Table 2.
UHPLC–HRMS data of cinnamon metabolites.
| Peak | Rt (min) |
m/z | Adduct type | Formula | Error (ppm) |
Major fragment ions | aTentative identification |
|---|---|---|---|---|---|---|---|
| 1 | 12.44 | 510.2186 | [M+C2H7N+H]+ | C19H28O13 | 0.95 | 510→171.0650(100). 267.0864(76) |
Cinnacassoside C |
| 487.1427 | [M+Na]+ | 1.0 | |||||
| 465.1605 | [M+H]+ | 0.5 | |||||
| 2 | 12.85 | 1153.2607 | [M+H]+ | C60H48O24 | -0.07 | 247.0605(33), 287.0549(100), 695.5070(24) | A-type PAC DP-4 (A=1) |
| 3 | 12.86 | 508.2491 | [M+C2H7N+H]+ | C20H30O12 | 0.49 | 508→133.0645(62), 151.0751(48), 265.1069(100) | 3-Methoxy-4-hydroxyphenylethyl 6-O-pentofuranosylhexopyranoside |
| 485.1633 | [M+Na]+ | 0.73 | |||||
| 463.1812 | [M+H]+ | 0.43 | |||||
| 4 | 13.05 | 579.1498 | [M+H]+ | C30H26O12 | 0.34 | 127.0386(96), 289.0706(100), 291.0862(88) | B-type PAC DP-2 |
| 5 | 13.24 | 579.1498 | [M+H]+ | C30H26O12 | 0.34 | 127.0388(100), 289.0708(82), 291.0865(82) | B-type PAC DP-2 |
| 6 | 13.91 | 494.2236 | [M+C2H7N+H]+ | C19H28O12 | 0.81 | 466→115.0387(75), 155.0700(100), 179.0700(94), 251.0912(90) | 3,4-Dimethoxyphenyl 6-O-apiofuranosylglucopyranoside |
| 471.1477 | [M+Na]+ | 0.86 | |||||
| 466.1922 | [M+NH4]+ | 0.64 | |||||
| 7 | 14.04 | 1153.2607 | [M+H]+ | C60H48O24 | −0.07 | 247.0595(56), 287.0549(100), 664.3065(30), 766.9262(30) | A-type PAC DP-4 (A=1) |
| 8 | 14.37 | 1441.3245 | [M+H]+ | C75H60O30 | 0.28 | 1441→287.0547(100), 672.6395(80),1031.6045(63), 1201.3632(69) | A-type PAC DP-5 (A=1) |
| 721.1664 | [M+2H]2+ | 0.65 | |||||
| 9 | 14.64 | 1441.3237 | [M+H]+ | C75H460O30 | −0.52 | 1441→247.0591(53), 287.0543(100), 289.0692(27) | A-type PAC DP-5 (A=1) |
| 721.1662 | [M+2H]2+ | 0.45 | |||||
| 10 | 15.31 | 579.1500 | [M+H]+ | C30H26O12 | 0.45 | 127.0387(97), 289.0705(74), 291.0861(100) | B-type PAC DP-2 |
| 11 | 15.43 | 1153.2600 | [M+H]+ | C60H48O24 | –0.71 | 247.0595(42), 287.0549(100), 289.0710(33) | A-type PAC DP-4 (A=1) |
| 12 | 15.55 | 524.2340 | [M+C2H7N+H]+ | C20H30O13 | 0.45 | 496→185.0807(100), 227.0914(24), 281.1021(28), 317.1232(13) | 3,4,5-Trimethoxyphenyl 6-O-apiofuranosylglucopyranoside |
| 501.1583 | [M+Na]+ | 0.87 | |||||
| 496.2029 | [M+NH4]+ | 0.87 | |||||
| 479.1758 | [M+H]+ | −0.12 | |||||
| 13 | 15.96 | 827.2940 | [2M+Na]+ | C18H26O10 | −0.50 | 420→115.0387(100), 133.0493(85), 223.0964(29), 295.1023(17) | Benzyl 6-O- pentofuranosylhexopyranoside |
| 448.2177 | [M+C2H7N+H]+ | −0.05 | |||||
| 425.1420 | [M+Na]+ | 0.43 | |||||
| 420.1866 | [M+NH4]+ | 0.18 | |||||
| 14 | 16.06 | 291.0866 | [M+H]+ | C15H14O6 | −0.22 | 123.0440(51), 139.0389(100), 165.0547(26) | bEpicatechin |
| 15 | 16.53 | 865.1976 | [M+H]+ | C45H36O18 | 0.16 | 287.0549(100), 301.0716(24), 533.1079(21), 575.1190(4) | A-type PAC DP-3 (A=1) |
| 16 | 16.57 | 374.1815 | [M+C2H7N+H]+ | C15H20O8 | 1.5 | 346→121.0646(8), 149.0595(67), 167.0702(100) | Dihydrocinnacasside |
