HPLC-qTOF-MS/MS-Based Profiling of Flavan-3-ols and Dimeric Proanthocyanidins in Berries of Two Muscadine Grape Hybrids FLH 13-11 and FLH 17-66
Abstract
:1. Introduction
2. Results
2.1. Metabolite Peak Profile Comparison among FLH 13-11, FLH 17-66, and Standards
2.2. HPLC-qTOF-MS/MS Based Characterization of Flavan-3-ol Aglycones, Conjugates, and Dimeric PAs Standards
2.3. Flavan-3-ol Aglycone Profiles in Extracts
2.4. Flavan-3-ol Conjugate Profiles in Extracts
2.5. Dimeric Proanthocyanidin Profiles in Extracts
3. Discussion
4. Materials and Methods
4.1. Chemical Agents and Standards
4.2. Plant Material
4.3. Extraction of Flavan-3-ols
4.4. High Performance Liquid Chromatograph-Quadrupole Time-of-Flight-Tandem Mass Spectrometer (HPLC-qTOF-MS/MS) Analysis
4.5. Structure Annotation
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Standards | MW (g/mol) | RT (min) | [M − H]⁻ (m/z) | [MS/MS] (m/z) |
---|---|---|---|---|
(+)-Catechin | 290.26 | 12.761 | 289.0558 | 109.0140- 121.0136- 123.0289- 125.0089- 137.0078- 145.088- 151.0230- 159.0238- 187.0227- 203.0529- 212.0308- 221.0634- 245.0640 |
(−)-Epicatechin | 290.27 | 15.619 | 289.0558 | 109.0137- 121.0131- 123.0286- 125.0089- 137.0079- 151.0218- 159.0276- 187.0225- 203.0532- 212.0306- 221.0627- 245.0619 |
(−)-Gallocatechin | 306.27 | 9.166 | 305.0495 | 109.0178- 121.0176- 123.0291- 125.0117- 137.0116- 151.0274- 159.0318- 167.0204- 175.0250- 179.0199- 186.0174- 203.0183- 219.0500 |
(−)-Epigallocatechin | 306.27 | 10.338 | 305.0518 | 109.0152- 121.0157- 123.0273- 125.0097- 137.0096- 151.0257- 159.0288- 167.0191- 175.0235- 179.0157- 189.0375- 203.0180- 219.0513 |
(−)-Catechin gallate | 442.37 | 23.590 | 441.0686 | 109.0153- 121.0145- 123.0298- 125.0095- 137.0092- 151.0245- 159.0293- 168.9982- 175.0565- 179.0196- 189.0382- 203.0543- 221.0658- 245.0653- 271.0450- 289.0552 |
(−)-Epigallocatechin gallate | 458.00 | 16.149 | 457.0565 | 109.0146- 121.0144- 122.9944- 125.0088- 137.0081- 151.0229- 159.0277- 168.9973- 179.0193- 192.9972- 204.0225- 221.0277- 244.0435- 269.0319- 287.0353- 305.0463 |
(−)-Gallocatechin gallate | 458.00 | 15.872 | 457.0577 | 109.0152- 121.0145- 122.9962- 125.0097- 137.0087- 151.0233- 159.0286- 168.9982- 179.0194- 189.0340- 203.0197- 221.0312- 245.0261- 269.0258- 287.0393- 305.0486 |
Procyanidin B1 | 578.52 | 10.441 | 577.1225 | 109.0138- 121.0139- 123.0284- 125.0081- 137.0077- 151.0232- 159.0269- 161.0097- 163.0197- 179.0178- 189.0348- 203.0529- 221.0645- 245.0625- 271.0448- 287.0327- 289.0541- 299.0364- 315.0697- 321.0582- 339.0693- 407.0601- 425.0709 |
