4909 597436389; 327; 240; 221; 194194; 150Rhodiola rosea [45]
14FlavoneLuteolinC15H10O6286.2363 287152; 241; 187 Zostera marina [11]; Propolis [42]; Lonicera japonicum [43]; Dracocephalum palmatum [46]
15FlavoneDiosmetinC16H12O6300.2629299 283; 256 Andean blueberry [24]; Lonicera japonicum [43]; Cirsium japonicum [47]; Mentha [48]
16FlavoneChrysoeriol [Chryseriol]C16H12O6300.2629 301286; 244; 203258229Rhus coriaria [23]; Mexican lupine species [44]; Dracocephalum palmatum [46]; Mentha [48]
17FlavoneDihydroxy-dimethoxy(iso)flavone *C17H14O6314.2895 315299; 271; 215; 169297; 271; 253; 229; 186269; 253; 145Propolis [42]; Rosmarinus officinalis [49]; Astragali radix [50]
18FlavoneCirsimaritin *C17H14O6314.2895 315299; 282; 254254226; 197; 181; 169; 153Ocimum [30]; Rosmarinus officinalis [49]
19FlavoneCirsiliol *C17H14O7330.2889 331298; 203270241Ocimum [30]
20FlavoneJaceosidin [5,7,4’-trihydroxy-6’,5’-dimetoxyflavone] *C17H14O7330.2889 331303; 285; 257; 231203; 184; 157185; 157; 127Mentha [48,51]
21Flavone5,6,4’-Trihydroxy-7,8-dimetoxyflavone *C17H14O7330.2889 331303; 257; 221; 203275; 221; 203245; 175; 143F. glaucescens; F. herrerae [9]; Mentha [48]
22FlavoneSyringetin *C17H14O8346.2883 347318; 291; 247; 219291; 261; 219273; 261; 243; 191C. edulis [9]
23FlavoneApigenin 7-sulfateC15H10O8S350.3001349 269225; 197; 159197Zostera marina [11]; G. linguiforme [9]; sulphates [12]
24FlavoneHydroxy-tetramethoxy(iso) flavone *C19H18O7358.342 359315256; 190 Propolis [42]
25FlavoneLuteolin 7-sulphateC15H10O9S366.2995 367287153; 259; 241; 219; 199; 179123Zostera marina [10,11]
26FlavoneChrysoeriol-7-sulphateC16H12O9S380.3261 381301;286258Zostera marina [10]
27FlavoneDiosmetin-7-sulphateC16H12O9S380.3261379 299284 Zostera marina [10,11]
28FlavoneLuteolin 7-O-glucoside [Cynaroside; Luteoloside]C21H20O11448.3769 449287213; 137185Zostera marina [10]; millet grains [34]; Propolis [42]; Mexican lupine species [44]; Mentha [51]; Thymus vulgaris [52]
29FlavoneLinarin [Acaciin; Buddleoside; Acacetin-7-O-Rutinoside; Linarigenin Glycoside] *C28H32O14592.5453 593575; 377; 197377197Dracocephalum palmatum [46]; Mentha [48,51,53]
30FlavoneApigenin 6-C-[6”-acetyl-2”-O-deoxyhexoside]-glucoside *C29H32O15620.5554 621561461433Passiflora incarnata [54]
31FlavoneAcacetin-acetyl-glucoside-rhamnoglucosideC34H36O22796.6364 797519240; 185 Mentha [52]
32FlavoneLuteolin 7,3’-disulphateC15H10O12S2446.3627 447287; 366241 Zostera marina [10]
33Flavan-3-olEpiafzelechin [(epi)Afzelechin] *C15H14O5274.2687 275244; 233; 216; 193; 175237; 213; 192; 175; 15; 145 Cassia granidis [7]; Cassia abbreviata [8]; A. cordifolia; F. glaucescens; F. herrerae [9]
34Flavan-3-olDerivative of (epi)Afzelechin *C15H16O5276.2845 277245; 229; 216; 207233; 215211
35Flavan-3-olCatechin [D-Catechol] *C15H14O6290.2681 291261; 173243; 191; 173; 143143; 125millet grains [34]; Camellia kucha [35]; Vaccinium macrocarpon [41]; Eucalyptus [55]; Radix polygoni multiflori [56]; Rh. rosea [57]
