Table 1.
Characterization of chemical compounds in young pear fruits by ultra-performance liquid chromatography coupled with electrospray ionization triple quadrupole mass spectrometry (UPLC-Q TRAP-MS/MS).
| Peak NO. | Rt (min) | Formula | [M − H]− (m/z) | MS/MS Fragments (m/z) | Tentative Identification |
|---|---|---|---|---|---|
| Polyphenol | |||||
| 1 | 0.81 | C7H12O6 | 191.1 | 172.9[M − H − H2O]− | Quinic acid a |
| 2 | 1.76 | C9H8O2 | 147.0 | 129.0[M − H − H2O]− | Cinnamic acid isomer |
| 3 | 2.06 | C12H16O7 | 317.1 # | 271.2[M − H]−, 160.9[M − H − C6H6O2]−, 109.0[M − H − Glc]− | Arbutin a |
| 4 | 2.77 | C30H24O12 | 575.3 | 449.0[M − H − C6H6O3]−, 285.2[M − H − C15H14O6]− | A-type procyanidin dimer |
| 5 | 3.19 | C16H18O9 | 353.3 | 191.1[M − H − caffeoyl]−, 179.2[M − H − quinoyl]− | 4-O-Caffeoylquinic acid (Cryptochlorogenic acid) a |
| 6 | 3.37 | C15H20O9 | 343.2 | 181.0[M − H − hexose]− | Dihydro-caffeoyl-O-hexoside |
| 7 | 3.48 | C30H26O12 | 577.3 | 425.2[M − H − C8H8O3]−, 288.9[M − H − C15H12O6]− | B-type procyanidin dimer |
| 8 | 3.51 | C15H20O8 | 327.2 | 147.1[M − H − hexose − H2O]− | Hydroxyphenylpropionic acid-O-hexoside |
| 9 | 3.76 | C15H20O10 | 359.3 | 197.1[M − H − hexose]− | Syringic acid-O-hexoside |
| 10 | 3.84 | C12H14O6 | 253.1 | 135.1[M − H − C3H6O2 − CO2]− | Caffeoylglycerol |
| 11 | 3.88 | C15H20O9 | 343.2 | 181.0[M − H − hexose]− | Dihydro-caffeoyl-O-hexoside |
| 12 | 4.11 | C15H14O6 | 289.1 | 245.3[M − H − CO2]−, 202.9[M − H − H2O − C3O2]− | (+)-Catechin a |
| 13 | 4.13 | C16H18O9 | 353.3 | 191.1[M − H − caffeoyl]−, 161.1[M − H − quinoyl − H2O]− | 3-O-Caffeoylquinic acid (Chlorogenic acid) a |
| 14 | 4.31 | C45H38O18 | 865.3 | 577.1[M − H − C15H12O6]−, 407.1[M − H − C15H12O6 − C8H8O3 − H2O]−, 289.0[M − H − 2C15H12O6]− | B-type procyanidin trimer |
| 15 | 4.38 | C16H18O9 | 353.3 | 191.1[M − H − caffeoyl]−, 173.0[M − H − caffeoyl − H2O]− | 5-O-Caffeoylquinic acid (Neochlorogenic acid) a |
| 16 | 4.64 | C22H18O10 | 441.3 | 325.1[M − H − C4H4O4]−, 163.0[M − H − C4H4O4 − caffeoyl]−, 118.9[p-coumaric acid − H − CO2]− | p-Coumaroylcaffeoyl malate |
| 17 | 4.89 | C30H26O12 | 577.3 | 425.1[M − H − C8H8O3]−, 407.0[M − H − C8H8O3 − H2O]−, 339.0[M − H − C8H8O3 − H2O − C3O2]−, 289.1[M − H − C15H12O6]−, 245.0[M − H − C15H12O6 − CO2]− | B-type procyanidin dimer |
| 18 | 4.98 | C45H38O18 | 865.3 | 577.0[M − H − C15H12O6]−, 287.1[M − H − C15H12O6 − C15H14O6]− | B-type procyanidin trimer |