Procyanidin B2 | 578.52 | 13.674 | 577.1224 | 109.0132- 121.0146- 123.0283- 125.0082- 137.0086- 151.0221- 159.0269- 161.0093- 163.0232- 179.0196- 189.0369- 203.0519- 221.0643- 245.0621- 271.0435- 286.0298- 289.0535- 297.0203- 315.0647- 339.0721- 407.0602- 425.0712 |
Compound | MW (g/mol) | Cultivar | Year of Harvest | Ret. Tim (min) | [M − H]− (m/z) | [MS/MS] (m/z) Profiles | Figure # | |
---|---|---|---|---|---|---|---|---|
2011 | 2012 | |||||||
(+)-Catechin | 290.26 | FLH 13-11 | √ | √ | 12.806 | 289.1574 | 109.0815- 123.1001- 137.0823- 145.0888- 151.1007- 163.1031- 173.0911- 191.1035- 203.1362- 219.1033- 247.1028 | Figure 3 |
FLH 17-66 | – | – | – | – | ||||
(−)-Catechin | 290.26 | FLH 13-11 | √ | √ | 12.872 | 289.1586 | 109.0824- 123.1012- 137.0835- 145.0903- 151.1025- 163.1047- 173.0926- 191.1046- 203.1395- 219.1048- 247.1045 | Figure S1 |
FLH 17-66 | – | – | – | – | ||||
(+)-Epicatechin | 290.27 | FLH 13-11 | √ | √ | 15.029 | 289.1574 | 109.0817- 123.1005- 137.0835- 151.1017- 161.1221- 175.1292- 188.1158- 203.1425- 212.1182- 221.1558- 247.1014 | Figure S2 |
FLH 17-66 | √ | – | 15.277 | 289.0377 | 109.0083- 123.0218- 137.0031- 148.9987- 159.0178- 173.0298- 191.0071- 202.0256- 221.0492- 245.0482 | |||
(−)-Epicatechin | 290.27 | FLH 13-11 | √ | √ | 15.629 | 289.1574 | 109.0819- 123.1007- 137.0831- 151.1016- 159.1082- 175.1354- 187.1087- 203.1421- 212.1219- 221.1560- 245.1602- 271.1448 | Figure 4 |
FLH 17-66 | √ | √ | 15.398 | 289.0357 | 109.0068- 123.0213- 136.9995- 151.0132- 159.0190- 173.0333- 187.0109- 203.0421- 221.0480- 246.9843 |
Compound | MW (g/mol) | Cultivar | Year of Harvest | Ret. Tim (min) | [MS]⁻ (m/z) | [MS/MS] (m/z) Profiles | Figure # | |
---|---|---|---|---|---|---|---|---|
2011 | 2012 | |||||||
(+)-Catechin 3-O-glucoside | 452.41 | FLH 13-11 | – | √ | 6.8 | 451.1255 | 101.0781- 108.9543- 109.0471- 110.9518- 112.9492- 125.0775- 149.0708- 169.0195- 195.2629- 206.0349- 229.0525- 247.1017- 276.9698- 350.9955- 404.0989 | Figure 5 |
FLH 17-66 | – | – | – | – | ||||
(−)-Catechin 3-O-glucoside | 452.41 | FLH 13-11 | – | √ | 6.991 | 451.1255 | 101.0752- 108.9545- 109.9014- 110.9520- 112.9487-125.0556- 132.8862- 149.0722- 201.1385- 215.1058- 245.1000- 263.1016- 273.0970- 301.7091- 337.1560- 350.9861- 393.1542- 408.0436 | Figure S3 |
FLH 17-66 | – | – | – | – | ||||
(+)-Epicatechin 3-O-glucoside | 452.41 | FLH 13-11 | – | – | – | – | Figure S4 | |
FLH 17-66 | √ | √ | 14.185 | 451.0948 | 100.9949- 112.9969- 124.9885- 136.9909- 152.0334- 168.9777- 188.9751- 216.9631- 229.9739- 246.9749- 258.9704- 272.9450- 287.9723- 300.9451- 343.9958- 391.0083 | |||
