Table 1.

Non-saponin compounds identified and quantified in Herniaria glabra (HG), H. polygama (HP), H. incana herb (HIh) purified extracts using UHPLC-QTOF-MS/MS.

	tR (min)	Compound	Neutral Formula	Mode	m/z	Δ *	Mσ **	Major Fragments (%)	HG,%	HP,%	HIh,%	Ref
1	1.89	3-CQA (Neochlorogenic acid)	C16H18O9	[M − H]− [2M − H]−	353.0872 707.1820	1.6 0.9	1.5 1.3	191.0558 (100) (C7H11O6), 179.0342 (80.5) (C9H7O4), 173.0342 (3.5) (C7H9O5), 161.0236 (4.8) (C9H5O3), 135.0439 (14.1) (C8H7O2)	_	_	1.27	[15]
2	2.56	Cis-3-pCoQA	C16H18O8	[M − H]− [2M − H]−	337.0923 675.1926	1.6 0.74	6.8 9.3	191.0559 (7.1) (C7H11O6), 173.0453 (4.1) (C7H9O5), 163.0390 (100) (C9H7O3), 155.0336 (2.3) (C7H7O4), 119.0487 (8.6) (C8H7O)	_	_	1.51	[15]
3	2.64	Trans-3-pCoQA	C16H18O8	[M − H]− [2M − H]−	337.0921 675.1919	2.5 1.8	4.3 8.6	191.0558 (37.6) (C7H11O6), 173.0449 (4.4) (C7H9O5), 163.0392 (100) (C9H7O3), 155.0343 (2.0) (C7H7O4), 119.0489 (9.2) (C8H7O)	_	_	0.31	[15]
4	2.81	a 5-CQA (Chlorogenic acid)	C16H18O9	[M − H]− [2M − H]−	353.0871 707.1822	0.7 1.0	1.9 23.5	191.0556 (100) (C7H11O6), 161.0244 (1.53) (C9H5O3)	_	TA	1.37	[15]
5	2.99	pCoA-4-O-hexoside	C15H18O8	[M − H]− [2M − H]−	325.0923 651.1925	1.8 0.8	9.7 11.4	163.0393 (100) (C9H7O3), 119.0490 (12.6) (C8H7O)	TA	TA	0.12	[15]
6	3.05	a 4-CQA (Cryptochlorogenic acid)	C16H18O9	[M − H]− [2M − H]−	353.0874 707.1829	1.2 −0.1	3.6 15.3	191.0552 (40.4) (C7H11O6), 179.0343 (84.5) (C9H7O4), 173.0446 (100) (C7H9O5), 161.0231 (2.7) (C9H5O3), 155.0330 (5.3) (C7H7O4), 135.0441 (13.9) (C8H7O2)	_	_	0.20	[15]
7	3.21	Cis-3-FerQA	C17H20O9	[M − H]− [2M − H]−	367.1025 735.2128	2.6 1.9	4.0 15.7	193.0500 (100) (C10H9O4), 173.0450 (4.0) (C7H9O5), 155.0343 (1.2) (C7H7O4), 149.0597 (2.0) (C9H9O2), 134.0363 (C8H6O2●) (6.1)	TA	TA	1.24	[15]
8	3.31	Trans-3-FerQA	C17H20O9	[M − H]− [2M − H]−	367.1030 735.2138	1.2 0.6	6.7 36.2	193.0502 (100) (C10H9O4), 173.0445 (5.5) (C7H9O5), 155.0338 (1.0) (C7H7O4), 149.0599 (4.3) (C9H9O2), 134.0365 (11.8) (C8H6O2●)	_	_	0.16	[15]
9	3.72	# Licoagroside B (maltol-3-O-[HMG-(1→6)]-β-glucoside)	C18H24O12	[M − H]− [2M − H]−	431.1189 863.2463	1.3 0.9	4.3 7.2	161.0448 (10) (C6H9O5), 125.0232 (100) (C6H5O3)	1.80	1.33	1.10	[14]
10	3.81	# (2R,3R)-Benzoyl-tartaric acid	C11H10O7	[M − H]−	253.0340	5.4	6.8	130.9969 (26.3) (C4H3O5), 121.0277 (100) (C7H5O2)	_	1.01	_	[15]
11	3.87	#Cis-2-hydroxy-4-methoxycinnamic acid 2-O-β-glucoside (cis-GMCA)	C16H20O9	[M − H]−	355.1017	5.2	4.9	193.0494 (100) (C10H9O4), 149.0591 (75.4) (C9H9O2), 134.0367 (5.5) (C8H6O2●)	_	5.76	_	[15]