| 19 | 5.07 | C45H36O18 | 863.3 | 573.3[M − H − C15H14O6]−, 289.2[M − H − C15H12O6 − C15H10O6]− | A-type procyanidin trimer |
| 20 | 5.28 | C16H18O9 | 353.3 | 191.1[M − H − caffeoyl]− | 1-O-Caffeoylquinic acid |
| 21 | 5.30 | C15H18O9 | 341.1 | 178.9[M − H − hexose]− | Caffeoyl-O-hexoside |
| 22 | 5.44 | C16H16O8 | 335.3 | 179.1[M − H − shikimoyl]− | Caffeoylshikimic acid |
| 23 | 5.45 | C19H30O8 | 431.2 # | 385.0[M − H]−, 223.1[M − H − Glc]− | Roseoside |
| 24 | 5.48 | C15H14O6 | 289.1 | 245.0[M − H − CO2]−, 202.9[M − H − H2O − C3O2]− | (−)-Epicatechin a |
| 25 | 5.53 | C16H18O8 | 337.3 | 190.9[M − H − p-coumaroyl]−, 163.2 [M − H − quinoyl]− | 4-p-Coumaroylquinic acid |
| 26 | 5.57 | C15H20O10 | 359.3 | 197.0[M − H − hexose]−, 160.9[M − H − hexose − 2H2O]− | Syringic acid-O-hexoside |
| 27 | 5.64 | C45H36O18 | 863.3 | 711.3[M − H − C8H8O3]−, 573.0[M − H − C15H14O6]−, 289.0[M − H − C15H12O6 − C15H10O6]− | A-type procyanidin trimer |
| 28 | 6.05 | C16H16O8 | 335.3 | 179.0[M − H − shikimoyl]−, 135.1 [M − H − shikimoyl − CO2]− | Caffeoylshikimic acid |
| 29 | 6.49 | C45H36O18 | 863.3 | 711.1[M − H − C8H8O3]−, 573.0[M − H − C15H14O6]−, 451.2[M − H − C15H12O6 − C7H8O2]−, 289.2[M − H − C15H12O6 − C15H10O6]− | A-type procyanidin trimer |
| 30 | 6.54 | C30H24O12 | 575.3 | 285.3[M − H − C15H14O6]− | A-type procyanidin dimer |
| 31 | 6.69 | C17H20O9 | 367.4 | 191.0[M − H − feruloyl]−, 193.2[M − H − quinoyl]− | 3-O-Feruloylquinic acid |
| 32 | 6.71 | C19H16O12 | 435.3 | 273.0[M − H − caffeoyl]−, 205.0[M − H − caffeoylmalonyl]− | Caffeoyl-malonyl-methylcitric aci |
| 33 | 7.01 | C45H38O18 | 865.3 | 577.1[M − H − C15H12O6]−, 451.1[M − H − C15H12O6 − C6H6O3]−, 407.1[M − H − C15H12O6 − C8H8O3 − H2O]−, 289.0[M − H − 2C15H12O6]− | B-type procyanidin trimer |
| 34 | 7.24 | C16H18O8 | 337.3 | 190.9[M − H − p-coumaroyl]−, 163.2 [M − H − quinoyl]− | 5-p-Coumaroylquinic acid |
| 35 | 7.35 | C30H26O12 | 577.3 | 289.3[M − H − C15H12O6]− | B-type procyanidin dimer |
| 36 | 7.40 | C17H20O9 | 367.4 | 205.1[M − H − caffeoyl]− | 4-O-Caffeoylquinic acid methyl ester |
| 37 | 7.58 | C30H24O12 | 575.3 | 285.2[M − H − C15H14O6]− | A-type procyanidin dimer |
| 38 | 7.61 | C32H38O20 | 741.4 | 301.1[M − H − Xyl-Rha-Gal]− | Quercetin-3-O-xylosylrhamnosylglucoside |
| 39 | 7.84 | C21H22O10 | 433.3 | 323.0[M − H − C6H6O2]−, 161.1[M − H − arbutin − H2O]− | Caffeoylarbutin |
