Screening and Identification of the Metabolites in Rat Plasma and Urine after Oral Administration of Areca catechu L. Nut Extract by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap–Orbitrap Tandem Mass Spectrometry
Abstract
:1. Introduction
2. Results and Discussion
2.1. Identification of the Major Components in ACNE by UHPLC-LTQ-Orbitrap
2.1.1. Alkaloids
2.1.2. Tannins
2.1.3. Amino Acid
2.2. Identification of the Major Metabolites in ACNE by UHPLC-LTQ-Qrbitrap
2.2.1. Prototypes (M1, M2, M3, M5, M6, M15, M17)
2.2.2. Methylated Metabolites (M19, M21)
2.2.3. Methylated and Sulfated Metabolites (M16)
2.2.4. Methylated and Glucuronidated Metabolites (M18)
2.2.5. Sulfated Metabolites (M12)
2.2.6. Glucuronidated Metabolites (M10)
2.2.7. Oxidative Metabolites (M4, M9)
2.2.8. Mercapturic Acid-Conjugated Metabolites (M7)
2.2.9. Oxidative and Mercapturic Acid Conjugated Metabolites (M13)
2.2.10. Dimer (M8)
2.2.11. Other Metabolites (M11, M14, M20)
3. Materials and Methods
3.1. Chemicals and Materials
3.2. Preparation of the Areca catechu L. Nut Extract
3.3. Animal and Sample Collection
3.4. Sample Preparation
3.5. Instrumentation and Analytical Conditions
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
Component | tR (Min) | [M + H]+ Ion (m/z) | Error (ppm) | Formula | Fragment Ions (m/z) | Identification |
---|---|---|---|---|---|---|
1 | 1.36 | 118.0861 | −1.568 | C5H11NO2 | 72.0806 | Valine |
2 | 1.70 | 128.0705 | −0.743 | C6H9NO2 | 110.0601, 81.0334 | Guvacine/Isoguvacine |
3 | 1.74 | 142.0862 | −0.085 | C7H11NO2 | 128.0745, 124.0758, 96.0807, 81.0333 | Arecaidine |
4 | 1.87 | 144.1018 | −0.869 | C7H13NO2 | 126.0915, 114.0913, 84.0806 | Methyl piperidine-3-carboxylate |
5 | 3.05 | 182.0810 | −0.822 | C9H11NO3 | 165.0548, 136.0760 | Tyrosine |
6 | 3.47 | 142.0862 | −0.115 | C7H11NO2 | 113.9638, 110.0602, 81.0334 | Guvacoline |
7 | 4.09 | 156.1018 | −0.115 | C8H13NO2 | 124.0757, 113.0597, 96.0807, 81.0333 | Arecoline |
8 | 7.81 | 156.1017 | −0.255 | C8H13NO2 | 128.1069, 113.0597, 81.0333 | Arecolidine |
9 | 8.68 | 579.1489 | −1.334 | C30H26O12 | 453.1197, 427.1039, 409.0937, 291.0874 | Procyanidin B2 |
10 | 9.48 | 291.0861 | −0.669 | C15H14O6 | 273.0762, 165.0548, 151.0392, 139.0392, 123.0443 | Catechin (C) |
11 | 9.53 | 205.0970 | −0.996 | C11H12N2O2 | 188.0917, 159.9331 | Tryptophan |
12 | 12.20 | 291.0860 | −0.978 | C15H14O6 | 273.0764, 165.0549, 151.0393, 139.0393, 123.0444 | Epicatechin (EC) |
Metabolite | tR (Min) | Selected Ion | Calculated Mass (m/z) | Error (ppm) | Formula | Fragmentation | Identification | Source |
---|---|---|---|---|---|---|---|---|
M1 | 1.75 | [M + H]+ | 128.0706 | −0.352 | C6H9NO2 | 110.0601, 81.0332 | Guvacine/Isoguvacine | Urine; Plasma |
M2 | 1.76 | [M + H]+ | 142.0862 | −0.740 | C7H11NO2 | 124.0759, 96.0809, 81.0334 | Arecaidine | Urine; Plasma |
