Comprehensive Phenolic Profiling of Cyclopia genistoides (L.) Vent. by LC-DAD-MS and -MS/MS Reveals Novel Xanthone and Benzophenone Constituents
Abstract
:1. Introduction
2. Results and Discussion
2.1. HPLC-DAD Method Development
2.2. LC-DAD-ESI-MS and -MS/MS Identification of Compounds Present in Hot Water Extracts of Unfermented and Fermented C. genistoides
2.2.1. Benzophenone Derivatives
Nr | tR (min) | Proposed Compound | λmax (nm) | Mode | Accurate Mass, exp. | Proposed Formula | Error (ppm) | Precursor Ion | LC-MS/MS Ions a,b |
---|---|---|---|---|---|---|---|---|---|
a | 4.06 | maclurin-di-O,C-hexoside | 235, 290, 320 sh | + | 587.1625 | C25H31O16 | −2.2 | 587 | 425, 407, 389, 371, 353, 341, 329, 305, 287, 275, 261, 243, 231, 219, 195, 177, 165, 153, 137, 121 |
− | 585.1469 | C25H29O16 | 2.2 | 585 | 495, 465, 385, 355, 333, 303, 285, 261, 223, 193, 165, 125 | ||||
b | 7.24 | iriflophenone-di-O,C-hexoside isomer | 234, 294 | + | 571.1664 | C25H31O15 | 0.2 | 571 | 373, 355, 337, 325, 313, 289, 279, 271, 261, 243, 231, 219, 195, 177, 165, 121 |
− | 569.1509 | C25H29O15 | 0.5 | 569 | 479, 449, 407, 385, 355, 341, 329, 317, 311, 287, 245, 197, 193, 167, 125 | ||||
c | 8.17 | maclurin-3-C-glucoside | 235, 290, 318 sh | + | 425.1080 | C19H21O11 | −0.4 | 425 | 353, 341, 329, 287, 261, 243, 231, 219, 195, 177, 165, 153, 137, 121 |
− | 423.0923 | C19H19O11 | −0.9 | 423 | 333, 303, 261, 223, 205, 193, 165, 151, 137, 125, 109 | ||||
d | 10.49 | iriflophenone-di-O,C-hexoside isomer | 225, 290 | + | 571.1503 | C25H31O15 | −5.6 | 571 | 373, 337, 325, 313, 289, 279, 271, 261, 243, 231, 219, 195, 177, 165, 121 |
− | 569.1511 | C25H29O15 | 0.9 | 569 | 479, 449, 385, 355, 317, 287, 245, 193, 167, 125 | ||||
f | 13.27 | iriflophenone-di-O,C-hexoside isomer | 225, 290 | + | 571.1639 | C25H31O15 | −4.2 | 571 | 425, 355, 337, 325, 313, 289, 279, 271, 261, 247, 231, 219, 195, 177, 165, 121 |
− | 569.1503 | C25H29O15 | −0.5 | 569 | 479, 449, 385, 355, 317, 287, 245, 193, 167, 125 | ||||
3 | 13.70 | iriflophenone-3-C-glucoside | 235, 295 | + | 409.1133 | C19H21O10 | −0.5 | 409 | 337, 325, 313, 279, 271, 261, 243, 231, 219, 195, 177, 165, 153, 121 |
− | 407.0967 | C19H19O10 | −2.7 | 407 | 317, 299, 287, 257, 245, 215, 201, 193, 167, 151, 137, 125 | ||||
i | 16.65 | iriflophenone-di-C-hexoside c | 225, 302 (weak) | + | 571.1655 | C25H31O15 | −1.4 | 571 | 481, 470, 463, 451, 433, 421, 403, 391, 379, 367, 355, 349, 337, 325, 313, 295, 285, 273, 261, 243, 231, 219, 189, 177, 121 |
− | 569.1509 | C25H29O15 | 0.5 | 569 | 479, 461, 431, 389, 359, 329, 317, 287, 239, 167 |
2.2.2. Xanthone Derivatives
Nr | tR (min) | Proposed Compound | λmax (nm) | Mode | Accurate Mass, exp. | Proposed Formula | Error (ppm) | Precursor Ion | LC-MS/MS Ions a,b |
---|---|---|---|---|---|---|---|---|---|