| 40 | 7.89 | C60H50O24 | 1153.3 | 739.1[M − H − C15H12O6 − C6H6O2]−, 449.2[C30H26O12 − H − H2O − C6H6O2]−, 287.1[C30H26O12 − H − C15H14O6]− | B-type procyanidin tetramer |
| 41 | 8.04 | C24H24O13 | 519.4 | 315.3[M − H − acetyl-hexose]− | Isorhamnetin-acylated-hexoside |
| 42 | 8.05 | C21H22O10 | 433.3 | 323.0[M − H − C6H6O2]−, 178.9[M − H − arbutin]−, 160.9[M − H − arbutin − H2O]−, 133.1[M − H − arbutin − H2O − CO]− | Caffeoylarbutin |
| 43 | 8.11 | C26H28O16 | 595.4 | 301.1[M − H − Ara-Gal]− | Quercetin-3-O-arabinosylgalactoside |
| 44 | 8.13 | C45H36O18 | 863.3 | 573.1[M − H − C15H14O6]−, 451.1[M − H − C15H12O6 − C7H8O2]−, 289.2[M − H − C15H12O6 − C15H10O6]− | A-type procyanidin trimer |
| 45 | 8.19 | C30H24O12 | 575.3 | 448.9[M − H − C6H6O3]−, 285.1[M − H − C15H14O6]− | A-type procyanidin dimer |
| 46 | 8.32 | C15H20O10 | 359.3 | 197.2[M − H − hexose]− | Syringic acid-O-hexoside |
| 47 | 8.41 | C9H8O3 | 163.0 | 118.9[M − H − CO2]− | Hydroxycinnamic acid |
| 48 | 8.43 | C17H20O9 | 367.4 | 205.0[M − H − caffeoyl]− | 3-O-Caffeoylquinic acid methyl ester |
| 49 | 8.63 | C26H28O16 | 595.4 | 301.1[M − H − Ara-Glc]− | Quercetin-3-O-arabinosylglucoside |
| 50 | 8.65 | C27H30O16 | 609.4 | 301.0[M − H − Rha-Gal] | Quercetin-3-O-rhamnosylgalactoside |
| 51 | 8.72 | C21H20O11 | 447.3 | 285.2[M − H − Glc]− | Luteolin-7-O-galactoside |
| 52 | 8.87 | C27H30O16 | 609.4 | 301.0[M − H − Rut]− | Rutin a |
| 53 | 8.91 | C45H38O18 | 865.3 | 577.1[M − H − C15H12O6]−, 451.1[M − H − C15H12O6 − C6H6O3]−, 407.1[M − H − C15H12O6 − C8H8O3 − H2O]−, 289.0[M − H − 2C15H12O6]− | B-type procyanidin trimer |
| 54 | 8.93 | C25H24O11 | 499.4 | 353.1[M − H − p-coumaroyl]−, 337.2[M − H − caffeoyl]−, 191.2[M − H − caffeoyl − p-coumaroyl]−, 163.1[p-coumaroyl − H]− | p-Coumaroylcaffeoylquinic acid |
| 55 | 8.98 | C21H20O12 | 463.2 | 301.2[M − H − Gal]− | Quercetin-3-O-galactoside (Hyperoside) a |
| 56 | 9.01 | C27H30O15 | 593.3 | 285.1[M − H − Rha-Gal]− | Kaempferol-3-O-rhamnosylgalactoside |
| 57 | 9.14 | C21H22O10 | 433.3 | 323.4[M − H − C6H6O2]−, 161.2[M − H − arbutin − H2O]−, 133.2[M − H − arbutin − H2O − CO]− | Caffeoylarbutin |
| 58 | 9.15 | C25H24O11 | 499.4 | 353. 1[M − H − p-coumaroyl]−, 336.9[M − H − caffeoyl]−, 191.1[M − H − caffeoyl − p-coumaroyl]−, 163.0[p-coumaroyl − H]− | p-Coumaroylcaffeoylquinic acid |
| 59 | 9.16 | C21H20O12 | 463.2 | 301.2[M − H − Glc]− | Quercetin-3-O-glucoside |
