Table 5.
Time-of-flight mass spectrometry (TOF-MS) and TOF-MS/MS. TOF-MS and TOF-MS/MS of tentatively identified metabolites. RT = Retention Time; RDB = Ring Double Bond equivalent value.
|
|
RT (min) |
Tentative Assignment | Formula | [M-H]− calc. (m/z) |
[M-H]− Found (m/z) |
Error (ppm) |
RDB | MS/MS Fragment Ions (m/z) and Relative Intensity (%) | ICBhA Content (%) |
PCBhA Content (%) |
|---|---|---|---|---|---|---|---|---|---|---|
| 1 | 0.275 | Hexytol | C6H14O6 | 181.0718 | 181.0716 | −0.9 | 0 | 113.0281, 101.0248 (100) | 0.97 | 0.19 |
| 2 | 0.295 | Disaccharide | C12H22O11 | 341.1094 | 341.1094 | 1.3 | 2 | 341.1094; 236.9674; 198.1265; 179.0553; 161.0459; 119.0363; 113.0252; 101.0253; 89.0254 (100) | 1.4 | 1.66 |
| 3 | 0.360 | Isocitric acid | C6H8O7 | 191.0197 | 191.0198 | 0.4 | 3 | 111.0087 (100); 87.0091 | 8.94 | 4.47 |
| 4 | 0.435 0.486 |
Caffeoyl aspartic acid | C13H13NO7 | 294.0619 | 294.0618 [2M-H]− 589.1321 |
−0.4 | 8 | 206.0828; 204.0697; 178.0527; 161.0236; 135.0466; 134.0384; 132.0318 (100); 115.0048; 88.0416 | 6.98 | 4.62 |
| 5 | 0.636 | Gallo(epi)catechin | C15H14O7 | 305.0667 | 305.0671 | 1.4 | 9 | 305.0671; 219.0667; 167.0353; 139.0403; 137.0248; 125.0248; 109.0299 | 1.42 | 1.65 |
| 6 | 0.615 | Procyanidin B type (e.g., B3) | C30H26O12 | 577.1352 | 577.1361 | 1.6 | 18 | 577.1377; 559.1285; 451.1040; 425.0886; 407.0777 (100); 339.0856; 299.0572; 289.0705 (98); 287.0556; 245.0825; 221.0810; 167.0377; 161.0240; 125.0141 | 2.02 | 1.03 |
| 7 | 0.749 | Coumaroyl aspartic acid | C13H13NO6 | 278.0670 | 278.0671 | 0.3 | 8 | 278.0672; 216.0653; 190.0857; 163.0382; 162.0560; 146.0610; 119.0503 (100); 117.0356; 115.0032; 93.0367 | 4.35 | 2.93 |
| 8 | 1.260 | Catechin | C15H14O6 | 289.0718 | 289.0720 [2M-H]− 579.1510 |
0.8 | 9 | 289.0718 (100); 245.0821; 203.0726; 179.0357; 125.0247; 109.0300 | 22.07 | 3.5 |
| 9 | 1.784 | Epicatechin | C15H14O6 | 289.0718 | 289.0714 | 0.8 | 9 | 289.0723; 245.0825; 221.0833; 203.0730; 187.0414; 175.0418; 125.0252; 123.0461; 109.0308 (100); 97.0305 | 4.67 | 32.75 |
| 10 | 4.217 | Clovamide | C18H17NO7 | 358.0932 | 358.0929 | −0.9 | 11 | 358.0899; 222.0396; 178.0503; 161.0237; 135.0448 (100); 134.6163; 133.0301; 86.1043 | 2.07 | 1.07 |
| 11 | 0.800 | Procyanidin B type (e.g., B1) | C30H26O12 | 577.1352 | 577.1363 | 2.0 | 18 | 577.1415; 559.1338; 451.1076; 425.0915; 407.0812 (100); 339.0900; 299.0568; 289.0738; 287.0578; 245.0837; 221.0829; 167.0361; 161.0255; 125.0254 | 2.08 | 10.25 |
| 12 | 4.255 | ((Epi)catechin trimer | C45H38O18 | 865.1985 | 865.1977 | −0.9 | 27 | 739.1742; 713.1592; 695.1486; 577.1418; 559.1302; 543.0984; 525.0872; 451.1069; 425.0919; 413.0909; 407.0808; 381.1008; 341.0693; 289.0740; 287.0581; 261.0427; 243.0311; 217.0522; 175.0417; 161.0259; 125.0260 | 2.24 | 1.5 |
| 13 | 5.190 | (Epi)catechin trimer | C45H38O18 | 865.1985 | 865.1977 | −0.9 | 27 | 739.1739; 713.1583; 695.1451; 587.1247; 577.1409; 561.1076; 543.0971; 525.0885; 449.0892; 425.0908; 407.0787; 381.1008; 341.0687; 289.0728; 287.0575; 261.0417; 245.0463; 217.0530; 175.0402; 161.0256; 125.0249 | 4.46 | 3.86 |
| 14 | 5.661 | Caffeoyl tyrosine | C18H17NO6 | 342.0983 | 342.0988 | 1.4 | 11 | 342.2398; 298.1083; 256.2008; 206.0473; 180.0675; 161.0242; 135.0452 (100); 119.0509; 107.0499; 93.0360 | 1.29 | 0.65 |
| 15 | 6.208 | Procyanidin B type (e.g., B4) | C30H26O12 | 577.1352 | 577.1367 | 1.6 | 18 | 577.1374; 451.1046; 425.0892; 407.0774; 339.0871; 299.0554; 289.0716 (100); 287.0559; 245.0818; 161.0244; 125.02416 | 4.64 | 7.04 |
