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. 2012 Feb 13;158(4):1893–1915. doi: 10.1104/pp.111.192328

Table II. Mass spectral data of flax phenolics.

Phenolic profiling was performed with reverse-phase UHPLC coupled to atmospheric pressure chemical ionization-ion trap-FT-ICR-MS. Accurate m/z values were obtained with FT-ICR-MS, whereas the MS2 and MS3 (in parentheses after the corresponding MS2 in italics) collision-induced dissociation spectra were recorded via ion-trap-MS. The relative abundance of each peak in inner and outer tissues is based on the selected ion current. Shorthand names of oligolignols/(neo)lignans are based on Morreel et al. (2004). p-Hydroxyphenyl, guaiacyl, and syringyl units as well as units derived from 5-hydroxyconiferyl alcohol, ferulic acid, and coniferaldehyde are designated H, G, S, 5H, FA, and G′, respectively. The linkage type is indicated in parentheses. The term “red” indicates reduced unit or adjacent linkage (Morreel et al., 2010a); e.g. Gred(8-8)G or G(8-8)Gred, Gred(8-8)Gred, Gred(8-5)G, and G(8-5)Gred refer to lariciresinol, secoisolariciresinol, isodihydrodehydrodiconiferyl alcohol, and dihydrodehydrodiconiferyl alcohol, respectively. A forward slash indicates that two units or two linkage positions are equally possible at this position in the shorthand name. In this case, the various structures are shown in Figure 3. hex, Hexose or hexoside; tR, retention time; a, intensity based on acetate adduct ion; nd, not detected. ?, MS2 spectrum matches the standard but not the retention time; ??, MS2 spectrum does not fully match that of the suggested compound based on the literature reference. “Compound” refers to the name of the compound: roman text indicates compounds identified for the first time in flax, boldface italic text indicates compounds previously identified in flax. Ref number after a compound name refers to a bibliographic reference for MS data (Supplemental Data S1), F Ref number after a compound name refers to a previous bibliographic reference (Supplemental Data S1) identifying the compound in flax, and S number after a compound name refers to the molecular structures presented in Figure 3. No bibliographic references for the MS data of S numbered compounds were available, and their MS-based structural elucidation is described in Supplemental Data S1. Asterisks indicate compounds described, to our knowledge, for the first time in plants.

tR Relative Abundance Ratio Outer-Inner m/z Formula Δppm m/z MS2 (MS3) Compound (Ref, F Ref, S, *)
Inner Outer
min
4.16 nd 4.5 × 104 Outer 367.10391 C17H19O9 1.24 191 (MS3: 173, 127, 85) Feruloyl quinic acid (Ref 1)
4.50 2.4 × 103 8.5 × 104 36.9 357.11952 C16H21O9 1.16 195 (MS3: 177, 151, 136, 123, 119) Dihydroferulic acid hex (Ref 2)
4.87 2.3 × 106 a 1.0 × 107 a 4.3 311.11488 C15H19O7 4.03 149 (MS3: 131) p-Coumaryl alcohol hex (S 1)