12	4.70	Trans-4-FerQA	C17H20O9	[M − H]−	367.1028	1.9	4.1	193.0501 (21.3) (C10H9O4), 191.0558 (40.6) (C7H11O6), 173.0455 (100) (C7H9O5), 155.0349 (4.0) (C7H7O4), 134.0372 (2.5) (C8H6O2●)	TA	TA	0.22	[15]
13	4.77	# 3-(2-glucosyloxy-4- methoxyphenyl)propanoic acid (GMPPA)	C16H22O9	[M − H]−	357.1174	4.9	0.7	195.0650 (100) (C10H11O4), 177.0541 (2.8) (C10H9O3), 151.0748 (10.7) (C9H11O2), 136.0512 (1.1) (C8H8O2●)	_	1.07	_	[15]
14	5.41	N-Malonyl-tryptophan	C14H14N2O5	[M + H]+	291.0969	2.3	4.6	273.0868 (19.0) (C14H13N2O4), 245.0916 (100) (C13H13N2O3), 227.0807 (24.9) (C13H11N2O2), 188.0702 (21.9) (C11H10NO2), 130.0647 (18.7) (C9H8N)	_	_	NC	[15]
15	5.52	#Trans-2-hydroxy-4- methoxycinnamic acid 2-O-β-glucoside (trans-GMCA)	C16H20O9	[M − H]−	355.1016	5.3	0.7	193.0494 (100) (C10H9O4), 149.0591 (36.5) (C9H9O2), 134.0357 (4.7) (C8H6O2●)	_	1.58	_	[15]
16	5.60	# Apiorutin (quercetin-3-O-[β-Api-(1→2)]-[α-Rha-(1→6)]-β-glucoside)	C32H38O20	[M − H]−	741.1868	2.1	5.9	609.1461 (0.5) (C27H29O16), 591.1362 (0.3) (C27H27O15), 300.0269 (100) (C15H8O7●), 271.0244 (4.5) (C14H7O6), 255.0299 (2.0) (C14H7O5), 178.9986 (2.0) (C8H3O5), 151.0028 (0.9) (C7H3O4)	1.50	0.33	_	[14]
17	5.83	Kaempferol-3-O-(dHex-(1→2))-[dHex-(1→2)]- hexoside	C33H40O19	[M − H]−	739.2080	1.5	29.0	575.1392 (0.6) (C27H27O14), 284.0316 (100) (C15H8O6●), 255.0291 (7.4) (C14H7O5), 227.0341 (4.5) (C13H7O4), 178.9973 (1.2) (C8H3O5), 151.0024 (1.5) (C7H3O4)	_	_	0.16	[15]
18	6.18	# Rutin (quercetin-3-O-[α-Rha-(1→6)]-β-glucoside)	C27H30O16	[M − H]−	609.1453	1.5	8.3	343.0459 (1.7) (C17H11O8), 300.0268 (100) (C15H8O7●), 255.0299 (1.0) (C14H7O5), 178.9986 (2.9) (C8H3O5), 151.0037 (1.8) (C7H3O4)	1.87	5.27	0.82	[14]
19	6.33	Quercetin-3-O- hexoside	C21H20O12	[M − H]−	463.0874	1.6	4.8	343.0459 (1.4) (C17H11O8), 300.0267 (100) (C15H8O7●), 255.0299 (1.1) (C14H7O5), 178.9965 (1.8) (C8H3O5), 151.0035 (1.5) (C7H3O4)	TA	0.22	0.18
20	6.76	Kaempferol-3-O-[dHex-(1→6)]- hexoside	C27H30O15	[M − H]−	593.1499	1.3	2.1	327.0502 (3.2) (C17H11O7), 285.0389 (53.9) (C15H9O6), 284.0317 (100) (C15H8O6●), 255.0300 (2.9) (C14H7O5), 227.0343 (1.7) (C13H7O4), 151.0035 (2.1) (C7H3O4)	_	_	0.19	[15]
21	6.95	Kaempferol-3-O-hexoside	C21H20O11	[M − H]−	447.0902	2.0	6.5	284.0322 (47.4) (C15H8O6●)	_	_	TA	[15]
22	6.96	Quercetin- 3-O-[HMG]- hexoside	C27H28O16	[M − H]−	607.1219	2.4	7.2	545.1280 (8.0) (C26H25O13), 505.0990 (37.2) (C23H21O13), 463.0874 (47.5) (C21H19O12), 300.0268 (100) (C15H8O7●), 271.0235 (2.9) (C14H7O6), 255.0292 (1.5) (C14H7O5), 178.9978 (3.1) (C8H3O5), 151.0028 (2.6) (C7H3O4)	_	_	TA	[15]