36Flavan-3-ol(epi)Catechin *C15H14O6290.2681 291261; 231; 209; 191; 173243; 215; 199; 179; 161233; 206; 180; 161; 138Andean blueberry [24]; millet grains [34]; Vaccinium macrocarpon [41]; Eucalyptus [55]; Rh. rosea [57]; Rubus occidentalis [58]
37Flavan-3-ol(epi)Afzelechin derivative *C18H16O10392.3136 393274245; 221; 205; 191; 175; 157237; 192; 176; 157
38Flavan-3-olCatechin derivative *C19H20O11424.3555 425291261; 173173
39Flavanone(2S)-Naringenin 4′-O-sulfate *C15H12O8S352.3160351 271269225Tamarix africana [59]
40AnthocyaninPelargonidin-3-O-glucoside (callistephin) *C21H21O10433.3854 433271153; 247; 225; 187; 163127Rubus ulmifolius [13]; Strawberry [14]; Vigna unguiculata [15]
41AnthocyaninCyanidin-3-O-glucoside [Cyanidin 3-O-beta-D-Glucoside; Kuromarin] *C21H21O11+449.3848 449287241; 153 Rubus ulmifolius [13]; Rapeseed petals [27]; Berberis ilicifolia; Berberis empetrifolia; Ribes maellanicum; Ribes cucullatum; Myrteola nummalaria; Gaultheria mucronata; Gaultheria antarctica; Rubus geoides; Fuchsia magellanica [60]; Oryza sativa [61]
42AnthocyaninPelargonidin-3-O-(6-O-malonyl-beta-D-glucoside) *C24H23O13519.4388 519271; 433153; 224 Strawberry [14]; Wheat [16]
43AnthocyaninCyanidin 3-(6”-malonylglucoside) *C24H23O14535.4310 535287; 449241; 153 Wheat [16]; Strawberry [14,62]
44Phenolic acids and derivativesZosteric acid [P-Sulfoxycinnamic acid; 4-Hydroxycinnamate Sulfate]C9H8O6S244.2212 245145; 202141 Zostera marina [11]
45Phenolic acids and derivativesCaffeic acid [(2E)-3-(3,4-Dihydroxyphenyl)acrylic acid] C9H8O4180.1574 181135; 163; 145; 121119 Zostera marina [11]; Vaccinium macrocarpon [41]; Lonicera japonicum [43]; Dracocephalum palmatum [46]; Radix polygoni multiflori [56]; Rubus occidentalis [58]
46Phenolic acids and derivativesCaffeic acid derivativeC9H18O6222.2356221181142 Embelia [63]
47Phenolic acids and derivatives3-O-caffeoylshikimic acid [3-Csa] *C16H16O8336.2934 337191; 173; 153123 Grataegi Fructus [64]
48Phenolic acids and derivativesRosmarinic acidC18H16O8360.3148359 161; 135133 Zostera marina [10,11]; Rosa rugosa [36]; Dracocephalum palmatum [46]; Rosmarinus officinalis [49]; Huolisu Oral Liquid [65]
49Phenolic acids and derivativesCaffeic acid derivativeC16H18O9Na377.2985376 341; 215179119Embelia [63]; Bougainvillea [66]
50Phenolic acids and derivativesEllagic acid pentoside [Ellagic acid 4-O-xylopyranoside] *C19H14O12434.3073433 257227; 157215Eucalyptus [40]; Strawberry [62]; Punica granatum [67]
51Phenolic acids and derivativesSagerinic acid *C36H32O16720.6297719 359161 Mentha [17]; Lamiaceae spp. [18]; Lepechinia [19]
52HydroxycoumarinUmbelliferone [Skimmetin; Hydragin] *C9H6O3162.1421 163145117 F. glaucescens [9]; Sanguisorba officinalis [20]; Actinidia chinensis [21]
53DihydrochalconePhloretin [Dihydronaringenin; Phloretol] *C15H14O5274.2687 275245; 175214; 175 G. linguiforme [9]; Eucalyptus [55]; Punica granatum [67]
OTHERS /
54Cyclohexanecarboxylic acidPerillic acidC10H14O2166.217 167149147137Mentha [48]
55Amino acidL-threanineC7H14N2O3174.1977 175157; 147; 125147; 129 Camelia kucha [35]
