Targeted and Untargeted Metabolomic Analyses Reveal Organ Specificity of Specialized Metabolites in the Model Grass Brachypodium distachyon
Abstract
:1. Introduction
2. Results and Discussion
2.1. Comparison of Metabolomics Profiles in Analyzed Brachypodium Organs and Lines
2.2. Pathway Enrichment Analysis
2.2.1. Most Represented Metabolic Pathways
2.2.2. Metabolic Pathways Distinguishing Bd21 and Bd3-1 Lines
2.3. Metabolite Identification with LC-MS Systems
2.3.1. Hydroxycinnamoyl-Quinic Acids
2.3.2. Esters of Hydroxycinnamic and Threonic Acids
2.3.3. Hydroxycinnamic Acid Amides
2.3.4. Flavonoid Glycosides
O-Glycosides
O,C-Glycosides
Di-C-Glycosides
2.3.5. Acylated Flavonoids
2.3.6. Flavan-3-ols
3. Material and Methods
3.1. Plant Material
3.2. Chemicals
3.3. Metabolite Profiling
3.4. Metabolite Identification
3.5. Bioinformatic Processing
3.6. Statistical Analysis
3.7. Pathway Enrichment Analyses
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Biological Pathway (KEGG) | Total | Hits | FDR | Impact |
---|---|---|---|---|
Flavonoid biosynthesis | 47 | 40 | 4.31 × 10−6 | 0.75288 |
Galactose metabolism | 27 | 25 | 2.72 × 10−5 | 1 |
Amino sugar and nucleotide sugar metabolism | 50 | 39 | 0.000177 | 0.92767 |
Valine, leucine and isoleucine biosynthesis | 22 | 20 | 0.000426 | 0.99998 |
Pentose and glucuronate interconversions | 17 | 16 | 0.000971 | 1 |
Flavone and flavonol biosynthesis | 12 | 12 | 0.001539 | 1 |
2-Oxocarboxylic acid metabolism | 12 | 12 | 0.001539 | 1 |
Pentose phosphate pathway | 19 | 16 | 0.010995 | 0.9532 |
Purine metabolism | 63 | 42 | 0.011504 | 0.67941 |
Tyrosine metabolism | 18 | 15 | 0.014584 | 0.79191 |
Ascorbate and aldarate metabolism | 18 | 15 | 0.014584 | 0.8806 |
Vitamin B6 metabolism | 11 | 10 | 0.026026 | 0.96153 |
Biological Pathway Enrichment (KEGG) | Total | Hits | FDR | Impact | |
---|---|---|---|---|---|
Roots | Galactose metabolism | 27 | 25 | 7.41 × 10−7 | 1 |
Diterpenoid biosynthesis | 47 | 32 | 0.001253 | 0.61959 | |
Flavonoid biosynthesis | 47 | 32 | 0.001253 | 0.64212 | |
Valine, leucine and isoleucine biosynthesis | 22 | 18 | 0.001253 | 0.68294 | |
Caffeine metabolism | 10 | 10 | 0.001636 | 0 | |
Pentose phosphate pathway | 19 | 15 | 0.007666 | 0.85473 | |
One carbon pool by folate | 8 | 8 | 0.007666 | 1 | |
Flavone and flavonol biosynthesis | 12 | 10 | 0.025063 | 0 | |
2-Oxocarboxylic acid metabolism | 12 | 10 | 0.025063 | 0 | |
Leaves | Flavonoid biosynthesis | 47 | 42 | 2.39 × 10−6 | 0.7644 |
Galactose metabolism | 27 | 24 | 0.001979 | 1 | |
Valine, leucine and isoleucine biosynthesis | 22 | 20 | 0.003065 | 0.8355 | |
Histidine metabolism | 17 | 16 | 0.004891 | 1 | |
Flavone and flavonol biosynthesis | 12 | 12 | 0.0054 | 0 | |
2-Oxocarboxylic acid metabolism | 12 | 12 | 0.0054 | 0 | |
Pentose phosphate pathway | 19 | 17 | 0.007434 | 0.99999 | |
