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. 2020 Mar 16;10(3):111. doi: 10.3390/metabo10030111

Table 1.

Chromatographic and Spectrometric Data of the Tentatively Identified Compounds in H. hirsuta Detected with a Generic LC-PDA-amMS Method for Moderately Polar Phytochemicals.

Com-Pound Number Compound a Molecular Formula RT (min) HESI Full MS b HESI ddMS2 Neutral Losses Max Abs. (nm) Literature
1 quinic acid c C7H12O6 1.54 neg 191.05611 -
pos - -
2 gallic acid c C7H6O5 4.06 neg 169.01412 -
pos - -
3 protocatechuic acid [3,4-dihydroxybenzoic acid] c C7H6O4 6.46 neg 153.01933 109.02950 109.02950: C6H6O2 259; 294
pos - -
4 caffeyl hexose C15H18O9 7.68 neg 341.08817 179.03439; 135.04439 179.03439: C9H8O4; 135.04439: C9H8O4 - CO2
pos 365.08380 [M+Na]+; 360.12839 [M+NH4]+ 181.04962; 163.03906; 145.02861; 135.04443 181.04962: C9H8O4; 163.03906: C9H8O4 - H2O; 145.02861: C9H6O4 - 2H2O; 135.04443: C8H6O2
5 asperulosidic acid C18H24O12 8.01 neg 431.11975; 499.10757 [M-H+NaFA]−; 863.24756 [2M-H]− 329.09064; 161.04463 329.09064: C14H18O9; 161.04463: C6H10O5
pos 433.13428 271.08188; 187.06091; 145.04990; 127.03919 271.08188: C18H24O12 - C6H10O5; 187.06091: C8H10O5; 145.04990: C6H8O4; 127.03919: C6H6O3
6 dihydrocaffeic acid c C9H10O4 8.07 neg 181.05041 -
pos - -
7 1-O-feruloylquinic acid d C17H20O9 8.76 neg 367.10349; 435.09108 [M-H+NaFA]− -
pos 369.11795 -
8 chlorogenic acid [3.4-dihydroxycinnamoylquinic acid; 5-Caffeoylquinic acid] c C16H18O9 8.94 neg 353.08685; 707.18355 [2M-H]− 191.05545 191.05611: C7H12O6 326
pos 355.10160; 377.08360 [M+Na]+; 731.17920 [2M+Na]+ 163.03897 163.03897: C9H6O3
9 isorhamnetin-3-O-rutinoside-7-O-glucoside d C34H42O21 9.27 neg 785.21631; 853.20349 [M-H+NaFA]− 623.16479; 476.09396; 315.05124; 300.02750; 271.02466 623.16479: C34H42O21 - C6H10O5; 315.05124: C16H12O7; 300.02750: C15H9O7; 271.02466: C14H7O6