23	7.00	Blumenin isomer (sesquiterpenoid cyclohexanone-hexuronosyl-hexoside)	C25H40O13	[M − H]−	547.2383	1.3	12.3	347.2062 (3.7) (C19H31O7), 209.1529 (1.7) (C13H21O2), 175.0239 (4.3) (C6H7O6), 161.0444 (1.5) (C6H9O5)	_	_	TA	[23]
24	7.17	Kaempferol-3-O-[HMG-(1→3/4)]-[dHex-(1→2)]-hexoside	C33H38O19	[M − H]−	737.1919	2.1	1.5	675.1922 (1.4) (C32H35O16), 635.1602 (5.7) (C29H31O16), 593.1528 (8.1) (C27H29O15), 429.0819 (0.7) (C21H17O10), 284.0317 (100) (C15H8O6●), 255.0293 (4.4) (C14H7O5), 227.0340 (2.0) (C13H7O4), 178.9974 (0.8) (C8H3O5), 151.0027 (0.9) (C7H3O4)	_	_	1.22 $	[15]
25	7.19	Nicotiflorin (kaempferol-3-O-[Rha-(1→6)]-glucoside)	C27H30O15	[M − H]−	593.1501	1.8	4.4	327.0498 (2.4) (C17H11O7), 285.0392 (100) (C15H9O6), 255.0291 (1.9) (C14H7O5), 227.0344 (0.9) (C13H7O4), 151.0027 (1.2) (C7H3O4)	0.44	0.44		[14]
26	7.58	# Narcissin (isorhamnetin-3-O-[α-Rhap-(1→6)]-β-glucoside)	C28H32O16	[M − H]−	623.1603	2.3	5.1	357.0609 (1.5) (C18H13O8), 315.0499 (100) (C16H11O7), 300.0266 (5.9) (C15H8O7●), 271.0244 (1.3) (C14H7O6), 151.0028 (0.7) (C7H3O4)	7.34	5.43	0.96	[14]
27	7.77	4,4′-Dimethoxy-2,2′-di-O-hexoside-truxinate (cyclodimer of GMCA)	C32H40O18	[M − H]−	711.2128	1.9	6. 9	549.1606 (12.9) (C26H29O13), 531.1497 (8.5) (C26H27O12), 369.0973 (51.4) (C20H17O7), 343.1181 (41.6) (C19H19O6), 299.1284 (23.7) (C18H19O4), 271.0970 (92.1), 256.0737 (2.7) (C15H12O4●), 193.0502 (100) (C10H9O4), 149.0599 (41.8) (C9H9O2), 134.0361 (8.2) (C8H6O2●)	_	TA	_	[15]
28	7.80	Kaempferol-3-O-[HMG-(1→3/4)]-hexoside	C27H28O15	[M − H]−	591.1344	1.9	5.6	529.1343 (13.8) (C26H25O12), 489.1031 (39.2) (C23H21O12), 447.0920 (31.8) (C21H19O11), 327.0499 (1.8) (C17H11O7), 284.0318 (100) (C15H8O6●), 255.0282 (1.4) (C14H7O5), 229.0503 (1.1) (C13H9O4), 151.0025 (0.9) (C7H3O4)	_	_	0.25
29	7.81	Isorhamnetin-3-O-hexoside	C22H22O12	[M − H]−	477.1030	1.7	12.8	357.0604 (3.0) (C18H13O8), 314.0422 (100) (C16H10O7●), 299.0195 (1.46) (C15H7O7), 285.0397 (1.3) (C15H9O6), 271.0220 (1.6) (C14H7O6), 151.0034 (2.0) (C7H3O4)	TA	TA	TA
30	9.10	a Herniarin (7-methoxy- coumarin)	C10H8O3	[M + H]+	177.0557	−5.8	1.9	177.0537 (100), 133.0659 (4. 3), 121.0658 (2.9)	_	1.59	_	[15]
31	9.94	# 7-O-Methylquercetin-3-O-[HMG-(1→6)]-[α-Rha-(1→2)]-β-galactoside	C34H40O20	[M − H]−	767.2035	0.7	17.0	705.2059 (0.4) (C33H37O17), 665.1726 (1.8) (C30H33O17), 623.1619 (4.8) (C28H31O16), 314.0429 (100) (C16H10O7●); 299.0196 (13.1) (C15H7O7), 271.0246 (2.4) (C14H7O6), 193.0145 (0.8) (C9H5O5), 165.0189 (1.5) (C8H5O4)	_	_	0.31	[15]