Vitamin B6 metabolism | 11 | 11 | 0.007908 | 0.99999 | |
Diterpenoid biosynthesis | 47 | 34 | 0.028047 | 0.69919 | |
Spikes | Flavonoid biosynthesis | 47 | 41 | 3.39 × 10−5 | 0.75288 |
Galactose metabolism | 27 | 25 | 0.000367 | 1 | |
Pentose phosphate pathway | 19 | 18 | 0.002628 | 0.99999 | |
Valine, leucine and isoleucine biosynthesis | 22 | 20 | 0.003264 | 0.8355 | |
Flavone and flavonol biosynthesis | 12 | 12 | 0.006808 | 0 | |
2-Oxocarboxylic acid metabolism | 12 | 12 | 0.006808 | 0 | |
Vitamin B6 metabolism | 11 | 11 | 0.011173 | 0.99999 | |
Pentose and glucuronate interconversions | 17 | 15 | 0.021023 | 0.85716 | |
Histidine metabolism | 17 | 15 | 0.021023 | 1 | |
Cysteine and methionine metabolism | 46 | 34 | 0.021023 | 0.75798 |
# | Fragmentation Pathway in MSn [m/z] | Identification | Exact mass of [M+H]+ or [M−H]; [Da] | ∆ ppm | Chemical Formula | λmax [nm] | Leaves | Roots | Spikes | ChEBI | Identification Level | References | |||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Negative Ionization | Positive Ionization | Ion Type | Measured | Calculated | |||||||||||
1 | MS2: 137, 90, 64 | Dopamine | [M+H]+ | 154.08638 | 154.0864 | 0.8102 | C8H11NO2 | * | * | * | 18243 | 2 | [49] | ||
2 | MS2: 165, 147, 136 MS3: 147, 123 | Tyrosine | [M+H]+ | 182.081 | 182.0812 | −1.1348 | C9H11NO3 | * | * | 18186 | 2 | [50] | |||
3 | MS2: 116, 86 | Leucine (Isoleucine) | [M+H]+ | 132.1018 | 132.1019 | −0.5152 | C6H13NO2 | * | * | * | 25017 | 2 | [50] | ||
4 | MS2: 163, 89 MS3: 131 | N-Caffeoyl-putrescine | [M+H]+ | 251.13862 | 251.139 | −1.589 | C13H18N2O3 | * | * | * | 17417 | 3 | [51] | ||
5 | MS2: 145, 120 MS3: 79 | Phenylalanine | [M+H]+ | 166.086 | 166.0863 | −1.3614 | C9H11NO2 | 260 | * | * | * | 28044 | 2 | [50] | |
6 | MS2: 727, 609, 559, 541, 483, 423, 303 MS3: 559, 423, 303 | (epi)Gallocatechin trimer | [M−H]− | 913.18583 | 913.1833 | 2.791 | C45H38O21 | * | * | * | 3 | [52] | |||
7 | MS2: 771, 711, 593, 543, 467, 303, 289 MS3: 697, 543, 289 | Proanthocyanidins trimer A-type | [M−H]− | 897.19086 | 897.1884 | 2.779 | C45H38O20 | * | 3 | [52] | |||||
8 | MS2: 305, 265, 223, 205, 161, 143, 125 MS3: 223, 205 | Caffeic acid derivative | [M−H]− | 367.12504 | 367.1246 | 1.24 | C17H20O9 | * | 149782 | 2 | [53] | ||||
9 | MS2: 269, 209, 167 | Vanilic acid-hexoside | [M−H]− | 329.0883 | 329.0878 | 1.5932 | C14H18O9 | * | * | 2 | [54] | ||||
10 | MS2: 218, 89 | p-Coumaroyl-N-putrescine | [M+H]+ | 235.1441 | 235.1441 | 0.0370 | C13H18N2O | 290sh | * | * | 70431 | 2 | [51] | ||
11 | MS2: 248, 177, 144, 114, 98 MS3: 145 | Feruloyl-N-putrescine | [M+H]+ | 265.15424 | 265.1547 | −1.16337 | C14H20N2O3 | * | * | 9299 | 3 | [51] | |||
12 | MS2: 233, 119 MS3: 117, 93 | MS2: 218, 176, 147, 114, 89, 73 MS3: 147 | p-Coumaroyl-N-putrescine | [M+H]+ | 235.14375 | 235.1441 | −1.507 | C13H18N2O | * | * | 3 | [51] | |||
