Table 2.

Metabolites identified in different organs of S. marianum extracts using UPLC-MS in negative ionization mode

No.	Rt (min.)	[M-H]−	Element composition	MSn ions m/z (-)	Identified compounds	Chemical class	Structure	Reference
1	1.36	331.25	C13H16O10	169.11, 125.11	Gallic acid hexoside	Phenolic acid glycoside		Li et al. 2003 [53]
2	1.57	327.26	C14H16O9	312.23, 192.13, 164.12	Bergenin	Phenolic acid glycoside		Li et al. 2013 [54]
3	1.69	341.29	C15H18O9	179.15, 135.15	Caffeic acid-O-hexoside	Phenolic acid glycoside		Singh et al. 2016 [55]
4	1.81	191.16	C7H12O6	147.16	Quinic acid	Phenolic acid		Haşimi et al. 2017 [56]
5	2.01	153.11	C7H6O4	109.11	Protocatechuic acid	Phenolic acid		Haşimi et al. 2017 [56]
6	2.32	167.14	C8H8O4	152.11, 123.14	Vanillic acid	Phenolic acid		Haşimi et al. 2017 [56]
7	2.48	197.17	C9H10O5	182.14, 153.17	Syringic acid	Phenolic acid		Haşimi et al. 2017 [56]
8	2.66	179.15	C9H8O4	135.15	Caffeic acida	Phenolic acid		Haşimi et al. 2017 [56]
9	7.91	163.15	C9H8O3	119.15	p-Coumaric acid	Phenolic acid		Haşimi et al. 2017 [56]
10	8.70	193.18	C10H10O4	178.15, 149.18	Ferulic acid	Phenolic acid		Haşimi et al. 2017 [56]
11	9.98	147.15	C9H8O2	103.15	Cinnamic acid	Unsaturated carboxylic acid		Haşimi et al. 2017 [56]
12	10.14	353.3	C16H18O9	179.15, 191.16	Chlorogenic acid	Phenolic acid		Haşimi et al. 2017 [56]
13	10.85	275.28	C15H16O5	201.25	Ursinoic acid	Terpenoid		Hines et al. 2017 [57]
14	11.01	133.08	C4H6O5	115.06 71.06	Malic acida	Dicarboxylic acid		Al Kadhi et al. 2017 [58]
15	11.12	115.06	C4H4O4	71.06	Fumaric acid	Dicarboxylic acid		Al Kadhi et al. 2017 [58]
16	11.74	607.49	C27H28O16	313, 295, 285.23, 151.1, 133.12	Kaempferol 3,7-dihexoside	Flavonoid		Said et al. 2017 [59]
17	12.18	609.51	C27H30O16	301.23, 272.21, 255.2, 151.1	Rutin	Flavonoid		Kumar et al. 2017 [60]
18	12.22	593.5113	C27H30O15	269.23, 151.1, 117.13	Apigenin 7-dihexoside	Flavonoid		Liu et al. 2010 [61]
19	12.31	623.54	C28H32O16	315.26, 300.22, 271.2, 151.1	Isorhamnetin-3-O-dihexoside	Flavonoid		Krasteva and Nikolov, 2008 [62]
20	12.39	579.53	C27H32O14	271.25, 151.1, 119.14, 107.09	Naringin	Flavonoid		Santoro et al. 2020 [63]
21	12.45	325.29	C15H18O8	163.15, 119.14	Coumaroyl hexoside	Phenolic acid glycoside		Li et al. 2003 [53]
22	12.51	491.38	C22H20O13	315.26, 300.22, 271.2, 151.1	Isorhamnetin-3-O-hexuronide	Flavonoid		Krasteva and Nikolov, 2008 [62]
23	12.71	447.37	C21H20O11	285.23, 151.1, 133.12	Luteolin-7-O-hexoside	Flavonoid		Santoro et al. 2020 [63]
24	12.80	477.4	C22H22O12	325, 315.26, 300.22, 271.2, 151.1	Isorhamnetin-3-O-hexoside	Flavonoid		Krasteva and Nikolov, 2008 [62]
25	12.89	431.37	C21H20O10	269.23, 151.1, 117.13	Apigenin-7-O-hexoside	Flavonoid		Liu et al. 2010 [61]
26	13.20	432.38	C21H21O10+	286.24, 151.1, 135.1	Cyanidin-3-O-deoxyhexoside	Flavonoid		Santoro et al. 2020 [63]
27	13.47	433.39	C21H22O10	271.25, 151.1, 119.14, 107.09	Naringenin 7-O- hexoside	Flavonoid		Santoro et al. 2020 [63]
28	13.53	457.36	C22H18O11	125.1, 169.11	(-)-Epigallocatechin gallate	Flavonoid gallic acid ester		Spáčil et al. 2010 [64]
29	13.91	461.40	C22H22O11	285.23, 151.1, 133.12	Rhamnocitrin-O-hexoside	Flavonoid		Said et al. 2017 [59]