32	10.20	7-O-Methylkaempferol-3-O-[dHex-(1→2)]-hexoside	C28H32O15	[M − H]−	607.1672	−0.6	1.6	298.0484 (100) (C16H10O6●), 283.0248 (10.2) (C15H7O6), 271.0610 (0.9) (C15H11O5), 255.0298 (1.1) (C14H7O5), 165.0190 (0.7) (C8H5O4)	_	_	0.51	[15]
33	10.72	# Oxytroflavoside A (7-O-methylkaempferol-3-O-[HMG-(1→6)]-[α-Rha-(1→2)]-β- galactoside)	C34H40O19	[M − H]−	751.2089	0.3	14.8	649.1772 (2.2) (C30H33O16), 607.1666 (4.4) (C28H31O15), 298.0481 (100) (C16H10O6●), 283.0247 (13.5) (C15H7O6); 271.0610 (0.9) (C15H11O5), 255.0298 (1.7) (C14H7O5), 165.0186 (0.7) (C8H5O4)	_	_	14.73	[15]
34	11.05	# 7-O-Methylkaempferol-3-O-[HMG-(1→6)]-[α-Rha-(1→2)]-β-glucoside	C34H40O19	[M − H]−	751.2090	0.2	4.4	649.1788 (1.4) (C30H33O16), 607.1670 (5.5) (C28H31O15), 298.0483 (100) (C16H10O6●), 283.0247 (13.3) (C15H7O6), 271.0616 (0.8) (C15H11O5), 255.0301 (1.5) (C14H7O5), 165.0188 (0.8) (C8H5O4)	_	_	0.91	[15]
35	11.26	# Oxytroflavoside C (main) (7-O-methylkaempferol-3-O-[HMG-(1→4)]-[α-Rha-(1→2)]-β-galactoside]) Oxytroflavoside B (minor) (7-O-methylkaempferol-3-O-[HMG-(1→3)]-[α-Rha-(1→2)]-β-galactoside)	C34H40O19	[M − H]−	751.2086	0.6	8.1	649.1779 (1.6) (C30H33O16), 607.1676 (8.8) (C28H31O15), 298.0483 (100) (C16H10O6●), 283.0249 (11.2) (C15H7O6), 271.0614 (1.0) (C15H11O5), 255.0303 (1.2) (C14H7O5), 165.0189 (0.7) (C8H5O4)	_	_	1.38 $	[15]
36
37	11.54	7-O-Methyl-kaempferol-3-O-[HMG-(1→3/4)]-hexoside	C28H30O15	[M − H]−	605.1515	−0.5	11.4	543.1516 (8.0) (C27H27O12), 503.1198 (27.1) (C24H23O12), 461.1093 (22.9) (C22H21O11), 341.0663 (1.8) (C18H13O7), 298.0482 (100) (C16H10O6●), 283.0247 (6.2) (C15H7O6); 255.0302 (1.0) (C14H7O5), 165.0192 (1.3) (C8H5O4)	_	_	0.32	[15]
38	11.77	7-O-Methyl-kaempferol-3-O-[dHex-(1→2)]-pentoside	C27H30O14	[M − H]−	577.1565	−0.5	13.5	413.0888 (1.0) (C21H17O9), 298.0490 (100) (C16H10O6●), 283.0250 (7.3) (C15H7O6), 255.0302 (1.0) (C14H7O5), 165.0188 (0.9) (C8H5O4)	_	_	0.12	[15]
		Sum							12.95	24.03	29.56

Notes: ^a Identification with an analytical standard. ^# Isolated and NMR confirmed. * Accuracy of mass measurements expressed in parts per million (ppm). ** Isotopic pattern fit factor (mσ). %—Percentage of a compound in the purified extracts. ^● Anionradical. ^$ Co-eluting peaks. CQA—caffeoylquinic acid; pCoQA—p-coumaroylquinic acid; FerQA—feruloylquinic acid; pCoA—p-coumaric acid; dHex—deoxyhexosyl; Rha—rhamnopyranosyl; Api—apifuranosyl; HMG—3-hydroxy-3-methylglutaryl; TA—trace amount; NC—not calculated; Ref.—references.