13 | MS2: 203, 159, 142, 116 | MS2: 188, 146 MS3: 146, 118 | Tryptophan | [M+H]+ | 205.097 | 205.0972 | −0.9744 | C11H12N2O2 | 285 | * | * | * | 27897 | 1 | Std |
14 | MS2: 299, 239, 209, 179, 137 MS3: | Hydroxybenzoic acid hexoside | [M−H]− | 299.0765 | 299.07728 | −2.349 | C13H16O8 | 282 | * | 16741 | 2 | [54] | |||
15 | MS2: 574, 467, 425, 407, 289 MS3: 245, 205, 177 | MS2: 595, 443, 427, 317, 307, 289 MS3: 289, 247 | Prodelphinidin B-type | [M−H]− | 593.13153 | 593.1301 | 2.472 | C30H26O13 | * | 75664# | 2 | [52,55] | |||
16 | MS2: 315, 153 MS3: 108 | Dihydroxybenzoic acid hexoside | [M−H]− | 315.0718 | 315.0722 | −1.1026 | C13H16O9 | 286 | * | 2 | [54] | ||||
17 | MS2: 160 MS3: 134, 132, 115 | Serotonin | [M+H]+ | 177.1019 | 177.1022 | −2.0138 | C₁₀H₁₂N₂O | 275, 298sh | * | * | 28790 | 1 | Std | ||
18 | MS2: 179, 135 MS3:117, 89, 75 | MS2: 163, 136,137 MS3: 136, 118 | Caffeoylthreonic acid | [M−H]− | 297.0611 | 297.0616 | −1.664 | C13H14O8 | * | * | * | 2 | [54] | ||
19 | MS2: 461, 225, 153 MS3: 108, 90 | Dihydroxybenzoic acid hexosyldeoxyhexoside | [M−H]− | 461.1299 | 461.1301 | −0.459 | C19H26O13 | 281 | * | 3 | [54] | ||||
20 | MS2: 863, 755, 695, 591, 407, 289, 243 MS3: 524, 283 | Catechin-gallocatechin-catechin | [M−H]− | 881.19622 | 881.1935 | 3.141 | C45H38O19 | * | 3 | [52,55] | |||||
21 | MS2: 179, 134, 119 | Caffeic acid | [M−H]− | 179.03439 | 179.035 | −3.307 | C9H8O4 | 304sh | * | * | 36281 | 1 | Std | ||
22 | MS2: 299, 239, 197, 153, 138 MS3: 182, 153,138, 121 | Syringic acid-hexoside | [M−H]− | 359.09827 | 359.09782 | 1.2393 | C15H20O10 | * | * | 2 | [54] | ||||
23 | MS2: 248, 177, 145 MS3: 177 | feruloyl-N-putrescine | [M+H]+ | 265.1548 | 265.1547 | 0.3229 | C14H20N2O3 | * | * | 3 | [51] | ||||
24 | MS2: 305, 289, 241, 225, 139 MS3: 223, 184, 139, 97 | MS2: 337, 305, 185, 153 MS3: 153, 125 | (epi)Gallocatechin O-hydroxybenzoate | [M−H]− | 425.08831 | 425.0878 | 1.187 | C22H18O9 | * | * | * | 3 | [52,55] | ||
25 | MS2: 439, 325, 305, 289, 191, 163, 131 MS3: 115 | (epi)Gallocatechin 3-O-gallate | [M−H]− | 457.07885 | 457.0776 | 3.859 | C22H18O11 | * | `3 | [52,55] | |||||
26 | MS2: 323, 193, 173, 135 MS3: 149, 135 | MS2: 353, 309, 274, 238, 177, 145 MS3: 145 | 5-Feruloylquinic acid | [M−H]− | 367.1028 | 367.1035 | −1.831 | C17H20O9 | 280sh, 320 | * | * | 86388# | 2 | [56] | |
27 | MS2: 607, 589, 333, 203 MS3: 333, 203 | Prodelphinidin A-type dimer (Prodelphinidin A1) | [M−H]− | 607.11102 | 607.1093 | 2.786 | C30H24O14 | * | [52,55] | ||||||
28 | MS2: 463, 301 | MS2: 465, 303, 229, 201 MS3: 303 | Quercetin di-O-hexoside | [M−H]− | 625.14292 | 625.141 | 3.035 | C27H30O17 | 253, 353 | * | 3 | [53,57] | |||
29 | MS2: 353, 179, 173 MS3: 109, 93 | MS2: 192, 165, 146 | 4-Caffeoylquinic acid | [M−H]− | 353.06743 | 353.0667 | 2.136 | C16H18O9 | 340sh, 305 | * | * | 75491 | 2 | [56] | |
