Table 1.

(Poly)phenolic compounds in rosemary extract identified by ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MSⁿ) in negative ionization mode under different mass spectrometry (MS) 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	Ident. d
1	Caffeic acid	6.82	179	135		x	x	Std
2	Medioresinol	7.18	387	207 b, 163, 369	163	x	x	[4,12]
3	p-Coumaric acid	7.93	163	119	119	x	x	[4]
4	Luteolin-rutinoside	8.78	593	285	285, 241, 175, 199, 217	x	-	[4,22]
5	Luteolin-hexoside	8.98	447	285, 378	285, 241, 267, 199, 175	x	x	[4]
6	Isorhamnetin-3-O-hexoside	9.28	477	315, 300, 357, 462	300	x	x	[4]
7	4-hydroxybenzoic acid	9.47	137	93, 137		x	x	[4]
8	Apigenin-7-O-glucoside	9.82	431	269	225, 149, 201, 183, 281	x	x	[23]
9	Hesperidin (Hesperetin-7-O-rutinoside)	9.87	609	301	286, 242, 257, 283, 125	x	x	Std
10	Homoplantaginin (Hispidulin 7-glucoside)	10.04	461	299, 446, 284, 341	284, 255, 179	x	x	[3]
11	Rosmarinic acid	10.11	359	161, 179, 197, 223	161, 133	x	x	Std
12	Luteolin-7-O-glucuronide	10.28	461	285	241, 217, 175, 199	x	x	[4]
13	Dihydroxy-dimethoxyflavone derivative	10.33	387	313, 343	298	x	-	[4,24]
14	Dihydroxy-dimethoxyflavone	10.71	313	298	269, 283, 297, 280	x	-	[4,24]
15	Medioresinol derivative	11.22	593	387, 561, 519	207, 163, 369	x	x	[12]
16	Dihydroxy-dimethoxyflavone	11.24	313	298	283, 297, 269, 150	x	-	[4,24]
17	Luteolin-3′-acetyl-O-glucuronide	11.25	503	285, 399, 443	241, 243, 217, 199, 175	x	x	[13,23]
18	Medioresinol-glucuronide	11.37	563	387, 531, 489	207, 163, 369	x	x	[12]
19	Eriodictyol	11.46	287	151	107	x	x	[25]
20	Isorhamnetin-rutinoside	11.51	623	315, 300	300	x	x	[4,22]
21	Luteolin	11.75	285	285, 241, 199, 217, 257, 151, 179, 213		x	x	[4,22,26]
22	Isorhamnetin	11.91	315	300, 301, 287	300, 216, 228, 256, 272	x	x	[4,22]
23	Trihydroxy-methoxyflavone	11.98	299	284	283, 227, 256, 212, 200	x	x	[3,27]
24	Methyl rosmarinate	12.36	373	179, 135, 305	135	x	x	[26]
25	Apigenin-7-O-rutinoside	12.58	577	269, 307	269, 225, 201, 181, 149	x	x	[4,22]
26	Apigenin	13.02	269	269, 225, 149, 201, 183	181, 197, 169, 224	x	x	[4,22]
27	Hispidulin-rutinoside	13.21	607	299, 284, 269, 323	284	x	-	[3,27]
28	Hesperetin	13.41	301	286, 242, 257, 283, 125	258, 242, 199, 174, 215	x	x	[28]
29	5,6,7,10-tetrahydro-7-hydroxy rosmariquinone derivative	14.88	345	301	301, 258, 283, 273, 217	x	x	[14]
30	Cirsimaritin	14.98	313	298	283, 297, 269	x	x	[4,12]
31	Carnosol methyl ether isomer	15.35	343	328, 299	313, 299, 285	x	x	[14]
32	Rosmanol	15.46	345	283, 301, 327	268, 240, 227, 265, 239	x	x	Std
33	Rosmadial isomer or rosmanol quinone	15.97	343	299, 315	284, 243, 213, 256, 281	x	x	[3,4,13]
34	Rosmanol isomer (epirosmanol)	16.22	345	283, 301, 327	268, 227, 240, 239, 265	x	x	[3]
35	Carnosol quinone	16.27	327	299, 258	284, 271	x	x	[29]
36	Isosakuranetin	16.44	285	270, 229, 214, 201, 242		x	x	[25]
37	Genkwanin	16.45	283	268	268	x	x	[3,4]
38	Carnosic acid hexoside	16.76	493	331, 373, 313, 179	287, 244	x	x	Std
39	Rosmanol isomer (epiisorosmanol)	17.18	345	301	301, 286	x	x	[12]
40	5,6,7,10-tetrahydro-7-hydroxy rosmariquinone derivative	17.41	345	301	301, 258, 283, 273, 217	x	x	[14]
41	Carnosol methyl ether isomer	17.78	343	299, 328, 285, 343, 315	284, 243, 281, 299, 256	x	x	[14]
42	Carnosol methyl ether isomer	17.99	343	328, 313, 343, 299, 285	313, 300, 285, 257	x	x	[14]
43	Carnosic acid derivative	18.15	455	331, 287	287, 244	x	x	Std
44	Rosmanol methyl ether	18.59	359	283, 329, 300	268, 240, 227, 265, 239	x	-	[14]
45	Rosmadial or rosmanol quinone	18.62	343	299	243, 216, 284	x	x	[14]
46	Epiisorosmanol methyl ether	18.79	359	315	300	x	-	[14]
47	Rosmanol methyl ether isomer	18.96	359	283, 329, 300	268, 240, 227, 265, 239	x	x	[14]
48	Carnosol	19.07	329	285	270, 285, 269, 201, 214	x	x	Std
49	Carnosic acid quinone	19.51	329	285	270, 285, 201, 227	x	x	[30]
50	4′-Methoxytectochrysin	19.76	297	282, 269, 297, 254	267, 281, 238	x	x	[20]
51	Rosmadial	19.87	343	315, 299	287, 269, 297	x	x	[3,4,13]
52	Rosmaridiphenol	20.09	315	285, 179, 135	285, 214, 201, 270	x	x	[3,31]
53	5,6,7,10-tetrahydro-7-hydroxy rosmariquinone	20.37	301	258, 283, 273, 217, 233	243, 257, 188, 215, 162	x	x	[14]
54	Carnosic acid	20.85	331	287	287, 244, 272, 217	x	x	Std
55	12-O-Methylcarnosic acid	21.87	345	301, 286	286	x	x	Std
56	Carnosol isomer	21.88	329	329, 314, 299, 285		x	x	[31]
57	Betulinic acid	23.71	455.5	327, 317, 353, 409, 437		x	x	Std

^a Fragment ions are listed in order of relative abundance; ^b MS² ions in bold were those subjected to MS³ fragmentation; ^c Exp. 1, detected under experimental condition 1 (carnosol), Exp. 2, experimental condition 2 (rosmarinic acid); ^d Ident., identification mode: [Reference] or Std (standard, compound identified by comparison of its retention time and MS data with that of a reference compound). Some compounds were defined as “derivatives” since parts of their spectra match those of their corresponding parent compounds but they cannot be fully elucidated.