pos 787.22931 641.17114; 479.11838 641.17114: C34H42O21 - C6H10O4; 479.11838: C34H42O21 - C6H10O4 - C6H10O5
10 chlorogenic acid c C16H18O9 9.36 neg 353.08781 191.05611 191.05611: C7H12O6
pos 355.10236 163.03897
11 Catechin c C15H14O6 11.21 neg 289.07176 - 279 Mbark et al.
pos - -
12 epicatechin c C15H14O6 11.25 neg 289.07176 - 280
pos - -
13 procyanidin B2 c C30H26O12 9.68 neg 577.13515 -
pos 579.14970 -
14 caffeic acid c C9H8O4 9.7 neg 179.03498 135.04515 135.04515: C9H8O4 - CO2
pos 181.04954 163.03915; 145.02861; 135.04443 163.03897: C9H8O4 - H2O
15 1-O-feruloylquinic acid d C17H20O9 10.51 neg 367.10358; 435.09106 [M-H+NaFA]− 193.05003; 173.04489; 134.03622 193.05003: C10H10O4; 173.04485: C7H10O5
pos 391.10001 [M+Na]+ 145.02855; 149.05952; 117.03381; 177.05475; 194.05750 145.02855: C9H4O2; 149.05952: C9H8O2; 117.03381: C8H4O; 177.05475: C10H10O4 - H2O
16 quercetin 3-rhamnosyl-(1->2)-rhamnosyl-(1->6)-glucoside or quercetin 3-rhamninoside C33H40O20 11.05 neg 755.20471; 823.19204 [M-H+NaFA]−; 1511.41418 [2M-H]− 300.02771; 271.02499; 255.02994 300.02771: C15H9O7; 271.02499: C14H8O6; 255.02994: C14H8O5
pos 757.21765; 611.16085 465.1033; 303.05008 465.1033: C33H40O20 - 2C6H10O4; 303.05008: C33H40O20 - 2C6H10O4 - C6H10O5
17 matairesinoside C26H32O11 11.3 neg 565.19336 [M-H+FA]− 339.12378; 329.13812; 327.12405; 324.09967; 312.09885; 309.07953; 297.07669 339.12378: C20H20O5; 329.13812: C19H22O5; 327.12405: C19H20O5; 324.09967: C19H17O5; 312.09885: C18H17O5; 309.07953: C18H14O5; 297.07669: C17H14O5 355
pos 543.18420 [M+Na]+; 538.22786 [M+NH4]+ 503.19199; 341.13672; 323.12738; 311.12756; 175.07526; 137.05983 503.19199: C26H30O10; 341.13672: C20H20O5; 323.12738: C20H18O4; 311.12756: C19H18O4; 175.07526: C11H10O2; 137.05983: C8H8O2
18 isorhamnetin-O-glycoside (one hexosyl and two deoxyhexosyl units) C34H42O20 11.74 neg 769.22040 [M-H]; 1539.44527 [2M-H]−; 632.32239 357.06104; 314.04349; 271.02512; 299.01981; 285.04065 632.32239: C34H42O20 - C6H10O4; 357.06104: C18H14O8; 314.04349: C16H11O7; 299.01981: C15H8O7; 285.04065: C15H10O6; 271.02512: C14H8O6 355
pos 771.23315; 625.17635; 479.11849 625.17743; 479.11874; 317.06540 625.17743: C34H42O20 - C6H10O4; 479.11874: C34H42O20 - 2C6H10O4; 317.06540: C34H42O20 - 2C6H10O4 - C6H10O5
19 quercetin 3-O-β-(2″-O-α-L-rhamnopyranosyl)-glucopyranoside C27H28O17 11.96 neg 623.12537; 1247.25657 [2M-H]− 301.03543 301.03543: C27H28O17 - C6H10O4 - C6H8O6 255; 355 van Dooren et al. (2016)
pos 625.13943; 479.08180 479.08240; 303.04999 479.08180: C27H28O17 - C6H10O4; 303.04999: C27H28O17 - C6H10O4 - C6H8O6
20 rutin c C27H30O16 12.08 neg 609.14667; 677.13349 [M-H+NaFA]− 300.02762; 271.02481; 255.02990; 243.02990 300.02755: C15H9O7; 271.02481: C14H8O6; 255.02990: C14H8O5; 243.02990: C13H8O5 256; 355 van Dooren et al. (2016)