30 | MS2: 665, 635, 563, 503, 473, 443, 383, 353 MS3: 353, 297 | Apigenin 6-C-hexoside-8-C-pentoside 7-O-hexoside | [M−H]− | 725.1924 | 725.1898 | −3.4967 | C32H38O19 | 266, 335 | 3 | [58] | |||||
31 | MS2: 489, 399, 369 MS3: 369 | Luteolin 6,8-di-C-hexoside | [M−H]− | 609.1435 | 609.1450 | −2.5141 | C27H30O16 | 262, 345 | * | * | 6553 | 2 | [58] | ||
32 | MS2: 577, 407, 289 MS3: 289, 143 | MS2: 579, 427, 291 | Procyanidin B-type dimer | [M−H]− | 577.13679 | 577.1351 | 2.843 | C30H26O12 | * | 75630 | 2 | [52,55] | |||
33 | MS3: 245, 205, 137, 125 MS3: 203 | MS2: 157, 139, 123 | (epi)Catechin | [M−H]− | 289.07255 | 289.0718 | 2.728 | C15H14O6 | * | 23053 | 2 | [55] | |||
34 | MS2:595, 483, 423, 305, 283 MS3 (609-483): 303, 179 MS3 (609-305): 289, 143 | MS2: 611, 443, 317 | Prodelphinidin B-type | [M−H]− | 609.12659 | 609.125 | 2.646 | C30H26O14 | * | 2 | [52] | ||||
35 | MS2: 275, 235, 218, 147, 118 MS3: 218, 147, 112 | N-p-Coumaroyl spermidine | [M+H]+ | 292.07275 | 292.0717 | 3.706 | C34H37N3O6 | 285sh | * | 2 | [59] | ||||
36 | MS2: 609, 301 MS3: 301, 272 | MS2: 627, 611, 465, 303 MS3: 369, 303 | Quercetin O-deoxyhexosylhexoside-O-hexoside | [M−H]− | 771.1991 | 771.189 | 0.1549 | C33H40O21 | 255, 353 | * | 3 | [58] | |||
37 | MS2: 463, 301 | MS2: 610, 551, 465, 303 MS3: 303 | Quercetin di-O-hexoside II | [M−H]− | 625.13971 | 625.141 | −2.099 | C27H30O17 | 253, 353 | * | * | 3 | [53,57] | ||
38 | MS2: 193, 134 | Ferulic acid | [M−H]− | 193.05024 | 193.0506 | −2.031 | C10H10O4 | 300sh, 326 | * | * | 17620 | 3 | [53,57] | ||
39 | MS2: 179, 135, 117 MS3:117, 89 | MS2: 299, 136 | Apigenin 7,4’-dimethyl ether | [M−H]− | 297.07752 | 297.0768 | 2.266 | C17H14O5 | * | 17620 | 2 | [60] | |||
40 | MS2: 233, 119 | MS2: 260, 217, 147, 114 MS3: 217, 98 | p-Coumaroylagmatine | [M+H]+ | 277.16547 | 277.1659 | −1.560 | C14H20N4O2 | 295sh | * | * | * | 32818 | 2 | [54] |
41 | MS2: 489, 447, 285, 254 MS3: 285, 254 | MS2: 567, 449, 287 | Luteolin di-O-hexoside | [M−H]− | 609.1477 | 609.1461 | 2.614 | C27H30O16 | 267, 348 | * | 2 | [61] | |||
42 | MS2: 311, 193, 149, 135 MS3: 135, 119 | Feruloylthreonic acid | [M−H]− | 311.07697 | 311.0772 | −0.87 | C14H16O8 | * | 3 | [57] | |||||
43 | MS2: 193, 173, MS3: 109, 93 | MS2: 404, 369, 277, 193 | 4-Feruloylquinic acid | [M−H]− | 367.1037 | 367.1035 | 0.7349 | C17H20O9 | * | 3 | [54] | ||||
44 | MS2: 562, 519, 477, 315 MS3: 357, 315, 285, 243, 199 | MS2: 641, 479, 317, 286 | Isorhamnetin di-O-hexoside | [M−H]− | 639.15509 | 639.1567 | −2.476 | C28H32O17 | 259, 369 | * | * | 60078 | 2 | [56] | |
45 | MS2: 695, 635, 593, 454, 473, 413, 311, 249 MS3: 473, 413 | Chrysoeriol 6-C-hexoside-8-C-pentoside 7-O-hexoside | [M−H]− | 755.20585 | 755.204 | 2.428 | C33H40O20 | 250, 348 | * | * | 3 | [57] | |||