g | 16.28 | tetrahydroxyxanthone-C-hexoside dimer c | 259, 317, 365 | + | 843.1610 | C38H35O22 | −0.5 | 843 | 843, 827, 807, 789, 772, 759, 743, 729, 711, 705, 693, 687, 675, 669, 657, 651, 639, 627, 603, 598, 585, 573, 562, 555, 531, 479, 425, 417 |
− | 841.1494 | C38H33O22 | 0.5 | 841, CE = 45 V | 841, 823 , 805, 751, 733, 721, 703, 673, 661, 631, 613, 601, 589, 559, 527, 477, 437, 419, 401, 365, 359, 329, 313, 299, 271, 259 | ||||
k | 18.31 | tetrahydroxyxanthone-C-hexoside dimer c | 259, 318, 368 | + | 843.1597 | C38H35O22 | −2.7 | 843 | 843, 825, 808, 789, 771, 753, 729, 705, 687, 669, 651, 639, 627, 603, 585, 573, 555, 472, 425 |
− | 841.1463 | C38H33O22 | 0.0 | 841, CE = 45 V | 841, 823, 805, 751, 733, 721, 703, 691, 673, 661, 631, 613, 601, 589, 559, 437, 419, 407, 373, 359, 329, 313, 299, 271, 259 | ||||
l | 19.02 | tetrahydroxyxanthone-di-O,C-hexoside | 259, 314, 367 | + | 585.1454 | C25H29O16 | −0.3 | 585 | 405, 387, 369, 357, 351, 339, 327, 313, 303, 299, 285, 273, 261 |
− | 583.1287 | C25H27O16 | −2.1 | 583 | 583, 565, 493, 463, 421, 403, 331, 313, 301, 271, 259 | ||||
n | 21.17 | aspalathin derivative of (iso)mangiferin | 261, 319, 372 | + | 873.2104 | C40H41O22 | 1.7 | 873 | 819, 807, 731, 694, 675, 658, 631, 627, 616, 604, 591, 573, 561, 541, 525, 507, 489, 475, 459, 447, 439, 423, 405, 387, 369, 357, 345, 327, 313, 303, 289, 273, 261, 247, 217, 196, 163, 151, 149, 139, 123 |
− | 871.1948 | C40H39O22 | 1.7 | 871 | 871, 751, 691, 601, 571, 557, 539, 449, 437, 421, 331, 301, 269, 243 | ||||
r | 23.26 | nothofagin derivative of (iso)mangiferin | 261, 319, 372 | + | 857.2137 | C40H41O21 | −0.3 | 857 | 677, 659, 641, 623, 599, 575, 557, 541, 523, 509, 487, 475, 463, 447, 439, 423, 405, 387, 369, 357, 327, 303, 285, 273, 257, 245, 231, 151, 139, 119, 107 |
− | 855.1984 | C40H39O21 | 0.8 | 855 | 855, 837, 765, 735, 675, 657, 585, 555, 421, 403, 331, 313, 301 | ||||
4 | 25.23 | mangiferin (2-C-β-d-glucopyranosyl-1,3,6,7-tetrahydroxyxanthone) | 258, 318, 366 | + | 423.0931 | C19H19O11 | 0.9 | 423 | 369, 351, 339, 327, 313, 303, 299, 285, 273, 257 |
− | 421.0770 | C19H17O11 | −0.2 | 421 | 331, 313, 301, 285, 271, 259 | ||||
5 | 25.86 | isomangiferin (4-C-β-d-glucopyranosyl-1,3,6,7-tetrahydroxyxanthone) | 255, 316, 365 | + | 423.0929 | C19H19O11 | 0.5 | 423 | 387, 369, 357, 341, 327, 313, 303, 285, 273 |
− | 421.0762 | C19H17O11 | −2.1 | 421 | 331, 313, 301, 285, 271, 259 | ||||
y | 37.41 | tetrahydroxyxanthone-C-hexoside isomer | 258, 317, 366 | + | 423.0930 | C19H19O11 | 0.7 | 423 | 369, 351, 339, 327, 313, 303, 299, 285, 273, 257 |
− | 421.0777 | C19H17O11 | 1.4 | 421 | 331, 313, 301, 285, 271, 259 | ||||
aa | 44.24 | tetrahydroxyxanthone-C-hexoside isomer | 258, 318, 366 | + | 423.0948 | C19H19O11 | 5.0 | 423 | 351, 339, 327, 313, 303, 299, 285, 273, 257 |
− | 421.0771 | C19H17O11 | 0.0 | 421 | 331, 313, 301, 285, 271, 259 | ||||