pos 611.15973 465.10267; 303.04999 465.10275: C21H22O12; 303.04993: C15H12O7
21 cynaroside c C21H20O11 12.2 neg 447.09364 - Wagner et al. (2013)
pos - -
22 hesperidin c C28H34O15 12.24 neg 609.18153 -
pos 611.19705 -
23 ferulic acid c C10H10O4 12.34 neg 193.05063 178.02643 178.02643: C9H7O4
pos 195.06519 177.0547; 145.02855; 135.04424; 117.03378 177.0547: C10H10O4 - H2O; 149.05984: C9H12O2; 145.02855: C9H4O2; 135.04424: C8H6O2; 117.03378: C8H4O
24 herniariasaponin 1 C54H56O32 12.59 neg 1215.2698 -
pos 1239.26343 [M+Na]+ -
25 isoquercetin c C21H20O12 12.61 neg 463.0882 300.02725; 271.02539; 255.02905; 243.02859; 151.00230 300.02725: C15H9O7; 271.02539: C14H8O6; 255.02905: C14H8O5; 243.02859: C13H8O5; 151.00230: C7H4O4
pos 465.10275 303.05008; 287.05533; 257.04483 303.05008: C15H10O7; 287.05533: C15H10O6; 257.04483: C14H8O5
26 p-coumaric acid c C9H8O3 12.62 neg 163.04007 119.05024 119.05024: C8H8O
pos 165.05462 147.04414 147.04414: C9H6O2
27 2-(3.4-Dihydroxyphenyl)-5.7-dihydroxy-4-oxo-4H-chromen-3-yl-6-O-(2-O-acetyl-α-L-arabinopyranosyl)-β-D-glucopyranoside C28H30O17 12.67 neg 637.14125; 1275.28809 [2M-H]− 463.09000; 300.02728 463.09000: C21H20O12; 300.02728: C15H9O7
pos 639.15543; 493.09749 465.10071; 303.04972 493.09749: C28H30O17 – C6H10O4; 465.10071: C21H20O12; 303.04972: C15H10O7
28 miquelianin [quercetin-3-O-glucuronide]c C21H18O13 12.89 neg 477.06746 301.03538; 271.02481 255.02990; 178.99860; 151.00368 301.03538: C15H10O7; 271.02481: C14H8O6; 255.02990: C14H8O5; 178.99860: C8H4O5; 151.00368: C7H4O4
pos 479.08202 303.04993; 257.04445 303.04993: C15H10O7; 257.04445: C14H8O5
29 narcissin [isorhametin-3-O-rutinoside] C28H32O16 12.89 neg 623.16211; 477.06749; 1247.33026 [2M-H]− 315.05072 477.06749: C28H32O16 - C6H10O4; 315.05072: C28H32O16 - C6H10O4 - C6H10O5 254; 355 van Dooren et al. (2016) Wagner et al. (2013)
pos 625.14606 479.11804; 317.06586 479.11804: C28H32O16 - C6H10O4; 317.06586: C28H32O16 - C6H10O4 - C6H10O5
30 avicularin [quercetin-3-O-arabinoside] c C20H18O11 13.16 neg 433.0782 301.03586 256; 355
pos 435.09219 -
31 apigetrin c C21H24O9 13.27 neg 431.09837 268.03827 268.03827: C15H9O5
pos 433.11292 -
32 astragalin [kaempferol 3-O-glucoside] c C21H20O11 13.34 neg 447.09381 284.03314; 255.03024; 227.03455 284.03314: C15H9O6; 255.03024: C14H8O5; 227.03455: C13H8O4 265; 348
pos 449.10814 -
33 quercitrin c C21H20O11 13.35 neg 447.09328 - 265; 346
pos 449.10784 -
34 salicylic acid c C7H6O3 14.07 neg 137.02442 93.03459 93.03459: C6H6O 236; 302
pos - -
35 herniariasaponin F C59H94O28 14.17 neg 1249.58482; 647.29342 501.32303; 439.32358 647.29342: C30H46O6 + C6H10O4; 501.32303: C30H46O6; 439.32358: C30H46O6 - H2O - CO2 Mbark et al. (2000)