46 | MS2: 519, 447, 357, 327 | MS2: 532, 464, 449, 431, 383, 353, 329, 299 MS3: 432, 413, 383, 353, 329, 320, 299 | Orientin 7-O-hexoside | [M−H]− | 609.1439 | 609.1450 | −1.8549 | C27H30O16 | 266, 349 | * | 3 | [58] | |||
47 | MS2: 369, 325, 163, 145, 119 MS3: 117, 95 | Sinapoyl-homovanillic acid | [M−H]− | 387.10814 | 387.1085 | −1.035 | C20H20O8 | * | 3 | [58] | |||||
48 | MS2: 191, 179, 173, MS3: 155, 111, 93, 71 | MS2: 146, 119, 79 | 4-p-Coumaroylquinic acid | [M−H]− | 337.0939 | 337.0929 | 2.6396 | C16H18O8 | 290sh | * | * | 1945 | 3 | [54] | |
49 | MS2: 290, 247, 232, 177, 152, 145, 114 MS3: 273, 247, 230, 177, 115 MS4: 145, 113 | Feruloylagmatine | [M+H]+ | 307.17636 | 307.1765 | −0.349 | C15H22N4O3 | 290sh, 320 | * | 1945 | 2 | [56] | |||
50 | MS2: 771, 651, 609, 429, 357, 327 MS3: 357, 327, 299 | Isoorientin 2”,6”-di-O-hexoside | [M−H]− | 771.19946 | 771.1989 | 0.6895 | C33H40O21 | 270, 344 | * | 75544 | 2 | [61] | |||
51 | MS2: 489, 447, 357, 327 MS3: 357, 327, 299 | MS2: 593, 449, 383, 329, 299 MS3: 431, 383, 353, 299 | Isoorientin 7-O-glucoside | [M−H]− | 609.1433 | 609.1450 | −2.7680 | C27H30O16 | 268, 348 | * | 75514 | 1 | Std; [58] | ||
52 | MS2: 489, 447, 327, 285, 255 MS3: 284, 226 | MS2: 449, 287, 269 MS3: 287, 259, 213 MS4: 213, 153, 133 | Luteolin 3′,7-di-O-glucoside | [M−H]− | 609.1475 | 609.1461 | 2.285 | C27H30O16 | 269, 343 | * | 75514 | 1 | Std | ||
53 | MS2: 593 MS3: 285, 185, 153, 131 | MS2: 595, 491, 449, 335, 311, 287 MS3: 449, 287 | Luteolin O-hexosyldeoxyhexoside-O-hexoside | [M−H]− | 755.20408 | 755.204 | 0.084 | C33H40O20 | 266, 349 | * | * | 3 | [57] | ||
54 | MS2: 623, 447, 315, 299 MS3: 357, 315, 299, 271, 255, 227 | MS2: 657, 641, 625, 609, 479, 317, 302, 273 MS3: 342, 317, 273 | Isorhamnetin O-hexosyldeoxyhexoside-O-hexoside | [M−H]− | 785.21381 | 785.2146 | −0.982 | C34H42O21 | 259, 369 | * | * | 3 | [53,57] | ||
55 | MS2: 477, 357, 315, 255, 217 MS3: 153 | Isorhamnetin hexoside | [M−H]− | 477.10435 | 477.1038 | 1.05 | C22H22O12 | 252, 369 | * | * | 3 | [53,57] | |||
56 | MS2: 315, 255 MS3: 153 | Isorhamnetin deoxyhexosylhexoside | [M−H]− | 623.1624 | 623.1618 | 1.0327 | C28H32O16 | - | * | 75752 or 75758 | 3 | [57] | |||
57 | MS2: 575, 502, 473, 413, 383 MS3 (593-473): 383, 353, 311 MS3 (593-502): 413, 383, 312 | MS2: 577, 559, 541, 529, 499, 457, 427 MS3 (595-529): 511, 427, 367 MS3 (595-577): 559, 529, 511, 481, 445, 427, 409, 380 | Apigenin 6,8-di-C-hexoside | [M−H]− | 593.1505 | 593.1512 | −1.2503 | C27H30O15 | 269, 339 | * | 3 | [53,57] | |||
58 | MS2:561, 519, 489, 459, 429, 399, 369 MS3:399, 369 MS4:341, 297 | MS2: 563, 545, 515, 497, 443, 413 MS3: 545, 515, 497, 485, 467, 395 MS4 (563-497): 413, 395, 312 MS4 (563-545): 509, 497, 467 | Luteolin 6-C-pentoside-8-C-hexoside | [M−H]− | 579.1492 | 579.1501 | −1.489 | C26H28O15 | 269, 348 | * | * | 69814 | 2 | [62] | |