| 351.1054 | [M+Na]+ | 1.0 | |||||
| 346.1501 | [M+NH4]+ | 0.46 | |||||
| 17 | 16.93 | 506.2238 | [M+C2H7N+H]+ | C20H28O12 | 1.2 | 478→115.0389(34), 133.0495(29), 167.0702(100) | Apiopaeonoside |
| 483.1479 | [M+Na]+ | 1.2 | |||||
| 478.1925 | [M+NH4]+ | 0.60 | |||||
| 18 | 16.96 | 314.1388 | [M+NH4]+ | C18H16O4 | 0.37 | 297→237.0909(24), 265.0860(100) |
2-Cinnamoyl-5-methoxyphenyl acetate |
| 297.1123 | [M+H]+ | 0.16 | |||||
| 19 | 17.18 | 867.2129 | [M+H]+ | C45H38O18 | −0.19 | 127.0388(80), 289.0706(100), 291.0863(60), 579.1486(26) | B-type PAC DP-3 |
| 20 | 17.23 | 865.1973 | [M+H]+ | C45H36O18 | −0.14 | 287.0548(100), 301.0711(32), 533.1029(28) | A-type PAC DP-3 (A=1) |
| 21 | 17.60 | 1155.2771 | [M+H]+ | C60H50O24 | 0.62 | 276.1558(100), 289.0701(85), 291.0869(100) | B-type PAC DP-4 |
| 22 | 17.62 | 328.1544 | [M+H]+ | C19H21NO4 | 0.07 | 265.0857(52), 297.1119(100) | Unknown alkaloid |
| 23 | 17.79 | 1443.3407 | [M+H]+ | C75H62O30 | 0.83 | 146.2928(100), 1138.4525(52) | B-type PAC DP-5 |
| 24 | 17.95 | 1153.2607 | [M+H]+ | C60H48O24 | −0.13 | 339.2633(97), 507.2888(94), 739.7498(100), 864.5703(97) | A-type PAC DP-4 (A=1) |
| 25 | 18.06 | 590.3176 | [M+C2H7N+H]+ | C26H40O12 | 0.84 | 590→383.2064(100) | Cinnacaside |
| 567.2418 | [M+Na]+ | 1.1 | |||||
| 545.2598 | [M+H]+ | 0.55 | |||||
| 26 | 18.12 | 1443.3405 | [M+H]+ | C75H62O30 | 0.63 | 173.4246(100), 1342.9332(76) | B-type PAC DP-5 |
| 27 | 18.51 | 183.0651 | [M+H]+ | C9H10O4 | −0.09 | 95.0491(62), 123.0440(100) | Dimethoxybenzoic acid |
| 28 | 18.56 | 330.1701 | [M+H]+ | C19H23NO4 | 0.35 | 192.1019(100) | Unknown alkaloid |
| 29 | 20.33 | 579.1502 | [M+H]+ | C30H26O12 | 0.50 | 127.0387(87), 289.0707(83), 291.0864(100) | B-type PAC DP-2 |
| 30 | 21.07 | 879.3253 | [2M+Na]+ | C20H28O10 | −0.47 | 446→117.0697(100) | Rosavin |
| 474.2236 | [M+C2H7N+H]+ | 0.48 | |||||
| 451.1577 | [M+Na]+ | 0.51 | |||||
| 446.2022 | [M+NH4]+ | 0.13 | |||||
| 31 | 22.96 | 147.0439 | [M+H]+ | C9H6O2 | −0.16 | 91.0541(29), 103.0540(100) | Coumarin |
| 32 | 25.08 | 875.4411 | [2M+Na]+ | C22H34O8 | 1.3 | 444→331.1904(100), 349.2014(76), 391.2127(66) | Cinnzeylanine |
| 472.2912 | [M+C2H7N+H]+ | 1.5 | |||||
| 449.2152 | [M+Na]+ | 0.61 | |||||
| 444.2598 | [M+NH4]+ | 1.4 | |||||
| 33 | 26.98 | 149.0598 | [M+H]+ | C9H8O2 | 0.63 | 103.0540(26), 131.0489(100) | bTrans-cinnamic acid |
| 34 | 28.15 | 859.3147 | [2M+Na]+ | C22H26O8 | −0.06 | 401→167.0703(100), 330.1099(93) | Syringaresinol |
| 401.1598 | [M-H2O+H]+ | 0.80 | |||||
| 35 | 28.49 | 133.0646 | [M+H]+ | C9H8O | −0.19 | 55.0178(100), 105.0697(31), 115.0541(88) | Cinnamaldehyde |
| 36 | 31.94 | 163.0755 | [M+H]+ | C10H10O2 | 0.14 | 55.0178(100), 107.0490(95), 135.0804(96) | Methoxycinnamaldehyde |
a
PAC: proanthocyanidin; DP: degree-of-poplymerization; A: No. of A-type linkage
b
Compound structures were confirmed by authentic standards