| 16 | 6.247 | Isoquercetrin | C21H20O12 | 463.0882 | 463.0887 | 1.1 | 12 | 463.0884; 301.0340; 300.0267 (100); 271.0243; 255.0293; 243.0289 | 1.74 | 0.67 |
| 18 | 6.386 | Procyanidin dimer A type hexoside isomer |
C36H34O17 | 737.1737 | 737.1737 | 0.1 | 25 | 737.1780; 611.1448; 539.1018; 449.0899 (100); 448.0808; 407.0783; 388.0595; 327.0509; 307.0605; 287.0557 | 2.51 | 2.26 |
| 19 | 6.398 | (Epi)catechin tetramer | C60H50O24 | 1153.2619 | 1153.2624 | 0.4 | 36 | 1153.2621; 1135.2792; 1001.2021; 983.2019; 575.1135; 289.0671; 287.0491; 245.0639; 161.0194; 125.0202 | 0.77 | 0.88 |
| 20 | 6.444 | (Epi)catechin trimer | C45H38O18 | 865.1985 | 865.1977 | −0.9 | 27 | 739.1762; 713.1582; 695.1488; 577.1423; 561.1118; 543.0994; 525.0885; 451.1085; 425.0915; 407.0814 (100); 381.1004; 299.0584; 289.0740; 287.0573; 245.0466; 161.0258; 125.0255 | 1.29 | 1.2 |
| 21 | 6.583 | Proanthocyanidin A type [(epi)catechin-(epi)gallocatechin] | C31H28O12 | 591.1508 | 591.1523 | 2.5 | 18 | 591.2831; 591.1525; 591.2002; 547.1555; 439.1032; 301.0703; 289.0698 (100); 245.0814; 215.0702; 203.0698; 149.0226; 137.0236; 109.0280 | 1.22 | 1.6 |
| 22 | 6.623 | p-Coumaroyl tyrosine | C18H17NO5 | 326.1034 | 326.1035 | 0.3 | 11 | 326.1046; 282.1143; 239.1091; 206.0461; 180.0664; 163.0401; 145.0292; 119.0498 (100); 117.0352; 93.0345 | 1.73 | 0.89 |
| 23 | 6.655 | (Epi)catechin ethyl dimer | C32H30O12 | 605.1665 | 605.1685 | 3.4 | 18 | 605.1675; 453.1197; 315.0875 (100); 289.0719; 271.0961; 245.0819; 229.0875; 205.0503; 163.0404; 151.0396; 137.0244; 109.0300 | 1.71 | 2.58 |
| 24 | 6.670 | Procyanidin dimer A type pentoside isomer |
C35H32O16 | 707.1618 | 707.1636 | 2.6 | 20 | 707.1663; 581.1345; 539.1020; 449.0895 (100); 448.0815; 407.0789; 325.0339; 287.0543; 125.0246 | 2.39 | 1.98 |
| 25 | 6.682 | Quercetin pentoside | C20H18O11 | 433.0776 | 433.0776 | 12 | −0.1 | 433.0776; 301.0344; 300.0274 (100); 271.0248; 255.0302; 227.0354; 199.0407; 178.9991; 151.0024; 107.0138 | ||
| 26 | 6.702 | Kaempferol rutinoside | C27H30O15 | 593.1512 | 593.1523 | 13 | 1.9 | 593.1512 (100); 593.2491; 549.2540; 447.0976; 429.0806; 285.0396; 284.0314 | 0.35 | 0.43 |
| 27 | 6.783 | Quercetin pentoside | C20H18O11 | 433.0776 | 433.0775 | 12 | −0.1 | 433.0775; 301.0345; 300.0272 (100); 271.0239; 255.0288; 243.0288; 227.0339; 151.0025 | 0.23 | 0.04 |
| 28 | 6.959 | Procyanidin dimer A type | C30H24O12 | 575.1195 | 575.1198 | 19 | 0.5 | 575.1236; 557.1144; 539.1008; 531.2619; 471.1195; 449.0897; 423.0719; 409.0994; 407.0784; 387.0591; 341.0620; 327.0501; 307.0631; 289.0729; 287.0547; 285.0414 (100); 267.0306; 241.0501; 217.0504; 163.0044; 161.0252; 137.0259; 125.0246; 109.0315 | 5.71 | 3.74 |
| 29 | 7.041 | Procyanidin B type (e.g., B2) | C30H26O12 | 577.1352 | 577.1360 | 1.5 | 18 | 577.1369; 425.0891; 407.0878; 289.0720 (100); 287.0565; 245.0819; 161.0239; 125.0244 | 0.55 | 0.67 |
| 30 | 7.144 | Quercetin deoxyhexoside (e.g., Q-rhamnoside) | C21H20O11 | 447.0933 | 447.0945 | 12 | 2.7 | 447.0959; 301.0361; 300.0285 (100) 283.0246; 271.0251; 255.0304; 243.0301; 227.0349; 211.0406; 178.9981; 151.0036; 121.0289 | 0.4 | 0.55 |
| 31 | 8.280 | (Epi)catechin ethyl dimer | C32H30O12 | 605.1665 | 605.1673 | 1.4 | 18 | 605.1693; 453.1168; 315.0867; 289.0714 (100); 271.0956; 245.0811; 229.0856; 205.0504; 179.0347; 163.0416; 151.0397; 137.0250; 109.0293 | 7.36 | 2.98 |
| 32 | 8.422 | Proanthocyanidin A type | C30H24O12 | 575.1195 | 575.1207 | 19 | 2.1 | 575.1215 (100); 449.0887; 407.0778; 394.0692; 287.0565; 271.0239; 243.0287; 229.0504; 161.0230; 137.0245; 125.0245 | 1.02 | 0.71 |