(−)-Epicatechin 3-O-glucoside | 452.41 | FLH 13-11 | – | – | – | – | Figure 6 | |
FLH 17-66 | – | √ | 14.382 | 451.0918 | 100.9883- 112.9861- 124.9861- 144.9843- 162.9523- 172.9705- 188.9668- 201.9933- 216.9551- 228.9873- 244.9449- 255.4556- 272.9346- 286.9428- 300.9102- 380.9437 | |||
(+)-Catechin gallate | 442.37 | FLH 13-11 | √ | √ | 23.159 | 441.1883 | 109.0819- 125.0805- 137.0829- 151.1012- 161.1235- 169.0794- 179.1017- 193.0835- 203.1424- 221.1560- 245.1601- 259.1415- 271.1424- 289.1571- 303.1370- 331.1358- | Figure 7 |
FLH 17-66 | √ | √ | 23.436 | 441.0366 | 109.0071- 125.0001- 136.9989- 151.0130- 161.0310- 168.9854- 179.0047- 192.9813- 203.0387- 211.0086- 221.0537- 245.0485- 256.0208- 289.0349 | |||
(−)-Catechin gallate | 442.37 | FLH 13-11 | √ | √ | 23.795 | 441.1883 | 109.0820- 125.0805- 137.0833- 151.1014- 169.0795- 179.1017- 193.0838- 203.1422- 221.1563- 245.1603- 271.1434- 289.1570- 303.1388- 331.1365 | Figure S5 |
FLH 17-66 | √ | √ | 23.84 | 441.04 | 109.0075- 125.0004- 136.9990- 151.0140- 161.0307- 168.9855- 187.0088- 203.0416- 221.0477- 245.0471- 259.0269- 271.0268- 289.0332 | |||
(+)-Epicatechin gallate | 442.37 | FLH 13-11 | – | √ | 25.094 | 441.1883 | 109.0821- 125.0805- 137.0831- 151.1013- 169.0792- 179.1019- 188.1141- 193.0832- 203.1421- 209.1312- 221.1577- 245.1607- 259.1414- 271.1441- 289.1568- 303.1366 | Figure S6 |
FLH 17-66 | √ | √ | 25.665 | 441.0366 | 109.0070- 125.0005- 137.0002- 146.0097- 151.0127- 163.0083- 188.0163- 203.0384- 221.0529- 235.1838- 245.0512- 265.3904- 289.0262- 342.0549- 379.8921 | |||
(−)-Epicatechin gallate | 442.37 | FLH 13-11 | √ | √ | 25.818 | 441.1892 | 109.0836- 125.0810- 137.0830- 151.1038- 164.0731- 179.1025- 187.1074- 195.0042- 203.1427- 221.1591- 245.1588- 254.1340- 275.1032- 289.1590- 301.1176- 315.1329- | Figure 8 |
FLH 17-66 | √ | √ | 26.312 | 441.0366 | 109.0065- 123.0209- 137.0003- 145.0019- 151.0112- 161.0320- 179.0064- 188.0159- 203.0415- 221.0426- 235.0150- 245.0452- 258.9808- 271.0298- 289.0319- 313.9907- 331.9910- 358.9829- 403.7133 | |||
(+)-Gallocatechin 3-O-glucoside | 468.00 | FLH 13-11 | – | – | – | – | Figure S7 | |
FLH 17-66 | √ | – | 17.476 | 467.9999 | 106.9921- 125.0015- 133.9739- 157.0012- 168.9887- 179.0102- 200.9870- 228.9835- 246.9902- 274.9884- 300.9626- 317.0175- 346.9813- 367.9021- 432.2409- 465.6268 | |||
(−)-Gallocatechin 3-O-glucoside | 468.00 | FLH 13-11 | – | – | – | – | Figure S8 | |
FLH 17-66 | √ | – | 17.656 | 467.9999 | 106.9969- 125.0027- 135.0205- 168.9884- 184.9934- 210.9862- 228.9798- 250.0131- 274.9883- 283.9547- 300.9604- 315.9707- 338.4035- 367.0427- | |||