pos 1273.58240 [M+Na]+; 1268.62600 [M+NH4]+; 1122.56885; 645.27747; 457.33133 771.25336 457.33133: C29H44O4; 771.25336: 2C6H10O5 + 2C6H10O4 + C5H8O4 + Na
36 acetylated medicagenic acid + two hexosyl + two deoxyhexosyl + one pentosyl moieties e C61H96O29 14.53 neg 1291.59644 1249.59241; 1231.57312; 821.43506; 543.33441; 501.32294; 483.31107; 439.32251 821.43506: C61H96O29 - 2C6H10O5 - C6H10O4; 543.33441: C32H48O7; 501.32294: C30H46O6; 483.31107: C30H46O6 - H2O; 439.32251: C30H46O6 - H2O - CO2
pos 1310.63818 [M+NH4]+ -
37 acetylated medicagenic acid + three hexosyl + one deoxyhexosyl moieties e C56H88O26 14.61 neg 1175.549 705.38928; 543.33337; 501.32281; 439.32205 705.38928: C32H48O7 + C6H10O5; 543.33337: C32H48O7; 501.32281: C30H46O6; 439.32205: C30H46O6 - H2O - CO2 Schröder et al. (1993)
pos 1194.59088 [M+NH4]+ -
38 medicagenic acid + two hexosyl + two deoxyhexosyl + two pentosyl + 1 glucuronic acid moiety e C70H110O38 14.89 neg 1557.6595; 1411.60317 1235.56738; 983.57922; 796.23248; 439.32043 1411.60317: C70H110O38 - C6H10O4; 1235.56738: C70H110O38 - C6H10O4 - C6H8O6; 439.32043: C29H44O3 Mbark et al. (2000)
pos 1581.65795 [M+Na]+ 1259.56189; 741.24219; 595.18250; 445.13116
39 zanhic acid + one hexose + four deoxyhexoses + two pentoses + one glucuronic acid moiety e C76H120O42 14.92 neg 1703.71708; 851.35632 [M-2H]2− 1381.62830; 823.41089; 517.31879; 455.31766; 839.40845 1381.62830: C76H120O42 - C6H10O4 - C6H8O6; 517.31879: C30H46O7; 455.31766: C30H46O7 - H2O - CO2; 839.40845: C30H47O7 + C6H10O4 + C6H8O6
pos 1727.71399 [M+Na]+; 1722.75891 [M+NH4]+ -
40 herniariasaponin E C55H86O25 15.03 neg 1145.5387; 1213.52771 [M-H+NaFA]−; 572.26715; 595.26941 [M-2H-FA]2− 543.33105; 483.31180; 439.32227; 601.19806; 439.32208 543.33105: C32H48O7; 483.31180: C30H46O6 - H2O; 439.32227: C30H46O6 - H2O - CO2; 601.19806: C5H8O4 + C6H10O4 + 2C6H10O5; 439.32208: C5H8O4 + C6H10O4 + C6H10O5 Mbark et al. (2000)
pos 1169.53381 [M+Na]+; 1164.57869 [M+NH4]+ 545.34430 545.34430: C32H48O7
41 acetylated medicagenic acid + three hexosyl moieties e C50H78O22 15.06 neg 1029.49191; 1075.49754 [M-H+FA]− 543.33105; 483.31180; 439.32227; 791.07910; 585.34424 543.33105: C32H48O7; 483.31180: C30H44O5; 439.32227; 791.07910: C29H28O26
pos 1048.53173 [M+NH4]+; 1053.48612 [M+Na]+ -
pos 1398.65376 [M+NH4]+ -
42 medicagenic acid + three deoxyhexosyl + one pentosyl + one glucuronic acid moiety e C59H92O28 15.12 neg 1247.569 925.48315; 501.31976
pos 1271.56687 [M+Na]+ 1127.49792; 949.47644; 701.34851; 525.32062; 447.14737
43 zanhic acid + three deoxyhexosyl + one pentosyl + one glucuronic acid moiety e C59H92O29 15.24 neg 1263.5657 1163.15430; 1081.94128
pos 1282.60583 [M+NH4]+ -