56Omega-5 fatty acidMyristoleic acid [Cis-9-Tetradecanoic acid] *C14H26O2226.3550 227209192; 139122F. glaucescens [9]
57Carotenoid3-OH-beta-apo-11-carotenalC15H22O2234.3340 235214; 157157140Carotenoids [68]
58Peptide5-Oxo-L-propyl-L-isoleucineC11H18N2O4242.2716 243141131 Potato leaves [25]
59Carotenoidbeta-apo-13-carotenalC18H26O258.4984 Carotenoids [68]
60Aporphine alkaloidAnonaineC17H15NO2265.3065 266219202 Magnolia [69]
61AnthraquinoneEmodin [6-Methyl-1,3,8-trihydroxyanthraquinone]C15H10O5270.2369 271241162 Radix polygoni multiflori [56]; Huolisu Oral Liquid [65]; [70]
62Omega-3 fatty acidLinolenic acid (Alpha-Linolenic acid; Linolenate)C18H30O2278.4296277 273; 233; 205273 Salviae [71]; rice [72]; Pinus sylvestris [73]
63Omega-9 unsaturated fatty acidOleic acid (Cis-9-Octadecenoic acid; Cis-Oleic acid)C18H34O2282.4614 283265; 223; 215; 188; 168197 Zostera marina [11]; Sanguisorba officinalis [20]; Huolisu Oral Liquid [65]
64CarotenoidApo-14’-ZeaxanthinalC22H30O2326.4735 327281; 329; 225; 173222 Carotenoids [74]
65Amino disaccharideTrehalosyl 2,4,6’- triamineC12H26N3O8340.3501 341276; 210; 331 [75]
66Omega-hydroxy-long-chain-fatty acidHydroxy docosanoic acidC22H44O3356.5830355 309305; 281287A. cordifolia [9]
67SterolStigmasterol [Stigmasterin; Beta-Stigmasterol]C29H48O412.6908 413301; 171189171A. cordifolia; F. pottsii [9]; Oryza sativa [61]; Olive leaves [76]; Hedyotis diffusa [77]
68SterolFucosterol [Fucostein; Trans-24-Ethylidenecholesterol] *C29H48O412.6908 413395; 301; 267; 189189 F. pottsii [9]; Oryza sativa [61]
69SterolBeta-Sitostenone [Stigmast-4-En-3-One; Sitostenone]C29H48O412.6908 413301; 269; 189; 171189; 171; 153 F. herrerae [9]; Cryptomeria japonica bark [78]; Xanthium sibiricum [79]; Terminalia laxiflora [80]
70Iridoid monoterpenoidDihydroisovaltrateC22H32O8424.4847 425365; 281309; 235253Rhus coriaria [23]
71SterolSigmast-4-en-6-beta-ol-3-oneC29H48O2428.6902 429297; 153261 Xanthium sibiricum [79]
72Anabolic steroid; Androgen; Androgen esterVebonolC30H44O3452.6686 453435; 336; 305; 209336; 309; 226292; 209; 139Rhus coriaria [23]; Hylocereus polyrhizus [81]
73Triterpenic acid1-Hydroxy-3-oxours-12-en-28-oic acidC30H46O4470.6838 471453; 337; 209209; 336; 435182Pear [82]
74Carotenoid(all-E)-lutein 3’-O-myristateC40H54O550.8562 551531; 501; 452; 431333; 303; 271314; 303Carotenoids [83]; Rosa rugosa [84]
75CarotenoidAntheraxanthin [All-Trans-Antheraxanthin]C40H56O3584.8708 585567; 493; 451; 395; 342;493;413; 383; 337475; 422; 409; 377Carotenoids [83]; Sarsaparilla [85]; Arbutus unedo [86]
76Carotenoid(all-E)-ViolaxanthinC40H56O4600.8702 601581; 540; 501; 415; 301523; 442; 290 Rosa rugosa [84]; Arbutus unedo [86]; Carica papaya [87]; Physalis peruviana [88]
77Chlorophylle derivativeChlorophyllide aC35H34MgN4O5614.9733 615579; 545; 528; 478508 [89,90]
* Compounds identified for the first time in Z. marina.

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Amaranth Oilseed Composition and Cosmetic Applications
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