(+)-Epigallocatechin 3-O-glucoside | 468.00 | FLH 13-11 | – | – | – | – | Figure S9 | |
FLH 17-66 | √ | √ | 18.234 | 467.9974 | 106.9919- 124.9998- 145.0057- 156.9997- 168.1867- 184.9947- 200.9880- 228.9807- 244.9756- 256.9695- 274.9827- 290.9684- 300.9618- 313.0098 | |||
(−)-Epigallocatechin 3-O-glucoside | 468.00 | FLH 13-11 | – | – | – | – | Figure S10 | |
FLH 17-66 | √ | √ | 18.875 | 467.9974 | 106.9919- 125.0000- 145.0007- 159.0135- 168.9849- 184.9949- 200.9831- 228.9837- 256.9720- 274.9860- 300.9609- 313.0135- 340.0573- 465.0236 | |||
O-Methylated (+)-Catechin gallate | 456.00 | FLH 13-11 | √ | √ | 22.362 | 455.3199 | 101.0748- 113.0764- 125.0799- 131.0919- 143.0946- 161.1074- 169.0767- 189.0931- 217.0827- 245.1269- 263.2316- 274.0943- 283.1247- 291.0934- 301.0835- 311.6865- 329.1163- 340.0422- 355.0671- 399.0656 | Figure S11 |
FLH 17-66 | – | – | – | – | ||||
O-Methylated (−)-Catechin gallate | 456.00 | FLH 13-11 | – | √ | 22.928 | 455.3199 | 101.0749- 113.0780- 125.0801- 132.0988- 143.0908- 161.1085- 173.0920- 191.0647- 217.0746- 247.0945- 263.2333- 295.0561- 311.1188- 340.0548- 355.0660- 375.2308- 399.0789 | Figure S12 |
FLH 17-66 | – | – | – | – | ||||
O-Methylated (+/−)-Epicatechin gallate | 456.00 | FLH 13-11 | √ | √ | 30.36 | 455.2054 | 107.0648- 11.0601- 125.0799- 139.1013- 149.0834- 169.0778- 173.0796- 185.1217- 191.1028- 202.1402- 217.0770- 226.1377- 235.1698- 259.1825- 270.1331- 285.1589- 303.1738- 315.0628- 335.0702- 361.2071 | Figure S13 |
456.00 | FLH 17-66 | – | √ | 30.839 | 455.0504 | 106.9945- 124.9977- 136.9965- 148.9984- 168.9866- 177.0170- 183.0117- 196.8803- 202.0292- 217.0550- 220.0302- 228.0043- 241.0177- 253.9952- 269.0249- 274.9825- 285.0435- 303.0430- 310.9758- 348.2291- 387.2122- 446.0391 | ||
O-Methylated (−)-Gallocatechin gallate | 472.40 | FLH 13-11 | √ | – | 24.923 | 471.2039 | 107.0656- 109.0812- 125.0809- 137.0832- 145.0904- 151.1014- 161.0884- 169.0798- 183.1141- 201.1258- 213.1294- 225.1304- 243.1426- 257.1262- 269.1280- 287.1421- 303.1401- 313.1232 | Figure S14 |
FLH 17-66 | – | – | – | – | ||||
O-Methylated (+)-Epigallocatechin gallate | 472.40 | FLH 13-11 | – | – | – | – | Figure S15 | |
FLH 17-66 | √ | – | 25.018 | 471.0486 | 106.9918- 125.0014- 151.0132- 160.9981- 168.9872- 183.0166- 201.0280- 213.0195- 225.0247- 243.0342- 257.0042- 269.0087- 288.0210- 303.0141 | |||
O-Methylated (−)-Epigallocatechin gallate | 472.40 | FLH 13-11 | – | – | – | – | Figure S16 | |
FLH 17-66 | √ | – | 25.347 | 471.0486 | 106.9950- 124.9992- 133.0056- 151.0090- 160.9945- 164.9891- 168.9837- 173.0359- 178.9967- 183.0169- 188.0060- 199.0158- 213.0245- 241.0151- 269.0020- 297.9831- 313.9682- 337.9594 |
