Table 1.

Identification of phytochemical compounds by UHPLC-MSⁿ in negative mode under different MS operating conditions.

ID	Compounds	RT (min)	[M − H]− (m/z)	MS2 Ion Fragments (m/z) a	MS3 Ion Fragments (m/z) a	Exp. 1 c	Exp. 2 c	Identification d
1	Quinic acid	0.57	191	173 b, 111, 127, 85, 93	111, 67	x	x	Std
2	l-malic acid	0.67	133	115, 87			x	[12]
3	Citric acid	0.77	191	111, 173	111, 67	x	x	[13]
4	Dihydroxyphenyllactic acid (Danshensu)	2.61	197	179, 73, 153	135	x		[14]
5	Protocatechuic acid hexoside	2.75	315	153, 109, 225	109	x		[15]
6	Dihydroxyphenylacetic acid	3.35	167	123			x	[16]
7	Hydroxybenzoic acid	4.12	137	137, 93			x	[17]
8	Caftaric acid	4.40	311	149, 179, 243, 135	103, 87, 131, 59, 149		x	Std
9	Hydroxyphenyllactic acid	4.47	181	163, 135, 73	119	x	x	[18]
10	Luteolin-8-C-glucoside (orientin)	4.83	447	357, 327				Std
11	3′-Caffeoylquinic (neochlorogenic acid)	4.96	353	191, 179, 135, 173	127, 173, 85, 93		x	Std
12	THDBCHMCA f	5.42	295	163, 113	118		x	[19]
13	Rosmanol	5.44	345	299	179, 119, 143, 113, 161		x	[20]
14	Coumaric acid	5.52	163	119		x		[17]
15	Salvianolic acid F	5.56	313	269, 203, 159	159, 109, 254, 269	x		[14]
16	Dicaffeic acid	5.74	341	281, 251, 179, 221, 323	179, 221, 135	x	x	[21]
17	5′-Caffeoylquinic (chlorogenic acid)	6.17	353	191, 179	127, 173, 85, 83		x	Std
18	Caffeic acid	6.25	179	135	135	x	x	Std
19	Ferulic acid derivative	6.88	489	193, 235, 295, 265	149, 134, 178	x		Std
20	Rosmarinic acid derivative	6.92	377	359	161, 179, 197, 223	x	x	Std
21	Rosmarinic acid derivative	7.08	377	359	161, 179, 197, 223	x	x	Std
22	Feruloylquinic acid	7.15	367	173, 193, 191	93, 111, 155, 71	x	x	[22]
23	Tetrahydroxy-dimethoxyflavone-hexoside	7.29	507	327, 345, 477, 489	312, 167, 295	x		[23]
24	Danshensu derivative	7.40	527	197, 179, 483	179, 73	x		[14]
25	Rosmarinic acid-O-caffeic acid	7.61	539	359, 495, 341, 179	161, 179, 197, 223	x	x	[14]
26	Salvianolic acid J/isomer	7.82	537	339	229, 295	x	x	[14]
27	Salicylic acid	7.85	137	93, 137			x	[17]
28	Rosmarinic acid-rutinoside	7.96	667	359, 487	161, 197, 179, 223	x		Std
29	Quercetin-rutinoside (rutin)	8.07	609	301, 343, 271, 255, 179	179, 151, 257, 273	x	x	Std
30	Salvianolic acid J/isomer	8.08	537	493, 295, 339	295, 313, 383	x	x	[14]
31	Luteolin-rutinoside	8.16	593	285	241, 285, 175, 199, 217	x	x	[24]
32	Rosmarinic acid-O-hexoside	8.25	521	359	161, 197, 179, 223	x	x	Std
33	Luteolin-hexoside	8.26	447	285	285, 241, 199, 175, 217	x		[24]
34	Luteolin-glucuronide	8.3	461	285	285, 241	x	x	[20]
35	Salvianolic acid B/E/isomer	8.43	717	519, 475, 339, 537	475, 339, 365	x	x	[14]
36	Narirutin (Naringenin-7-O-rutinoside)	8.45	625 (579) e	579	271	x	x	Std
37	Salvianolic acid D	8.53	417	373, 175, 273, 399	175, 197, 223		x	[14]
38	Sagerinic acid	8.66	719	359, 539, 521, 341	161, 179, 197, 223	x		[16]
