Table 1.

The identified compounds in E6 extract from Achillea biebersteinii using an HPLC-ESI-Q-TOF-MS/MS (Rt = retention time, Delta = difference between experimental and calculated mass (mmu), DBE = double bond equivalents).

No.	Ionization Mode	Rt [min]	Molecular Formula	m/z Experimental	m/z Calculated	Delta [ppm]	DBE	Tentative Identification	MS/MS Fragments	Ref. **	Fraction No.
1	[M − H]−	6.9	C5H8O4	131.035	131.0350	−0.13	2	Glutaric acid	88,113		12
2	[M − H]−	7.0	C15H18O3	245.0465	245.1183	1.29	7	Achillin	211,179,171,101	[28]
3	[M − H]−	7.1	C6H12O7	195.051	195.0510	0.13	1	Gluconic acid	59,71,129		12
4	[M − H]−	7.5	C7H12O6	191.0561	191.0561	0.006	2	Quinic acid	85,173,111	[26,29]
5	[M − H]−	7.8	C9H8O4	179.0343	179.0350	3.79	6	Caffeic acid *	136	comparison with a standard, [13,27,30,31]
6	[M − H]−	8.0	C16H18O8	337.0923	337.0929	10.33	8	Coumaroyl-quinic acid Isomers		[14]
7	[M − H]−	8.3	C4H5O5	133.0138	133.0142	3.33	2	Malic acid	115, 89, 71
8	[M − H]−	8.7	C6H8O7	191.0193	191.0197	2.22		Isocitric acid	173, 129,111,87
9	[M − H]−	11.0	C6H8O7	191.0190	191.0197	3.78		Citric acid	129, 111, 87
10	[M − H]−	12.4	C4H6O4	117.0193	117.0195	−1.42	2	Succinic acid	73,99,67		12
11	[M − H]−	14.5	C7H10O5	173.0455	173.0451	2.57	3	Shikimic acid	85,111,129		12
12	[M − H]−	14.6	C16H18O10	369.0819	369.0827	2.22	8	Fraxetin-8-O-glucoside	173,304,129,111		25,27
13	[M − H]−	15.0	C13H16O9	315.0704	315.0722	5.55	6	Protocatechuic acid glucoside	153,161,109		12
14	[M − H]−	15.3	C16H18O9	353.0867	353.0878	0.58	8	3-Caffeoylquinic acid *	191,173	comparison with a standard [13,14,31]	12
15	[M − H]−	15.2	C15H18O9	341.0886	341.0878	−2.32	7	Caffeoylglucoside (Isomer I)	251, 203, 179, 161	[32]	27
16	[M − H]−	15.7	C15H18O9	341.0899	341.0878	−6.12	7	Caffeoylglucoside (Isomer II)	281, 251, 179, 161	[32]	27
17	[M − H]−	15.8	C26H28O14	563.1401	563.1406	0.94	13	Schaftoside or isoschaftoside	353,191	[28,33]	25,27
18	[M − H]−	15.85	C16H18O9	353.0864	353.0878	0.02	8	5-Caffeoylquinic acid *	191,173	comparison with a standard [13,14,31]	12
19	[M − H]−	16.2	C16H18O9	353.0868	353.0878	2.84	8	4-Caffeoylquinic acid *	191,173	comparison with a standard [13,14,31]	12
20	[M − H]−	16.6	C21H20O12	477.0674	477.0675	0.13	13	Quercetin-O- glucopyranose	301,255,178,151		25
21	[M − H]−	16.9	C25H24O12	515.1178	515.1195	5.23	14	1,3-Dicaffeoylquinic acid (cynarin) *	353	comparison with a standard [13,14,31]	25,27
22	[M − H]−	17.9	C17H26O4	293.1768	293.1758	−3.29	5	Gmelinin B	111,193,163		25,27
23	[M − H]−	18.1	C15H10O6	285.0398	285.0405	2.31	11	Kaempferol	113,137	[14,26,27]
24	[M − H]−	18.2	C14H6O8	300.9959	300.999	10.23	12	Ellagic acid	129, 179, 151,
25	[M − H]−	18.3	C10H10O4	193.0536	193.0506	−15.29	6	Ferulic acid	161, 134	comparison with a standard [26,27,31]	25,27
26	[M − H]−	18.5	C17H14O8	345.0609	345.0616	4.6	11	Axillarin	315,287,129,81	[28]
27	[M − H]−	19.7	C18H16O8	359.0772	359.0772	0.67	11	Jaceidin	301,258,286,344, 329	[28]
28	[M + H]+	15.8	C21H20O10	433.2009	433.1129	2.58	12	Isovitexin	428,367	[28]
29	[M + H]+	17.9	C15H10O5	271.0601	271.0601	0	11	Apigenin		[27,29,30,31]

* indicates compounds previously identified in A. biebersteinii extract; ** compounds previously identified in Achillea species.