30	14.21	415.37	C21H20O9	253.23, 135.1, 117.13	Daidzein-7-O-hexoside	Flavonoid		Santoro et al. 2020 [63]
31	14.44	441.37	C22H18O10	125.1, 109.1, 169.11	Catechin gallate	Flavonoid gallic acid ester		Spáčil et al. 2010 [64]
32	14.95	445.4	C22H22O10	283.26, 268.23, 224.23	Trifolirhizin	pterocarpanoid glycoside		Ye et al. 2012 [65]
33	15.10	473.41	C23H22O11	269.23, 151.1, 117.13	Apigenin 7- hexuronide, Et ester	Flavonoid		Liu et al. 2010 [61]
34	15.33	429.4	C22H22O9	267.26, 132.16, 135.1	Ononin	Flavonoid		Santoro et al. 2020 [63]
35	15.48	519.52	C26H32O11	357.38, 339.36, 221.23, 191.2	Dehydrodiconiferyl alcohol-hexoside	Neolignan		Letourneau and Volmer, 2021 [66]
36	15.54	161.13	C9H6O3	133.12	4-Hydroxycoumarin	Coumarin derivative		Ren et al. 2016 [67]
37	15.62	145.14	C9H6O2	117.13	Coumarina	O-hydroxycinnamic acid (Aromatic compound)		Ren et al. 2016 [67]
38	15.80	149.17	C9H10O2	131.15	p-Coumaryl alcohola	Monolignol		Liu et al. 2010 [61]
39	15.89	175.16	C10H8O3	147.15	4-Methylumbelliferone	Coumarin derivative		Ren et al. 2016 [67]
40	15.99	181.21	C10H14O3	163.19	2-Hydroxymethyl-5-(2-hydroxypropan-2-yl) phenol	Aromatic compound		Dictionary of Natural Products 30.2 Chemical Search
41	16.09	181.21	C10H14O3	163.19	p-Mentha-1,3,5-triene-2,7,8-triol	Aromatic compound		Dictionary of Natural Products 30.2 Chemical Search
42	16.13	217.2	C12H10O4	175.16	4-Methylumbelliferyl acetate	Coumarin derivative		Leonart et al. 2017 [68]
43	16.31	301.23	C15H10O7	272.21, 255.2, 151.1	Quercetina	Flavonoid		Kumar et al. 2017 [60]
44	16.43	303.24	C15H12O7	285.22, 275.23, 151.1, 125, 175	Taxifolin (Dihydroquercetin)	Flavonoid		Chen et al. 2016 [69]
45	16.56	305.26	C15H14O7	125.1	Epigallocatechin	Flavonoid		Spáčil et al. 2010 [64]
46	16.61	285.23	C15H10O6	151.1, 133.12	Kaempferol	Flavonoid		Said et al. 2017 [59]
47	16.70	287.24	C15H12O6	151.1, 135.14	Dihydrokaempferol (Aromadendrin)	Flavonoid		Said et al. 2017 [59]
48	16.77	315.26	C16H12O7	300.22, 271.2, 151.1	Isorhamnetin	Flavonoid		Krasteva and Nikolov, 2008 [62]
49	16.89	269.23	C15H10O5	151.1, 117.13	Apigenin	Flavonoid		Liu et al. 2010 [61]
50	17.10	269.23	C15H10O5	241.22, 225.23	Genistein	Flavonoid		Ye et al. 2012 [65]
51	18.38	271.25	C15H12O5	151.1, 119.14, 107.09	Naringenin	Flavonoid		Santoro et al. 2020 [63]
52	19.27	273.26	C15H14O5	151.1, 121.16	Phloretin	Chalcone derivative		Bystrom et al. 2008 [70]
53	20.13	329.28	C17H14O7	314.25, 299.22, 271.21	Tricin	Flavonoid		Kang et al. 2016 [71]
54	20.63	283.26	C16H12O5	269.23, 151.1, 117.13	Genkwanin (7-methoxyapigenin)	Flavonoid		Liu et al. 2010 [61]
55	23.55	239.25	C15H12O3	130.14, 102.13	2’,4’-Dihydroxychalcone	Chalcone derivative		Zhang et al. 2014 [72]
56	23.87	207.25	C15H12O	130.14, 102.13	Chalcone	α,β-unsaturated ketone		Motiur Rahman et al. 2013 [73]
57	24.93	497.43	C25H22O11	463, 453, 179, 125, 480, 470, 375, 355	Silyamandin	Flavonolignan		Csupor et al. 2016 [74]
58	24.99	479.41	C25H20O10	151, 451.1, 255.03, 466.09	2,3-Dehydrosilybin	Flavonolignan		Csupor et al. 2016 [74]
59	25.05	481.43	C25H22O10	463, 453, 179, 125, 433, 423, 355, 337, 325	Silychristin	Flavonolignan		Csupor et al. 2016 [74]
60	25.23	481.43	C25H22O10	463, 453, 179, 125, 409, 151, 301	Silydianin	Flavonolignan		Csupor et al. 2016 [74]