Compounds | MW (g/mol) | Cultivar | Year of Harvest | Ret. Tim (min) | MS⁻ (m/z) | [MS/MS] (m/z) Profiles | Figure # | |
---|---|---|---|---|---|---|---|---|
2011 | 2012 | |||||||
Procyanidin A2 | 576.51 | FLH 13-11 | √ | √ | 35.193 | 575.2385 | 125.0804- 137.0830- 151.0966- 161.0901- 169.0802- 175.1030- 191.0990- 201.1213- 217.1222- 229.1250- 243.1107- 257.1236- 271.1085- 287.1407- 351.0316- 394.1682- 407.1760- 449.1959 | Figure 9 |
FLH 17-66 | √ | √ | 35.684 | 575.0652 | 109.0070- 124.9985- 136.9988- 152.9935- 160.9962- 168.9837- 175.0088- 187.0083- 199.0077- 215.0015- 227.000- 230.9939- 242.9965- 257.0099- 270.9877- 285.0011- 296.9985- 312.9930- 327.0119- 378.0426- 394.0270- 407.0324- 425.0363- 449.0414 | |||
Procyanidin B1 [epicatechin-(4β→8)-catechin] | 578.52 | FLH 13-11 | √ | – | 10.008 | 577.2579 | 109.0823- 125.0812- 137.0845- 151.0997- 161.0911- 179.1013- 187.1092- 205.1215- 217.1259- 229.1257- 245.1596- 256.1226- 273.1247- 281.1328- 289.1590- 297.1640- 339.1805- 381.1925- 393.1828- 407.1804- 425.1916- 451.2157 | Figure S17 |
FLH 17-66 | – | √ | 10.068 | 577.0828 | 108.9944- 124.9868- 136.9845- 152.9751- 160.9802- 174.9912- 203.0163- 229.9978- 245.0179- 254.9655- 272.9779- 289.0023- 297.9319- 312.9674- 339.0092- 406.9878 | |||
Procyanidin B2 [epicatechin-(4β→8)-epicatechin] | 578.52 | FLH 13-11 | √ | √ | 13.528 | 577.2551 | 109.0809- 125.0801- 137.0810- 149.0838- 161.0938- 165.0838- 175.1065- 191.1055- 205.1202- 229.1258- 245.1590- 269.1261- 289.1558- 329.1543- 367.2092- 393.1943- 407.1765- 439.2095- 533.2681 | Figure 10 |
FLH 17-66 | √ | √ | 13.21 | 577.0828 | 109.0032- 124.9960- 136.9946- 151.0073- 160.9936- 175.0059- 187.0037- 203.0321- 221.0419- 229.0106- 245.0374- 254.9878- 268.9982- 280.9984- 289.0235- 339.0328- 389.0147- 407.0181- 425.0330 | |||
Procyanidin B4 [catechin-(4β→8)-epicatechin] | 578.52 | FLH 13-11 | √ | √ | 12.24 | 577.2551 | 109.0814- 125.0805- 137.0823- 149.0852- 165.0824- 179.1032- 191.1036- 201.1267- 205.1212- 227.1137- 247.1403- 269.1262- 289.1557- 329.1593- 353.1942- 367.2122- 393.1957- 407.1776- 425.1887- 439.2070 | Figure S18 |
FLH 17-66 | – | √ | 12.407 | 577.0828 | 109.0231- 125.0156- 137.0162- 149.0119- 163.0261- 165.0054- 177.0335- 191.0167- 201.0358- 215.0238- 227.0187- 241.0249- 269.0177- 289.0338- 367.0710- 404.0440- 439.0388- 541.0047 | |||