44 medicagenic acid + two hexosyl + three deoxyhexosyl + two pentosyl + one glucuronic acid moiety e C76H120O42 15.33 neg 1703.7174 1381.62830; 1219.22852; 879.30701; 843.52264; 823.41089; 501.32275; 439.31934
pos 1727.71399 [M+Na]+; 1722.75891 [M+NH4]*+ -
45 medicagenic acid + one hexosyl + four deoxyhexosyl + two pentoses + one glucuronic acid moiety e C76H120O41 15.52 neg 1687.7229 1365.63477; 998.50537; 823.42078
pos 1711.71936 [M+Na]+ -
46 medicagenic acid + three deoxyhexosyl + two pentosyl + one glucuronic acid moiety d,e C64H100O32 15.12; 15.62 neg 1379.6127 1057.52454; 925.48077; 823.41821; 501.32251; 439.32050 1057.52454: C64H100O32 - C6H8O6 - C6H10O4; 925.48077: C64H100O32 - C6H8O6 - C6H10O4 – C5H8O4; 823.41821: C35H68O21; 501.32251: C30H46O6; 439.32050: C30H46O6 - H2O - CO2
pos 1403.60791 [M+Na]+ 1259.54272; 1081.51782; 847.40808; 579.18964
47 medicagenic acid + one hexosyl + two deoxyhexosyl + two pentosyl + one glucuronic acid moiety e C64H100O33 15.67 neg 1395.6069 439.32248; 1219.58301 439.32248: C30H46O6 - H2O - CO2; 1219.58301: C64H100O33 - C6H8O6 Charrouf et al. (1995)
pos 1419.60059 [M+Na]+ -
48 herniariasaponin B C65H102O33 15.83 neg 1409.6244 1087.53479; 823.41272; 501.32300; 439.32343 1087.53479: C65H102O33 - C6H10O4 - C6H8O6; 823.41272; 501.32300: C30H46O6; 439.32343: C30H46O6 - H2O - CO2 Charrouf et al. (1995)
pos 1433.61982 [M+Na]+; 1428.66283 [M+NH4]+; 1411.63638 -
49 acetylated medicagenic acid + one deoxyhexosyl + two pentosyl moieties e C47H74O19 16 neg 941.47546 501.32312; 439.32037; 821.43097; 543.33167 821.43097: C47H74O19 - C5H8O4; 543.33167: C32H48O7; 501.32312: C30H46O6; 439.32037: C30H46O6 - H2O - CO2
pos 960.51593 [M+NH4]+; 965.47021 [M+Na]+ 463.14227: C17H27O13Na
50 quercetin c C15H10O7 16.4 neg 301.03538 271.02539; 178.99774; 151.00273; 121.02832 271.02539: C14H8O6; 178.99774: C8H4O5; 151.00273: C7H4O4; 121.02832: C7H6O2 255; 372
pos 303.04993 285.03964; 257.04440; 229.04947; 201.05476; 165.01811; 153.01846; 137.02357 285.03964: C15H8O6; 257.04440: C14H8O5; 229.04947: C13H8O4; 201.05476: C12H8O3; 165.01811: C8H4O4; 153.01846: C7H4O4; 137.02357: C7H4O3
51 acetylated medicagenic acid + one hexosyl + two deoxyhexosyl + one pentosyl + one glucuronic acid moietye C61H94O30 16.76 neg 652.28625 [M-2H]2−; 1305.57764 439.32321; 585.20691 439.32321: C29H43O3; 585.20691: C5H8O4 + 2C6H10O4 + C6H10O5
pos 1329.57288 [M+Na]+; 1324.61719 [M+NH4]+ -
52 naringenin c C15H12O5 16.8 neg 271.06120 253.05069 253.05069: C15H10O4
pos 273.07575 -
53 apigenin c C15H10O5 17.73 neg 269.04555 225.05510; 151.00255; 117.03339 225.05510: C14H10O3; 151.00255: C7H4O4
pos 271.06010 153.01845 153.01845: C7H4O4
54 isorhamnetin c C16H12O7 17.87 neg 315.05103 300.02762; 271.02399; 243.02707; 216.04128; 164.01071; 151.00258 300.02762: C15H9O7
pos 317.06555 302.04205; 285.03882; 153.01846 153.01846: C7H4O4