M3 | 1.78 | [M + H]+ | 144.1018 | −0.661 | C7H13NO2 | 126.0915, 114.0915, 84.0806 | Methyl piperidine-3-carboxylate | Urine; Plasma |
M4 | 1.96 | [M + H]+ | 158.0811 | −0.315 | C7H11NO3 | 140.0529, 112.0870 | Arecaidine N-oxide | Urine; Plasma |
M5 | 3.28 | [M + H]+ | 142.0862 | −0.388 | C7H11NO2 | 113.0597, 110.0601, 81.0333 | Guvacoline | Urine; Plasma |
M6 | 3.58 | [M + H]+ | 156.1018 | −0.418 | C8H13NO2 | 124.0758, 113.0598, 96.0807, 81.0333 | Arecoline | Urine |
M7 | 4.31 | [M + H]+ | 319.1319 | −1.000 | C13H22N2O5S | 287.1068, 277.1223, 190.0901, 156.1022 | Arecoline mercapturic acid | Urine; Plasma |
M8 | 5.58 | [M + H]+ | 343.1862 | −0.417 | C16H26N2O6 | 172.0974 | Arecoline N-oxide dimer | Urine; Plasma |
M9 | 5.79 | [M + H]+ | 172.0966 | −1.103 | C8H13NO3 | 154.0866, 140.0710, 112.0759 | Arecoline N-oxide | Urine; Plasma |
M10a | 7.60 | [M − H]− | 465.1025 | −0.586 | C21H22O12 | 289.0719 | Glucuronidation of C/EC | Urine |
M11 | 7.67 | [M + H]+ | 144.1019 | −0.175 | C7H13NO2 | 126.0916, 98.0965, 84.0807 | N-methylnipecotic acid | Urine; Plasma |
M12a | 7.90 | [M − H]− | 369.0282 | 1.872 | C15H14O9S | 289.0723 | Sulfation of C/EC | Urine |
M10b | 8.12 | [M − H]− | 465.1037 | 1.973 | C21H22O12 | 289.0721 | Glucuronidation of C/EC | Urine |
M12b | 8.22 | [M − H]− | 369.0282 | 2.279 | C15H14O9S | 289.0723 | Sulfation of C/EC | Urine |
M13 | 8.33 | [M + H]+ | 335.1270 | −0.369 | C13H22N2O6S | 317.1172, 303.1019, 293.1173, 206.0851, 172.0973 | Arecoline N-oxide mercapturic acid | Urine; Plasma |
M14 | 8.41 | [M + H]+ | 170.0812 | −0.057 | C8H11NO3 | 152.0711 | Norepinephrine | Urine; Plasma |
M10c | 8.47 | [M − H]− | 465.1024 | −0.715 | C21H22O12 | 289.0716 | Glucuronidation of C/EC | Plasma |
M15 | 8.60 | [M + H]+ | 579.1491 | −1.023 | C30H26O12 | 453.1199, 427.1041, 409.0938, 291.0875 | Procyanidin B2 | Urine; Plasma |
M16a | 9.20 | [M − H]− | 383.0435 | 1.020 | C16H16O9S | 303.0879, 137.0249 | Sulfation + methylation of C/EC | Urine |
M17a | 9.31 | [M + H]+ | 291.0865 | 0.602 | C15H14O6 | 273.0766, 165.0550, 151.0394, 139.0394, 123.0444 | Catechin(C) | Urine; Plasma |
M10d | 9.53 | [M − H]− | 465.1031 | 0.790 | C21H22O12 | 289.0721 | Glucuronidation of C/EC | Plasma |
M18a | 9.86 | [M − H]− | 479.1187 | 0.579 | C22H24O12 | 303.0877, 289.0716, 175.0249 | Methylation + glucuronidation of C/EC | Urine |
M18b | 10.12 | [M − H]− | 479.1179 | −1.132 | C22H24O12 | 303.0873, 289.0715, 175.0247 | Methylation + glucuronidation of C/EC | Urine |
M19a | 10.16 | [M + H]+ | 305.1020 | 0.083 | C16H16O6 | 287.0921, 179.0707 | Methylation of C/EC | Urine; Plasma |
M19b | 10.50 | [M + H]+ | 305.1021 | 0.280 | C16H16O6 | 287.0923, 179.0708 | Methylation of C/EC | Urine; Plasma |
M16b | 10.73 | [M − H]− | 383.0430 | −0.259 | C16H16O9S | 303.0876, 137.0249 | Sulfation + methylation of C/EC | Urine |
M16c | 11.73 | [M − H]− | 383.0427 | −1.225 | C16H16O9S | 303.0882, 137.0250 | Sulfation + methylation of C/EC | Urine |