cc | 50.68 | schoepfin A derivative of (iso)mangiferin | 261, 317, 368 | + | 841.2220 | C40H41O20 | 3.4 | 841 | 661, 643, 621, 583, 559, 541, 523, 509, 491, 475, 463, 439, 431, 423, 405, 387, 357, 351, 327, 303, 273, 257, 231 |
− | 839.2026 | C40H39O20 | −1.1 | 839 | 839, 821, 749, 719, 677, 551, 539, 527, 461, 449, 431, 421, 403, 331, 301, 271 |
Nr | tR (min) | Proposed Compound | λmax (nm) | Mode | Accurate Mass, exp. | Proposed Formula | Error (ppm) | Precursor Ion | LC-MS/MS Ions a,b |
---|---|---|---|---|---|---|---|---|---|
Amino Acids | |||||||||
1 | 2.83 | tyrosine | 225, 233, 274 (weak) | + | 182.0818 | C9H12NO3 | 0.5 | 182 | 182, 148, 136, 119, 107, 95, 91, 77 |
2 | 4.89 | phenylalanine | 225, 233, 259 (weak) | + | 166.0871 | C9H12NO2 | 1.8 | 166 | 120, 103, 91, 77 |
Glycosylated phenolic acids | |||||||||
e | 11.14 | dihydroxybenzoic acid-O-pentoside | 247, 289 sh, 314 | − | 285.0607 | C12H13O8 | −1.1 | 285 | 153, 152, 109, 108 |
h | 16.57 | dihydroxybenzoic acid-O-dipentoside | 290 (weak) | − | 417.1032 | C17H21O12 | −0.2 | 417 | 417, 285, 241, 153, 152, 109, 108 |
j | 16.77 | phenyllactic acid 2-O-hexoside | nd | − | 327.1080 | C15H19O8 | 0.0 | 327 | 165, 147, 103 |
m | 19.18 | coumaric acid-O-(pentosyl)hexoside | nd c | − | 457.1336 | C20H25O12 | −2.2 | 457 | 457, 325, 163, 119 |
o | 21.52 | caffeic acid-O-(pentosyl)hexoside | 225, 277 | − | 473.1281 | C20H25O13 | −3.0 | 473 | 473, 341, 323, 179, 135 |
Flavones | |||||||||
6 | 27.60 | apigenin-6,8-di-C-glucoside (vicenin-2) | 270, 330 | + | 595.1652 | C27H31O15 | −1.8 | 595 | 505, 457, 439, 427, 421, 409, 403, 391, 379, 355, 349, 337, 325, 307, 295 |
− | 593.1514 | C27H29O15 | 1.3 | 593 | 593, 575, 503, 485, 473, 455, 413, 395, 383, 365, 353 | ||||
10 | 48.10 | diosmetin-7-O-rutinoside (diosmin) | 260, 319 (weak) | + | 609.1819 | C28H33O15 | 0.0 | 609 | 301 |
− | 607.1673 | C28H31O15 | 1.6 | 607 | 299, 284 | ||||
Dihydrochalcones | |||||||||
x | 33.54 | 3-hydroxyphloretin-3',5'-di-C-hexoside | 285 | + | 615.1926 | C27H35O16 | 0.2 | 615 | 513, 495, 477, 465, 447, 435, 423, 411, 399, 381, 369, 357, 345, 327, 313, 301, 259, 247, 235, 217, 205, 193, 165, 123 |
− | 613.1771 | C27H33O16 | 0.3 | 613 | 505, 493, 475, 433, 415, 403, 385, 373, 361, 331, 251, 239, 209 | ||||
z | 39.26 | phloretin-3',5'-di-C-glucoside | 286 | + | 599.1971 | C27H35O15 | −0.8 | 599 | 497, 479, 461, 449, 431, 419, 413, 407, 395, 383, 377, 365, 353, 341, 329, 301, 259, 247, 235, 107 |
− | 597.1830 | C27H33O15 | 1.8 | 597 | 489, 477, 459, 429, 417, 399, 387, 369, 357, 345, 327, 315 |
2.2.3. Flavanones
Nr | tR (min) | Proposed Compound | λmax (nm) a | Mode | Accurate Mass, exp. | Proposed Formula | Error (ppm) | Precursor Ion | LC-MS/MS Ions b,c |
---|---|---|---|---|---|---|---|---|---|
p | 22.44 | eriodictyol-O-hexose-O-pentose | 225, 282 | + | 583.1705 | C26H31O15 | 7.2 | 583 | 356, 289, 219, 195, 154 |