55 luteolin c C15H10O6 18.09 neg 285.04046 199.03967; 151.00212; 133.02821 199.03967: C12H8O3; 151.00212: C7H4O4; 133.02821: C8H6O2
pos 287.05501 153.01787; 135.04414 153.01787: C7H4O4; 135.04414: C8H6O2
56 kaempferol c C15H10O6 18.09 neg 285.04046 - 265; 364
pos 287.05501 258.05115; 231.06519; 165.01807; 153.01816; 121.02866 258.05115: C14H9O5; 231.06519: C13H10O4; 165.01807: C8H4O4; 153.01816: C7H4O4; 121.02866: C7H4O2
57 miquelianin [quercetin 3-O-glucuronide] c C21H18O13 12.89–13.49 neg 477.0675 301.03552; 271.02505; 255.03020;178.99788; 151.00258 257; 357
pos 479.0824 303.04993; 257.04370
58 herniariasaponin G C53H84O24 14.61 neg 1103.52829; 574.26304 [M-2H+FA]− 821.43842; 501.32306; 439.32156 821.43842: C36H70O20; 501.32306: C30H46O6; 439.32156: C30H46O6 -H2O - CO2 van Dooren et al. (2016)
pos 1127.52344 [M+Na]+; 1122.56841 [M+NH4]+; 811.44629; 503.33636; 457.33087 973.50128; 811.45264; 649.39624; 503.33704; 457.33188 811.44629: C53H84O24 - C5H8O4 - C6H10O5; 503.33636: C30H46O6; 973.50128: C53H84O24 - C5H8O4; 649.39624: C53H84O24 - C5H8O4 - 2C6H10O5
59 medicagenic acid + two hexosyl + two deoxyhexosyl + two pentosyl + one glucuronic acid moiety e C70H110O38 14.89–15.38 neg 1557.6595; 1411.60317 1235.56738; 983.57922; 796.23248; 439.32043 1411.60317: C70H110O38 - C6H10O4
pos 1581.65795 [M+Na]+ 1259.56189; 741.24219; 595.18250; 445.13116
60 medicagenic acid + one hexosyl + two deoxyhexosyl + two pentosyl + one glucuronic acid moiety e C64H100O33 14.92–15.67 neg 1395.6069 1219.583
pos - -
61 herniariasaponin H d C70H110O37 15.12; 15.66; 15.72 neg 1541.6657 1446.38293; 1219.58069; 823.41711; 501.32587 1219.58069: C70H110O37 - C5H8O4 - C6H8O6; 823.41711: C70H110O37 - C6H10O5 - 2C5H8O4 - 2C6H10O4; 501.32587: C30H46O6 van Dooren et al. (2016)
pos 1565.66118 [M+Na]+; 1560.70778 [M+NH4]+ 1243.57349; 905.31189; 741.24255
62 chlorogenic acid d C16H18O9 7.31; 8.88 neg 353.08685 191.05544; 179.03427; 173.04494 191.05544: C7H12O6; 179.03427: C9H8O4; 173.04494: C7H12O6 - H2O
pos 355.1016; 377.08360 [M+Na]+ 163.03915; 145.02861; 135.04443 163.03915: C9H8O4 - H2O; 145.02861: C9H8O4 - 2H2O; 135.04443: C8H8O2
63 1-O-feruloylquinic acid d C17H20O9 9.20–10.62 neg 367.10349; 435.09108 [M-H+NaFA]− 193.05003; 173.04485; 134.03622 Jaiswal et al. (2011)
pos 369.11748; 391.09949 [M+Na]+ 145.02855; 149.05952; 117.03381; 177.05475; 194.05750

a If not specified otherwise: tentative identification based on accurate mass b Deprotonated and protonated molecules in negative and positive mode, respectively, unless stated otherwise c Identification with an analytical standard d Tentatively identified compound or an isomer e Tentative identification of saponins that have never been reported before in H. hirsuta.