59 | MS2: 399, 387, 205, 181 MS3: 372, 203 | Sinapoyl-homovanillic acid derivative | [M−H]− | 597.18205 | 597.1825 | −0.742 | 260, 335 | * | * | * | 75566 | 2 | [58] | ||
60 | MS2: 609, 489, MS3: 489, 429, 309 MS4: 309 | Isoorientin 2″-O-hexoside 7-O-[6″-sinapoyl]-hexoside | [M−H]− | 977.26068 | 977.2568 | 3.929 | C44H50O25 | 263, 340 | * | 3 | [58] | ||||
61 | MS2: 469, 307, 161 MS3: 307, 161 | Hydroxycoumarin hexoside-pentoside | [M−H]− | 469.13626 | 469.1351 | 2.367 | C20H24O12 | * | 3 | [62] | |||||
62 | MS2: 307, 161, 145 MS3: 161, 145, 113 | p-Coumaroyl-caffeic acid pentoside | [M−H]− | 439.12554 | 439.1246 | 2.175 | C23H22O10 | 286sh, 315 | * | 3 | [56] | ||||
63 | MS2: 163, 135, 119 MS3: 119 | p-Coumaroylthreonic acid | [M−H]− | 281.0672 | 281.0667 | 1.864 | C13H14O7 | 290sh | * | 3 | [56] | ||||
64 | MS2: 561, 489, 459, 399, 369, 327 MS3: 441, 399, 369 MS4: 341, 313 | MS2: 563, 545, 515, 497, 485, 473, 413 MS3: 545, 515, 473, 449, 413, 365 MS4 (563-473): 455, 437, 367, 341 MS4 (563-515): 449, 431, 413 | Luteolin 6-C-hexoside-8-C-pentoside | [M−H]− | 579.1368 | 579.1355 | 2.17 | C26H28O15 | 262, 345 | * | 3 | [54] | |||
65 | MS2: 697, 535, 373, 329, 178 MS3: 299, 284, 269, 178, 161 | Hydroxypinoresinol di-O-hexoside | [M−H]− | 697.23658 | 697.2366 | 2.377 | C32H42O17 | 278 | * | * | 3421 | 2 | [62] | ||
66 | MS2: 489, 429, 327, 309, 285 MS3: 327, 298 MS4: 297, 175 | Isoorientin 6”-O-hexoside | [M−H]− | 609.1440 | 609.1450 | −1.6214 | C27H30O16 | 266, 347 | * | 75353 | 3 | [58] | |||
67 | MS2: 449, 303, 285 MS3: 285 | Quercetin O-deoxyhexosylhexoside | [M+H]+ | 611.1594 | 611.1607 | −2.0245 | C27H30O16 | 255, 353 | * | * | 2 | [62] | |||
68 | MS2: 575, 533, 503, 473, 431, 311 MS3: 413, 383, 311 | Isovitexin 6”-O-hexoside | [M−H]− | 593.15198 | 593.1520 | 1.3952 | C27H30O15 | 268, 335 | * | 3 | [53,57] | ||||
69 | MS2: 533, 503, 473, 413, 383, 341, 293 MS3: 312, 293 | MS2: 433, 415, 397, 367, 337, 313, 283 MS3: 415, 397, 367, 337, 313, 283367, 283 MS4:283 | Isovitexin 2”-O-glucoside | [M−H]− | 593.15094 | 593.15119 | −0.42709 | C27H30O15 | 268, 335 | * | 1 | Std; [58] | |||
70 | MS2: 489, 429, 369, 357, 339, 309 MS3: 429, 369, 351, 339, 309, 243 | MS2: 449, 431, 383, 353, 329, 299 MS3: 431, 413, 383, 353, 329, 299 MS4: 299 | Isoorientin 2”-O-glucoside | [M−H]− | 609.1476 | 609.1461 | 2.45 | C27H30O16 | 269, 348 | * | 17379 | 1 | Std; [58] | ||
71 | MS2:429, 411, 357, 327, 283 MS3: 297, 283 MS4: 269 | MS2: 431, 383, 353, 329, 299 MS3: 299 | Isoorientin | [M−H]− | 447.0939 | 447.0933 | 1.4239 | C21H20O11 | * | * | 17965 | 1 | Std | ||
72 | MS2: 545, 503, 473, 443, 413, 383, 353, 325 MS3 (563-353): 353, 325, 297 MS3 (563-443): 383, 353, 297, 191 | MS2: 547, 529, 511, 451, 337 MS3: 530, 499, 482, 458, 391 MS4: 512, 397 | Apigenin 6-C-glucoside-8-C-arabinoside | [M−H]− | 563.1409 | 563.1406 | 0.5600 | C26H28O14 | 265, 335 | * | * | 17965 | 1 | Std | |