Procyanidin B5 [epicatechin-(4β→6)-epicatechin] | 578.52 | FLH 13-11 | √ | √ | 21.369 | 577.2193 | 109.0808- 125.0802- 137.0823- 151.1006- 161.0891- 165.0832- 179.0649- 187.1050- 205.1192- 229.1270- 245.1575- 271.1073- 289.1563- 316.1109- 329.1598- 339.1809- 359.1454- 381.1959- 407.1782- 425.1849- 439.2071- 451.2220- 463.1951 | Figure S19 |
FLH 17-66 | – | √ | 21.467 | 577.0828 | 109.0011- 124.9934- 136.9912- 151.0032- 160.9909- 175.0013- 187.0008- 203.0265- 214.9922- 227.0197- 245.0321- 255.9888- 270.9718- 280.9948- 289.0166- 315.9665- 339.0265- 407.0129- 463.0166 | |||
Procyanidin B6 [catechin-(4β→6)-catechin] | 578.52 | FLH 13-11 | √ | √ | 12.886 | 577.2551 | 109.0813- 125.0800- 137.0824- 151.1011- 161.0883- 165.0837- 179.1019- 187.1074- 205.1203- 229.1273- 245.1579- 273.1228- 289.1562- 329.1583- 339.1792- 357.1931- 407.1774- 425.1894-439.2095- 451.2070 | Figure S20 |
FLH 17-66 | – | – | – | – | ||||
Procyanidin B7 [epicatechin-(4β→6)-catechin] | 578.52 | FLH 13-11 | √ | √ | 20.289 | 577.2551 | 109.0793- 125.0802- 137.0822- 149.0840- 165.0846- 179.1029- 189.1219- 207.1402- 229.1203- 243.1446- 271.1450- 289.1552- 301.1616- 329.1578- 353.1956- 377.1962- 407.1900- 425.1968- 439.2060- 449.2324- 475.2127- 509.2548- 533.2597- 559.2447 | Figure S21 |
FLH 17-66 | – | – | – | – | ||||
Procyanidin B8 [catechin-(4β→6)-epicatechin] | 578.52 | FLH 13-11 | √ | – | 11.255 | 577.2579 | 109.0822- 125.0815- 137.0833- 151.1016- 161.0898- 165.0855- 175.1072- 187.1098- 205.1217- 229.1266- 245.1602- 256.1230- 273.1279- 289.1577- 299.1461- 329.1573- 339.1795- 381.2008- 407.1800- 425.1916- 439.2084- 451.2077 | Figure S22 |
FLH 17-66 | – | – | – | – |
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Yuzuak, S.; Ballington, J.; Xie, D.-Y. HPLC-qTOF-MS/MS-Based Profiling of Flavan-3-ols and Dimeric Proanthocyanidins in Berries of Two Muscadine Grape Hybrids FLH 13-11 and FLH 17-66. Metabolites 2018, 8, 57. https://doi.org/10.3390/metabo8040057
Yuzuak S, Ballington J, Xie D-Y. HPLC-qTOF-MS/MS-Based Profiling of Flavan-3-ols and Dimeric Proanthocyanidins in Berries of Two Muscadine Grape Hybrids FLH 13-11 and FLH 17-66. Metabolites. 2018; 8(4):57. https://doi.org/10.3390/metabo8040057
Chicago/Turabian StyleYuzuak, Seyit, James Ballington, and De-Yu Xie. 2018. "HPLC-qTOF-MS/MS-Based Profiling of Flavan-3-ols and Dimeric Proanthocyanidins in Berries of Two Muscadine Grape Hybrids FLH 13-11 and FLH 17-66" Metabolites 8, no. 4: 57. https://doi.org/10.3390/metabo8040057
APA StyleYuzuak, S., Ballington, J., & Xie, D. -Y. (2018). HPLC-qTOF-MS/MS-Based Profiling of Flavan-3-ols and Dimeric Proanthocyanidins in Berries of Two Muscadine Grape Hybrids FLH 13-11 and FLH 17-66. Metabolites, 8(4), 57. https://doi.org/10.3390/metabo8040057