M17b | 11.99 | [M + H]+ | 291.0864 | 0.293 | C15H14O6 | 273.0767, 165.0551, 151.0394, 139.0394, 123.0445 | Epicatechin(EC) | Urine; Plasma |
M16d | 12.72 | [M − H]− | 383.0429 | −0.729 | C16H16O9S | 303.0882, 137.0250 | Sulfation + methylation of C/EC | Urine |
M19c | 12.94 | [M + H]+ | 305.1020 | −0.015 | C16H16O6 | 287.0923, 179.0708 | Methylation of C/EC | Urine; Plasma |
M16e | 13.01 | [M − H]− | 383.0436 | 1.334 | C16H16O9S | 303.0876, 137.0250 | Sulfation + methylation of C/EC | Plasma |
M20 | 13.06 | [M + H]+ | 184.0968 | −0.271 | C9H13NO3 | 166.0865, 152.0710 | Epinephrine(EP) | Urine |
M16f | 13.29 | [M − H]− | 383.0432 | 0.289 | C16H16O9S | 303.0875, 137.0249 | Sulfation + methylation of C/EC | Plasma |
M18c | 13.70 | [M − H]− | 479.1183 | −0.297 | C22H24O12 | 303.0876, 289.0718, 175.0249 | Methylation + glucuronidation of C/EC | Plasma |
M12c | 13.89 | [M − H]− | 369.0271 | −0.946 | C15H14O9S | 289.0722 | Sulfation of C/EC | Plasma |
M18d | 13.93 | [M − H]− | 479.1179 | −1.007 | C22H24O12 | 303.0876, 289.0717, 175.0249 | Methylation + glucuronidation of C/EC | Plasma |
M21 | 14.27 | [M + H]+ | 321.0943 | −2.549 | C16H16O7 | 303.1331, 289.0689 | Methylation of epigallocatechin(EGC) | Urine |
M16g | 14.34 | [M − H]− | 383.0432 | 2.378 | C16H16O9S | 303.0883, 137.0250 | Sulfation + methylation of C/EC | Plasma |
M19d | 14.35 | [M + H]+ | 305.1018 | −0.507 | C16H16O6 | 287.0920, 179.0706 | Methylation of C/EC | Urine |
M12d | 14.68 | [M − H]− | 369.0270 | −1.352 | C15H14O9S | 289.0722 | Sulfation of C/EC | Plasma |
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Li, L.; Luo, Z.; Liu, Y.; Wang, H.; Liu, A.; Yu, G.; Li, M.; Yang, R.; Chen, X.; Zhu, J.; et al. Screening and Identification of the Metabolites in Rat Plasma and Urine after Oral Administration of Areca catechu L. Nut Extract by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap–Orbitrap Tandem Mass Spectrometry. Molecules 2017, 22, 1026. https://doi.org/10.3390/molecules22061026
Li L, Luo Z, Liu Y, Wang H, Liu A, Yu G, Li M, Yang R, Chen X, Zhu J, et al. Screening and Identification of the Metabolites in Rat Plasma and Urine after Oral Administration of Areca catechu L. Nut Extract by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap–Orbitrap Tandem Mass Spectrometry. Molecules. 2017; 22(6):1026. https://doi.org/10.3390/molecules22061026
Chicago/Turabian StyleLi, Lulu, Zhiqiang Luo, Yang Liu, Hao Wang, Aoxue Liu, Guohua Yu, Mengwei Li, Ruirui Yang, Xinjing Chen, Jialian Zhu, and et al. 2017. "Screening and Identification of the Metabolites in Rat Plasma and Urine after Oral Administration of Areca catechu L. Nut Extract by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap–Orbitrap Tandem Mass Spectrometry" Molecules 22, no. 6: 1026. https://doi.org/10.3390/molecules22061026