73 | MS2: 455, 503, 473, 443, 383, 353, 337 MS3: 353, 325, 297, 203 MS4: 325, 297 | Apigenin 6-C-pentoside-8-C-hexoside | [M−H]− | 563.1416 | 563.1406 | 1.7191 | C26H28O14 | 266, 335 | * | * | * | 9047 | 2 | [62] | |
74 | MS2: 447, 357, 327, 285 MS3: 339, 311, 297, 285 | MS2: 431, 383, 299 MS3: 299 MS4: 183, 121 | Orientin | [M−H]− | 447.0926 | 447.0933 | −1.4845 | C21H20O11 | * | * | 7781 | 3 | [62] | ||
75 | MS2: 503, 473, 443, 383, 353 MS3: 365, 325, 221 | MS2: 547, 500, 457 MS3: 511, 493, 409 | Apigenin 6-C-pentoside-8-C-hexoside | [M−H]− | 563.14198 | 563.1406 | 2.4 | C26H28O14 | 266, 335 | 75589 | 3 | [62] | |||
76 | MS2: 593, 503, 473, 431, 311, 297, 283 MS3: 311, 283 | MS2: 577, 559, 529, 409, 475, 433, 415, 397, 367, 337, 313, 283 MS3: 559, 529, 498, 415, 397, 367, 337, 283 MS4: 175 | Isovitexin 7-O-glucoside | [M−H]− | 593.1506 | 593.1215 | −0.9416 | C27H30O15 | 265, 335 | * | * | * | 75439 | 1 | Std; [58] |
77 | MS2: 653, 491, 329 MS3: 315, 299 | Tricin di-O-glucoside | [M−H]− | 653.17377 | 653.1723 | 2.216 | C29H34O17 | 266, 369 | * | 2 | [58] | ||||
78 | MS2: 463, 301 MS3: 301, 286 | Chrysoeriol di-O-hexoside | [M+H]+ | 625.1755 | 625.1763 | −1.3123 | C28H32O16 | 246, 266, 347 | * | 3 | [57] | ||||
79 | MS2: 574, 533, 503, 473, 413, 383 MS3: 413, 383 MS4: 355, 312 | MS2: 577, 559, 529, 499, 463, 409, 356 MS3: 541, 529, 499, 452, 427, 377 MS4: 427, 355 | Chrysoeriol 6-C-hexoside-8-C-pentoside | [M−H]− | 593.1518 | 593.1512 | 1.0147 | C27H30O15 | 250, 348 | * | 3 | [57] | |||
80 | MS2: 577, 503, 457, 383, 353 MS3: 383, 353 | Apigenin 6-C-hexoside-8-C-deoxyhexoside | [M−H]− | 577.15643 | 577.1563 | 0.262 | C27H30O14 | 266, 335 | * | * | 2 | [62] | |||
81 | MS2: 574, 533, 503, 473, 413, 383 MS3: 413, 383 MS4: 352, 338, 312 | MS2: 577, 541, 457, 529, 511, 409, 389, 345 MS3: 559, 529, 511, 427 MS4: 511 | Chrysoeriol 6-C-pentoside-8-C-hexoside | [M−H]− | 593.15277 | 593.1512 | 2.658 | C27H30O15 | 246, 267, 346 | * | 3 | [62] | |||
82 | MS2: 371, 209, 175 MS3: 209, 121 | MS2: 387, 373, 369, 211, 193 MS3: 211 | Blumenol C-hexoside-glucuronide | [M−H]− | 547.23957 | 547.2396 | −0.081 | C25H39O13− | 255 | * | * | * | 2 | [58] | |
83 | MS2: 341, 311, 283 MS3: 283, 237, 117 | MS2: 415, 397, 367, 337, 283 MS3: 283, 271 | Isovitexin | [M−H]− | 431.0994 | 431.0984 | 2.4502 | C21H20O10 | 268, 336 | * | 18330 | 1 | Std; [58] | ||
84 | MS2: 503, 443, 323 MS3: 323, 308 MS4: 308 | MS2: 607, 591, 542, 463, 445, 397, 367, 343, 313, 265 MS3: 445, 427, 397, 367, 343, 313 | Isoscoparin 2”-O-glucoside | [M−H]− | 623.1611 | 623.1618 | −1.1011 | C28H32O16 | 250, 348 | * | * | 75518 | 1 | Std; [58] | |