− | 581.1508 | C26H29O15 | 0.3 | 581 | 581, 445, 419, 401, 313, 299, 287, 161, 151, 135, 125 | ||||
q1 | 22.90 | eriodictyol-O-hexose-O-pentose | 225, 282 d | + | 583.1436 | nd e | 583 | 289, 261, 195, 163 | |
− | 581.1519 | C26H29O15 | 2.2 | 581 | 581, 445, 419, 401, 299, 287, 161, 151, 135, 125 | ||||
q2 | 22.90 | eriodictyol-O-hexose-O-deoxyhexose | 225, 282 d | + | 597.1788 | C27H33O15 | −5.2 | 597 | 473, 313, 289, 195, 163 |
− | 595.1656 | C27H31O15 | −1.2 | 595 | 595, 459, 433, 313, 287, 169, 161, 151, 135, 125 | ||||
s | 24.38 | eriodictyol-O-hexose-O-deoxyhexose | 225, 282 | + | 597.1826 | C27H33O15 | 1.2 | 597 | 355, 289, 219, 195, 163 |
− | 595.1666 | C27H31O15 | 0.5 | 595 | 595, 459, 433, 313, 287, 169, 161, 151, 135, 125 | ||||
t | 28.54 | naringenin derivative | 278 (weak) | + | 567.1711 | C26H31O14 | −0.5 | 567 | 573, 569, 478, 452, 414, 404, 381, 372, 352, 339, 330, 301, 285, 273, 261, 236, 196, 173 |
− | 565.1545 | C26H29O14 | −2.1 | 565 | 565, 445, 419, 299, 271, 257, 227, 199, 179, 169, 149, 145, 125, 117 | ||||
u | 28.95 | naringenin derivative | 280 | + | 567.1668 | C26H31O14 | −8.1 | 567 | 285, 273, 261, 195 |
− | 565.1558 | C26H29O14 | 0.2 | 565 | 565, 445, 419, 299, 271, 257, 209, 203, 169, 149, 145, 125 | ||||
v | 29.28 | naringenin-O-hexose-O-deoxyhexose | 281 | + | 581.1891 | C27H33O14 | 3.6 | 581 | 351, 339, 315, 297, 285, 273, 261, 231, 219, 195, 165, 153, 147 |
− | 579.1722 | C27H31O14 | 1.4 | 579 | 579, 485, 459, 433, 415, 313, 271, 253, 209, 151, 145, 125 | ||||
w | 30.36 | naringenin-O-hexose-O-deoxyhexose | 280 | + | 581.1866 | C27H33O14 | −0.7 | 581 | 351, 339, 315, 297, 285, 273, 261, 251, 231, 219, 195, 147 |
− | 579.1722 | C27H31O14 | 1.4 | 579 | 579, 485, 459, 433, 415, 313, 271, 253, 209, 169, 151, 145, 125 | ||||
7 | 33.35 | eriodictyol-7-O-rutinoside (eriocitrin) | 281 | + | 597.1812 | C27H33O15 | −1.2 | 597 | 289 |
− | 595.1664 | C27H31O15 | 0 | 595 | 595, 459, 287, 175, 151, 135, 125, 107, 83 | ||||
8 | 39.47 | naringenin-7-O-rutinoside (narirutin) | 280 | + | 581.1856 | C27H33O14 | −2.4 | 581 | 339, 315, 289, 285, 273, 263, 245, 219, 195, 163, 153, 147 |
− | 579.1688 | C27H31O14 | −4.5 | 579 | 313, 295, 271, 151 | ||||
9 | 43.58 | hesperetin-7-O-rutinoside (hesperidin) | 283 | + | 611.1976 | C28H35O15 | 0.0 | 611 | 303 |
− | 609.1834 | C28H33O15 | 2.5 | 609 | 301 | ||||
bb | 44.43 | naringenin-O-deoxyhexose(1→2) hexose | nd d | + | 581.1869 | C27H33O14 | −0.2 | 581 | 315, 273, 231, 219, 195, 153, 147 |
− | 579.1691 | C27H31O14 | −4.0 | 579 | 579, 485, 459, 433, 415, 313, 271, 253, 209, 177, 151, 145, 125 |
2.2.4. Amino Acids
2.2.5. Glycosylated Phenolic Acids
2.2.6. Flavones
2.2.7. Dihydrochalcones
2.3. HPLC-DAD Method Validation
Phenolic Standard | Number of Calibration Points, n | Wavelength, nm | Linearity Range, µg on-column | Regression Equation a | Correlation Coefficient, r2 |
---|---|---|---|---|---|