5.61 nd 7.0 × 104 Outer 551.17932 C26H31O13 4.18 389, 341, 193 (MS3: 341, 193, 181, 151) G(8-O-4)FA hex (Ref 3)
5.83 1.1 × 104 5.4 × 105 49.1 551.17898 C26H31O13 3.57 389, 341, 193 (MS3: 341, 193) G(8-O-4)FA hex (Ref 3)
5.86 3.2 × 106 a 1.2 × 107 a 3.8 341.12541 C16H21O8 3.57 179 (MS3: 161, 146) Coniferin (Ref 2, F Ref 1)
5.92 2.2 × 104 8.4 × 105 38.2 551.17745 C26H31O13 0.79 389, 341, 193 (MS3: 341, 193) G(8-O-4)FA hex (Ref 3)
6.71 7.7 × 103 4.6 × 105 59.7 551.17807 C26H31O13 1.91 389, 341, 193 (MS3: 341, 193) G(8-O-4)FA hex (Ref 3)
6.98 5.0 × 103 a 1.8 × 104 a 3.6 431.15684a C19H27O11a 2.21 371, 209 (MS3: 194, 191) Syringin (Ref 2)
7.01 1.3 × 104 8.9 × 104 6.8 537.19884 C26H33O12 2.03 375, 345, 327 (MS3: 345, 327) G(8-O-4)G hex?? (Ref 2, F Ref 2)
7.37 5.6 × 102 5.6 × 104 100 355.10375 C16H19O9 0.83 295, 235, 217, 193, 175 (MS3: 178, 149, 134) Feruloyl hex (Ref 1, F Ref 3)
7.59 1.5 × 103 a 1.7 × 104 a 11.3 401.14582a C18H25O10a 1.25 341, 179 (MS3: 179) Coniferyl alcohol hex? (Ref 2, F Ref 1)
7.88 nd 1.4 × 104 Outer 385.11444 C17H21O10 1.09 325, 265, 247, 223, 205 (MS3: 208, 179, 164) Sinapoyl hex (Ref 1)
8.42 nd 3.4 × 104 Outer 533.16680 C26H29O12 0.66 371, 353, 341 (MS3: 353, 341, 327, 191) G(8-5)FA hex (Ref 2)
8.52 7.8 × 102 1.5 × 104 19.2 389.12484 C20H21O8 1.67 341, 193, 181, 165 (MS3: 178, 149, 134) G(8-O-4)FA (Ref 3)
8.76 5.6 × 104 a 5.8 × 105 a 10.4 537.19854 C26H33O12 1.47 375 (MS3: 327, 195, 165) G(t8-O-4)G hex (Ref 2, F Ref 2)
9.37 nd 2.0 × 104 Outer 355.10379 C16H19O9 0.94 327, 235, 217, 193, 175 (MS3: 178, 149, 134) Feruloyl hex (Ref 1, F Ref 3)
9.37 nd 1.6 × 104 Outer 551.17696 C26H31O13 −0.10 491, 389, 193 (MS3: 341, 193) G(8-O-4)feruloyl hex (Ref 3)
9.66 4.8 × 103 1.3 × 104 2.7 179.07169 C10H11O3 1.80 164, 161, 146 (MS3: 146) Coniferyl alcohol (Ref 1, F Ref 4)
10.91 1.9 × 103 8.9 × 104 46.8 551.17778 C26H31O13 1.39 461, 389, 341, 193 (MS3: 341, 193) G(8-O-4)feruloyl hex (Ref 3)
10.97 8.5 × 103 a 1.8 × 105 21.2 627.23060a C29H39O15a 1.84 567, 405 (MS3: 357, 209, 195, 165) G(8-O-4)S hex (S 2)
11.17 1.1 × 104 1.8 × 105 16.4 537.19789 C26H33O12 0.26 507, 489, 375, 357, 301, 271, 195 G(e8-O-4)G hex (Ref 2, F Ref 2)
11.40 2.1 × 104 3.1 × 105 14.8 523.21976 C26H35O11 2.44 361 (MS3: 346, 313, 179, 165) Secoisolariciresinol hex (S 3)
11.55 8.3 × 103 1.1 × 105 13.4 521.20407 C26H33O11 2.37 359, 329 (MS3: 299, 178) Lariciresinol hex (S 4)
12.00 2.8 × 103 2.3 × 104 8.2 601.23007 C31H37O12 1.70 553, 421, 405, 403, 373, 357, 225, 195 G(8-O-4)S(8-O-4)G (S 5)*
12.18 7.8 × 105 a 4.5 × 106 a 5.8 579.21004a C28H35O13a 2.98 519, 357, 339, 327 (MS3: 324) G(8-5)G hex (Ref 2, F Ref 5, 6)
12.32 1.1 × 103 a 1.8 × 104 a 16.4 595.20322a C28H35O14a −0.02 535, 373, 193 (MS3: 355, 193,179) G(8-O-4)5H hex (Ref 4)
12.43 5.7 × 104 4.3 × 104 0.8 375.14573 C20H23O7 2.14 327, 195, 165 G(t8-O-4)G (Ref 5, F Ref 2)