39	Salvianolic acid E	8.78	717	519, 537, 555, 673, 339	339, 321, 295, 229	x	x	[14]
40	Rosmarinic acid	8.86	359	161, 179, 197, 223	161, 133	x	x	Std
41	Sagerinic acid isomer	8.99	719	359	161, 179, 197, 223		x	[25]
42	Salvianolic acid A derivative	9.08	897	493, 295	295, 313, 179		x	Std
43	Lithospermic acid	9.44	537	493, 359	359, 313, 295	x	x	Std
44	Salvianolic acid B	9.61	717	519, 321	321, 339, 279, 197, 179	x	x	Std
45	Dehydro-Rosmarinic acid	9.70	343	161, 179, 135, 223, 197	161, 133	x	x	Std
46	Salvianolic acid B/E/isomer	9.75	717	519, 357, 555, 673, 321	321, 357, 339	x	x	[14]
47	Rosmarinic acid-dihexoside	9.83	683	521	359, 161, 197, 223	x		Std
48	G(8-O-4)5H	9.88	373	179, 161, 135, 355, 197	135, 161	x		[14]
49	Salvianolic acid A	10.02	493	295, 313, 383, 203	159, 277, 109, 267	x	x	Std
50	Acacetin derivative	10.12	637	591, 283	283, 268	x	x	[18]
51	Salvianolic acid A isomer	10.25	493	295, 331, 383	159, 277, 109, 267	x	x	[19]
52	Rosmarinic acid derivative	10.70	551	519, 359, 313	339	x	x	[20]
53	Danshensu derivative	10.87	689	527, 491	197, 179, 347, 161	x	x	[14]
54	Danshensu derivative	10.90	691	529, 493, 511	197, 179, 349, 151	x	x	[14]
55	Danshensu derivative	11.07	689	527	197, 179, 347	x	x	[14]
56	Rosmarinic acid derivative	11.07	691	359, 511, 341, 529	161, 179, 197, 223	x		Std
57	Apigenin	11.17	269	269, 225, 149, 241	181, 197, 225, 183	x		[26]
58	Salvianolic acid A isomer	11.22	493	359, 357, 313	161, 179, 197, 223	x	x	[19]
59	Cyclolariciresinol	11.26	359	345, 161	329, 326	x	x	[27]
60	Salvianolic acid B derivative	11.40	879	519, 699, 339	339	x		[25]
61	Rosmarinic acid derivative	12.33	571	525	341, 359, 161, 179, 221		x	Std
62	Rosmarinic acid derivative	12.69	525	359, 341, 161, 179	161, 179, 197, 223	x		Std
63	Rosmarinic acid derivative	13.04	507	359, 341, 179	161, 179, 197, 223	x	x	Std
64	Rosmarinic acid derivative	13.24	849	359, 687, 669	161, 179, 197, 223	x	x	Std
65	Acacetin	13.54	283	268, 269	268, 269, 240	x	x	[18]
66	Rosmarinic acid derivative	13.82	507	359, 341, 179	161, 179, 197, 223	x	x	Std

^a Fragment ions are listed in order of relative abundances; ^b MS² ions in bold were those subjected to MS³ fragmentation; ^c Exp. 1, detected under experimental condition 1 (epicatechin); Exp. 2, experimental condition 2 (rosmarinic acid); ^d Identification means identification mode: [Reference number] or Std (compound identified by comparing retention times and MS data with those of reference compounds). Some compounds have been considered “derivatives” since parts of their spectra match those of their corresponding parent compounds but they cannot be fully identified; ^e The molecular ion is a formic acid adduct (+46); ^f THDBCHMCA: 1,2,6,7-tetrahydroxy-5H-dibenzo[a,d]cycloheptene-5-methyl-11-carboxylic acid.