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.