12.51 1.3 × 104 2.8 × 105 21.5 521.20381 C26H33O11 1.87 359, 329 Lariciresinol hex (S 4)
12.58 2.1 × 104 a 5.6 × 105 a 26.7 581.22511a C28H37O13a 1.97 521, 359, 341, 329 (MS3: 326) IDDDC hex (S 6)
12.69 3.6 × 104 3.1 × 104 0.9 375.14569 C20H23O7 2.04 G(8-O-4)G (Ref 5, F Ref 2)
12.73 2.7 × 103 a 3.2 × 104 11.9 549.19884a C27H33O12a 1.98 489, 327, 309, 297 H(8-5)G hex (S 7)*
13.41 2.6 × 104 nd Inner 523.21918 C26H35O11 1.33 361 (MS3: 346, 343, 313, 179, 165) Secoisolariciresinol hex (S 3)
13.58 4.4 × 103 5.5 × 104 12.5 717.27850 C36H45O15 2.94 699, 669, 555, 525, 507 (MS3: 537, 525, 507, 477, 359, 329, 195) G(8-O-4)Gred/G(8-8)G/Gred hex (S 8)*
13.62 2.0 × 103 a 3.9 × 104 19.5 579.20903a C28H35O13a 1.23 519, 339, 327 G(8-5)G hex (Ref 2, F Ref 5, 6)
13.62 nd 1.3 × 105 Outer 517.17154 C26H29O11 0.01 337, 193 (MS3: 277, 217, 193, 175) Feruloyl coniferin (S 9)*
13.81 3.8 × 103 2.5 × 104 6.6 571.22002 C30H35O11 2.69 523, 391, 375, 343, 327, 195 G(8-O-4)G(8-O-4)G (Ref 5)
13.89 1.5 × 103 8.9 × 104 59.3 521.20347 C26H33O11 1.22 503, 359, 341, 329, 179, 161 IDDDC hex (S 6)
13.90 1.1 × 104 7.9 × 104 7.2 553.20917 C30H33O10 2.26 505, 339 (MS3: 487, 475, 457) G(t8-O-4)G(8-5)G (Ref 5)
14.08 6.6 × 103 1.1 × 105 16.7 519.18875 C26H31O11 3.01 501, 357 (MS3: 342, 327, 311, 151, 136) Pinoresinol hex (S 10)
14.21 4.9 × 103 a 2.4 × 103 a 0.5 433.15153a C22H25O9a 2.60 373 (MS3: 355, 325, 195, 177) G(8-O-4)G′ (Ref 5)
14.31 4.0 × 103 a 2.1 × 104 a 5.3 433.15157a C22H25O9a 2.69 G(8-O-4)G′ (Ref 5)
14.50 7.6 × 102 2.0 × 104 26.3 521.20325 C26H33O11 0.80 503, 491, 359, 341 (MS3: 329, 314), IDDDC hex (S 6)
14.72 1.0 × 103 1.5 × 104 15 405.15636 C21H25O8 2.14 357, 225 (MS3: 342) S(t8-O-4)G (Ref 6)
15.00 4.9 × 103 6.0 × 104 12.2 375.14579 C20H23O7 2.30 327, 195, 165 (MS3: 312) G(t8-O-4)G (Ref 5, F Ref 2)
15.06 3.4 × 103 3.5 × 103 1.1 569.20468 C30H33O11 3.24 521, 391, 177, 162 G(8-O-4)G(8-O-4)G′ (S 11)*
15.24 2.6 × 103 4.5 × 103 1.7 373.13006 C20H21O7 2.10 355, 343, 325, 249, 231, 219, 203, 193, 179 G(8-O-4)5H ? (Ref 6)
15.28 4.2 × 103 3.9 × 103 0.9 601.23041 C31H37O12 2.26 551, 421, 373, 225, 195 G(8-O-4)S(8-O-4)G (S 5)*
15.71 3.0 × 104 1.8 × 105 6 583.21962 C31H35O11 1.95 535, 369, 357 (MS3: 505) G(t8-O-4)S(8-5)G (Ref 5)
15.80 1.7 × 103 8.5 × 103 5 571.21852 C30H35O11 0.06 523, 391, 343, 195 G(8-O-4)G(8-O-4)G (Ref 5)
15.91 2.4 × 103 1.4 × 104 5.8 571.21980 C30H35O11 2.30 523, 449, 301, 271, 195 G(8-O-4)G(8-O-4)G (Ref 5)
15.99 3.1 × 103 5.6 × 103 1.8 601.23037 C31H37O12 2.20 553, 421, 225, 195 G(8-O-4)S(8-O-4)G (S 5)*
16.06 1.2 × 103 7.0 × 103 5.8 747.28685 C37H47O16 −0.15 585, 537 (MS3: 537, 359, 345, 343) S(t8-O-4)Gred/G(8-8/5)G/Gred hex (S 12)*
16.13 1.9 × 103 1.7 × 104 8.9 571.21975 C30H35O11 2.21 523, 497, 449, 301, 271 G(8-O-4)G(8-O-4)G (Ref 5)
16.42 2.9 × 103 2.4 × 104 8.3 571.21976 C30H35O11 2.23 523, 391, 343, 301, 271, 195 G(8-O-4)G(8-O-4)G (Ref 5)