85 | MS2: 491, 373, 329 MS3: 315, 175 | Tricin hexosylmalonate | [M−H]− | 577.12073 | 577.1199 | 1.45 | C26H26O15 | - | * | * | 75518 | 3 | [53] | ||
86 | MS2: 515, 473, 443, 413, 383, 353 MS3: 325, 297 MS4: 267 | MS2: 517, 499, 481, 469, 433, 415, 397, 308 MS3:481, 463, 445, 433, 409, 379 MS4: 463, 445, 433, 397, 373, 351, 329 | Apigenin 6-C-pentoside-8-C-pentoside | [M−H]− | 535.1458 | 535.1446 | 2.2345 | C25H26O13 | 265, 335 | * | * | 3 | [53] | ||
87 | MS2: 371, 341, 298 MS3: 327, 313, 298 | MS2: 455, 427, 409, 397, 367, 343, 313 MS3 (463-397): 379, 313, 301, 298 MS3 (463-445): 427, 397, 367, 313, 253 MS4 (445-367): 339, 324 MS5 (367-339): 324, 311 | Isoscoparin | [M−H]− | 461.1089 | 461.1089 | 0.0285 | C22H22O11 | * | * | 18200 | 2 | [62] | ||
88 | MS2: 476, 329, 314 MS3: 314, 299 | MS2: 331, MS3: 315, 287, 270 | Tricin 7-O-glucoside | [M−H]− | 491.1192 | 491.1195 | −0.6682 | C23H24O12 | 266, 368 | * | * | 75349 | 1 | Std | |
89 | MS2: 329, 314, 299 MS3: 314, 299 | MS2: 493, 331, 315 MS3: 315, 269 | Tricin O-hexosyldeoxyhexoside | [M−H]− | 637.1769 | 637.1774 | −0.733 | C29H34O16 | 265, 367 | * | * | * | 131777 | 3 | [58] |
90 | MS2: 329, 313 MS3: 314 | MS2: 493, 475, 331 MS3: 331, 315 MS4: 315, 269 | Tricin O-deoxyhexoside-O-hexoside | [M−H]− | 637.19042 | 639.19196 | −2.3961 | C29H34O16 | 266, 367 | * | 3 | [53,57] | |||
91 | MS2: 607, 299, 284 | MS2: 463, 301 | Chrysoeriol O-hexosyldeoxyhexoside | [M−H]− | 607.16864 [M−H]− | 607.1668 | 2.959 | C28H32O15 | 249, 250, 345 | * | * | * | 3 | [53,57] | |
92 | MS2: 313, 299 MS3: 299, 285, 161 MS4: 271, 203, 161 | MS2: 315, 270, 253 MS3: 299, 270, 242, 207, 153 | Tricin | [M−H]− | 329.06758 | 329.0667 | 2.747 | C17H14O7 | * | * | 59979 | 3 | [53,57] | ||
93 | MS2: 383, 267, 249, 193, 134, 113 | Feruloylhydroxycitric acid | [M−H]− | 383.06252 | 383.062 | 1.4026 | C16H16O11 | * | * | 176361 | 3 | [58] |
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Piasecka, A.; Sawikowska, A.; Jedrzejczak-Rey, N.; Piślewska-Bednarek, M.; Bednarek, P. Targeted and Untargeted Metabolomic Analyses Reveal Organ Specificity of Specialized Metabolites in the Model Grass Brachypodium distachyon. Molecules 2022, 27, 5956. https://doi.org/10.3390/molecules27185956
Piasecka A, Sawikowska A, Jedrzejczak-Rey N, Piślewska-Bednarek M, Bednarek P. Targeted and Untargeted Metabolomic Analyses Reveal Organ Specificity of Specialized Metabolites in the Model Grass Brachypodium distachyon. Molecules. 2022; 27(18):5956. https://doi.org/10.3390/molecules27185956
Chicago/Turabian StylePiasecka, Anna, Aneta Sawikowska, Nicolas Jedrzejczak-Rey, Mariola Piślewska-Bednarek, and Paweł Bednarek. 2022. "Targeted and Untargeted Metabolomic Analyses Reveal Organ Specificity of Specialized Metabolites in the Model Grass Brachypodium distachyon" Molecules 27, no. 18: 5956. https://doi.org/10.3390/molecules27185956