61	25.47	481.43	C25H22O10	463, 453, 179, 125, 435, 301, 283, 273, 257, 423	Silybin A	Flavonolignan		Csupor et al. 2016 [74]
62	25.69	481.43	C25H22O10	463, 453, 179, 125, 435, 301, 283, 273, 257, 423	Silybin B	Flavonolignan		Csupor et al. 2016 [74]
63	25.81	481.43	C25H22O10	463, 453, 179, 125, 435, 301, 283, 273, 257	Isosilybin A	Flavonolignan		Csupor et al. 2016 [74]
64	25.99	481.43	C25H22O10	463, 453, 179, 125, 435, 301, 283, 273, 257	Isosilybin B	Flavonolignan		Csupor et al. 2016 [74]
65	26.05	323.36	C20H20O4	201.24	Glabridin	Flavonoid		Aoki et al. 2005 [75]
66	26.15	465.43	C25H22O9	151	Silandrin	Flavonolignan		Csupor et al. 2016 [74]
67	26.28	407.48	C25H28O5	119.14, 287.33	6,8-Diprenylnaringenin	Prenyl flavonoid		Nikolic and van Breemen, 2012 [76]
68	26.35	633.88	C37H62O8	471.74, 357.55, 339.53	24-Methylenelanost-8-ene-3,25,28-triol, 3-O-hexoside	Lanostane triterpenoid		Wu et al. 2011 [77]
69	26.41	483.66	C30H44O5	465.64, 421.64	Silymin A	Ursane triterpenoid		Ahmed et al. 2007 [78]
70	26.46	469.72	C31H50O3	371.53, 353.51	3,25-Dihydroxy-24-methylenelanost-8-en-7-one	Lanostane triterpenoid		Wu et al. 2011 [77]
71	26.50	179.19	C13H8O	151.18, 137.15	12-Tridecene-4,6,8,10-tetraynal	Unsaturated fatty aldehyde		Suzuki et al. 1980 [79]
72	26.58	179.19	C13H8O	164.16, 149.13	1,3-Tridecadiene-5,7,9,11-tetrayne, 1,2-epoxide	Unsaturated fatty epoxide		Suzuki et al. 1980 [79]
73	26.63	291.41	C18H28O3	273.39, 247.4	12-oxo-phytodienoic acid	Unsaturated fatty acid		Brenna, 2013 [80]
74	26.70	277.42	C18H30O2	259.4, 233.41	Linolenic acid	Unsaturated fatty acid		Brenna, 2013 [80]
75	26.74	279.44	C18H32O2	261.42, 235.43	Linoleic acida	Unsaturated fatty acid		Brenna, 2013 [80]
76	26.83	281.45	C18H34O2	263.43, 237.44	Oleic acid	Unsaturated fatty acid		Brenna, 2013 [80]
77	26.88	241.35	C17H22O	223.33, 226.32	2,9,16-Heptadecatriene-4,6-diyn-8-ol	Unsaturated aliphatic alcohol		El Sayed et al. 2020 [81]
78	27.03	309.51	C20H38O2	291.49, 265.5	Gadoleic acid	Unsaturated fatty acid		Brenna, 2013 [80]
79	27.14	293.46	C19H34O2	262.43, 221.4, 81.14	Linoleic acid methyl ester	Unsaturated fatty acid methyl ester		Fagerquist et al. 1999 [82]; Härtig, 2008 [83]
80	27.18	295.48	C19H36O2	264.45, 221.4, 55.1	16-octadecenoic acid methyl ester	Unsaturated fatty acid methyl ester		Fagerquist et al. 1999 [82]; Härtig, 2008 [83]
81	27.24	227.36	C14H28O2	209.34, 183.35	Myristic acid	Saturated fatty acid		Brenna, 2013 [80]
82	27.32	255.42	C16H32O2	237.4, 211.41	Palmitic acid	Saturated fatty acid		Brenna, 2013 [80]
83	27.41	283.47	C18H36O2	265.45, 239.46	Stearic acid	Saturated fatty acid		Brenna, 2013 [80]
84	27.51	311.52	C20H40O2	293.5, 267.51	Arachidic acid	Saturated fatty acid		Brenna, 2013 [80]
85	27.66	339.58	C22H44O2	321.56, 295.57	Behenic acid	Saturated fatty acid		Brenna, 2013 [80]
86	27.88	295.52	C20H40O	277.5, 71.14	Phytol	Acyclic diterpene alcohol		El Sayed et al. 2020 [81]
87	28.30	409.63	C28H42O2	394.6, 379.57, 151.19	(R)-gamma-Tocotrienol	Fat soluble vitamin		Zhao et al. 2010 [84]

^aThe standards used for retention times comparison and semi-quantitation of the annotated compounds were caffeic acid, malic acid, quercetin, coumarin, p-coumaryl alcohol, lanosterol, and linoleic acid