16.64 1.4 × 103 1.3 × 105 92.8 547.18218 C27H31O12 0.15 367 (MS3: 307, 265, 247, 223, 205, 190, 179, 164) Sinapoyl coniferin (S 13)*
16.65 1.6 × 104 a 1.2 × 104 a 0.75 419.17204a C22H27O8a 2.14 359, 329 (MS3: 329) Lariciresinol (Ref 8, F Ref 7)
16.75 2.9 × 103 9.2 × 104 31.7 714.25241 C34H40O14N3 1.07 696, 533, 517 (MS3: 337, 193, 175), 337 Nitrogen-containing derivate of feruloyl coniferin (S 14)*
16.87 9.5 × 104 3.0 × 104 0.3 357.13516 C20H21O6 2.23 339, 327, 221, 203, 191 (MS3: 324, 203, 123) DDC (Ref 5, F Ref 2)
17.13 1.1 × 103 1.6 × 103 1.5 557.24022 C30H37O10 1.79 539, 509, 415, 361 G(e8-O-4)Gred(8-8)Gred (S 15)
17.18 2.9 × 103 2.2 × 103 0.8 373.13008 C20H21O7 2.15 355, 343, 193, 179 (MS3: 164, 161, 146) G(8-O-4)5H (Ref 6)
17.37 1.5 × 104 4.8 × 103 0.3 555.22464 C30H35O10 1.93 525, 507, 477, 329 G(e8-O-4)Gred(8-8)G (Ref 7)
17.74 9.4 × 103 4.5 × 103 0.5 553.20920 C30H33O10 2.31 535, 523, 505, 339, 327, 195, 165 (MS3: 324) G(t8-O-4)G(8-5)G (Ref 7)
17.78 2.1 × 103 1.1 × 104 5.2 745.27291 C37H45O16 2.15 583 (MS3: 535, 387, 195), 535, 387) G(t8-O-4)S(8-8)G hex (S 16)
17.90 4.7 × 103 2.1 × 104 4.5 745.27362 C37H45O16 3.10 583, 535, 387 G(8-O-4)S(8-8)G hex (S 16)
18.49 1.0 × 103 nd Inner 551.19358 C30H31O10 2.38 503, 373 G(8-5)G(8-O-4)G′ (Ref 5)
18.59 9.5 × 102 4.1 × 103 4.3 745.27205 C37H45O16 0.99 583, 535, 387 G(8-O-4)S(8-8)G hex (S 16)
19.09 1.5 × 103 7.1 × 103 4.7 553.20831 C30H33O10 0.70 535, 523, 505, 339, 327, 195 G(t8-O-4)G(8-5)G (Ref 5)
19.12 1.7 × 103 1.6 × 103 0.9 521.18310 C29H29O9 2.67 473, 337, 325, 190 H(8-O-4)G(8-5)G′ (S 17)*
19.17 4.7 × 102 3.0 × 103 6.4 583.21915 C31H35O11 1.14 535, 339, 327, 225 S(t8-O-4)G(8-5)G (Ref 5)
19.39 2.4 × 103 1.4 × 104 5.8 553.20907 C30H33O10 2.08 523, 505, 357, 339, 303 G(t8-O-4)G(8-5)G (Ref 5)
19.59 5.7 × 104 1.8 × 104 0.3 583.21852 C31H35O11 0.06 535, 369, 357 G(t8-O-4)S(8-5)G (Ref 5)
19.74 2.3 × 104 7.1 × 103 0.3 551.19348 C30H31O10 2.19 503, 485, 337, 325, 218 G(t8-O-4)G(8-5)G′ (Ref 5)
19.89 2.8 × 103 3.1 × 103 1.1 357.13497 C20H21O6 1.70 342, 339, 327, 311, 151, 136 (MS3: 136) Pinoresinol (Ref 5, F Ref 7,8)
20.11 5.9 × 103 2.1 × 103 0.4 585.23525 C31H37O11 1.90 537, 359, 195 G(t8-O-4)Sred/S(8-8/5)G/Gred (S 18)
20.20 2.6 × 103 1.2 × 103 0.5 747.26721 C40H43O14 1.85 699, 551, 503, 337 G(t8-O-4)G(8-O-4)G(8-5)G′ (S 19)*
20.30 1.2 × 104 4.6 × 103 0.4 583.21863 C31H35O11 0.25 535, 369, 357 G(e8-O-4)S(8-5)G (Ref 5)
20.92 2.2 × 103 8.1 × 102 0.4 551.19354 C30H31O10 2.30 533, 503, 367, 355, 218 H(t8-O-4)S(8-5)G′ (S 20)*
21.11 9.9 × 102 2.6 × 103 2.6 613.22927 C32H37O12 0.36 565, 369, 357 S(t8-O-4)S(8-5)G (Ref 5)
21.70 1.9 × 103 4.2 × 103 2.2 583.21974 C31H35O11 2.15 535, 369, 357 G(t8-O-4)S(8-5)G (Ref 5)
21.80 3.2 × 104 7.5 × 103 0.2 581.20430 C31H33O11 2.52 551, 533, 515, 367, 355, 218 G(t8-O-4)S(8-5)G′ (Ref 5)