Maclurin | 6 | 320 | 0.0202–0.2527 | y = 2034.4 x + 1.3312 | 0.9999 |
Mangiferin b | 7 | 320 | 0.0364–3.6422 | y = 2114.9 x + 1.9834 | 0.9999 |
Vicenin-2 b | 8 | 320 | 0.0060–0.9008 | y = 1647.0 x – 2.3668 | 0.9995 |
Aspalathin | 6 | 288 | 0.0301–0.3760 | y = 2305.6 x + 3.9468 | 0.9999 |
Eriocitrin | 6 | 288 | 0.0200–0.2500 | y = 1607.5 x + 1.7281 | 0.9999 |
Narirutin | 7 | 288 | 0.0200–0.3340 | y = 1584.9 x + 1.7940 | 0.9999 |
Hesperidin | 6 | 288 | 0.0776–0.9700 | y = 1631.5 x + 2.1973 | 0.9999 |
2.4. Quantification of Phenolic Compounds
Nr | Compound | Unfermented Extract | Fermented Extract |
---|---|---|---|
a | Maclurin-di-O,C-hexoside a | 0.096 | 0.117 |
b | Iriflophenone-di-O,C-hexoside b | 6.101 | 5.540 |
c | Maclurin-3-C-glucoside a | 0.173 | 0.041 |
A | Unidentified compound c | 0.159 | 0.105 |
3 | Iriflophenone-3-C-glucoside | 1.222 | 0.498 |
k | Tetrahydroxyxanthone-C-hexoside dimer d | nq e | 0.074 |
l | Tetrahydroxyxanthone di-O,C-hexoside d | 0.190 | 0.080 |
s | Eriodictyol-O-hexose-O-deoxyhexose f | 0.143 | 0.100 |
4 | Mangiferin | 13.791 | 6.966 |
5 | Isomangiferin | 1.617 | 0.907 |
6 | Vicenin-2 | 0.493 | 0.420 |
v | Naringenin-O-hexose-O-deoxyhexose g | 0.147 | 0.206 |
w | Naringenin-O-hexose-O-deoxyhexose g | 0.441 | 0.219 |
7 | Eriocitrin | 0.045 | 0.041 |
x | 3-Hydroxyphloretin-3',5'-di-C-hexoside h | 0.125 | 0.029 |
y | Tetrahydroxyxanthone-C-hexoside isomer d | 0.109 | 0.053 |
z | Phloretin-3',5'-di-C-glucoside i | 0.273 | 0.145 |
9 | Hesperidin | 0.374 | 0.268 |
3. Experimental Section
3.1. Chemicals
3.2. Sample Preparation
3.3. HPLC-DAD Method Development
3.4. Optimized HPLC-DAD Method
3.5. LC-DAD-ESI-MS and -MS/MSAnalyses
3.6. HPLC-DAD Method Validation
3.7. Quantification of Phenolic Compounds in Freeze-Dried Aqueous Extracts of C. genistoides
4. Conclusions
Supplementary Materials
Supplementary Files
Supplementary File 1Acknowledgments
Author Contributions
Conflicts of Interest
References
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Beelders, T.; De Beer, D.; Stander, M.A.; Joubert, E. Comprehensive Phenolic Profiling of Cyclopia genistoides (L.) Vent. by LC-DAD-MS and -MS/MS Reveals Novel Xanthone and Benzophenone Constituents. Molecules 2014, 19, 11760-11790. https://doi.org/10.3390/molecules190811760
Beelders T, De Beer D, Stander MA, Joubert E. Comprehensive Phenolic Profiling of Cyclopia genistoides (L.) Vent. by LC-DAD-MS and -MS/MS Reveals Novel Xanthone and Benzophenone Constituents. Molecules. 2014; 19(8):11760-11790. https://doi.org/10.3390/molecules190811760
Chicago/Turabian StyleBeelders, Theresa, Dalene De Beer, Maria A. Stander, and Elizabeth Joubert. 2014. "Comprehensive Phenolic Profiling of Cyclopia genistoides (L.) Vent. by LC-DAD-MS and -MS/MS Reveals Novel Xanthone and Benzophenone Constituents" Molecules 19, no. 8: 11760-11790. https://doi.org/10.3390/molecules190811760