| 60 | 9.17 | C30H26O12 | 577.3 | 425.1[M − H − C8H8O3]−, 289.0[M − H − C15H12O6]− | B-type procyanidin dimer |
| 61 | 9.25 | C25H24O12 | 515.5 | 353.1[M − H − caffeoyl]−, 191.0[M − H − 2caffeoyl]− | Di-O-caffeoylquinic acid |
| 62 | 9.26 | C21H20O11 | 447.3 | 285.0[M − H − Glc]− | Luteolin-7-O-glucoside (Luteoloside) a |
| 63 | 9.30 | C45H38O18 | 865.3 | 577.2[M − H − C15H12O6]−, 406.9[M − H − C15H12O6 − C8H8O3 − H2O]−, 289.0[M − H − 2C15H12O6]− | B-type procyanidin trimer |
| 64 | 9.38 | C27H30O15 | 593.3 | 285.1[M − H − Rha-Glc]− | Kaempferol-3-O-rhamnosylglucoside |
| 65 | 9.44 | C21H18O11 | 445.3 | 401.0[M − H − CO2]−, 357.2[M − H − 2CO2]−, 313.2[M − H − 3CO2]−, 225.2[M − H − C6H8O6 − CO2]−, 181.1[M − H − C6H8O6 − 2CO2]− | Apigenin-O-glucuronide or isomer |
| 66 | 9.46 | C30H24O12 | 575.3 | 539.0[M − H − H2O − H2O]−, 449.1[M − H − C6H6O3]−, 407.1[M − H − CO2 − C7H8O2]−, 285.1[M − H − C15H14O6]− | A-type procyanidin dimer |
| 67 | 9.51 | C45H34O18 | 861.3 | 735.1[M − H − C6H6O3]−, 693.2[M − H − CO2 − C7H8O2]−, 571.2[M − H − C15H14O6]− | A-type procyanidin trimer |
| 68 | 9.54 | C21H22O9 | 417.2 | 307.3[M − H − C6H6O2]−, 163.1[M − H − arbutin]−, 145.1[M − H − arbutin − H2O]− | p-Coumaroylarbutin |
| 69 | 9.65 | C17H20O9 | 367.4 | 205.0[M − H − caffeoyl]−, 191.1[M − H − caffeoyl − methyl]− | 5-O-Caffeoylquinic acid methyl ester |
| 70 | 9.69 | C45H36O18 | 863.3 | 575.0[M − H − C15H12O6]−, 449.0[M − H − C15H12O6 − C6H6O3]− | A-type procyanidin trimer |
| 71 | 9.70 | C19H16O12 | 435.3 | 273.1[M − H − caffeoyl]−, 205.3[M − H − caffeoylmalonyl]−, 161.1[M − H − caffeoylmalonyl − CO2]− | Caffeoyl-malonyl-methylcitric acid |
| 72 | 9.75 | C21H18O11 | 445.3 | 401.2[M − H − CO2]−, 357.2[M − H − 2CO2]−, 313.1[M − H − 3CO2]−, 225.1[M − H − C6H8O6 − CO2]− | Apigenin-O-glucuronide or isomer |
| 73 | 9.76 | C27H30O15 | 593.3 | 285.1[M − H − Rut]− | Kaempferol-3-O-rutinoside a |
| 74 | 9.78 | C23H22O13 | 505.3 | 445.2[M − H − CH3COOH]−, 301.1[M − H − acetyl-Gal]− | Quercetin-acylated-galactoside |
| 75 | 9.80 | C28H32O16 | 623.5 | 315.0[M − H − Gal-Rha]− | Isorhamnetin-3-O-rhamnosylgalactoside |
| 76 | 9.87 | C25H24O12 | 515.5 | 353.0[M − H − caffeoyl]− | 3,4-O-Dicaffeoylquinic acid (Isochlorogenic acid B) a |
| 77 | 9.92 | C27H30O14 | 577.3 | 269.1[M − H − Rut]− | Apigenin rutinoside |
| 78 | 9.95 | C28H32O16 | 623.5 | 315.0[M − H − Rut]− | Isorhamnetin-3-O-rutinoside a |
| 79 | 10.07 | C21H20O11 | 447.3 | 285.0[M − H − Glc]− | Kaempferol-3-O-galactoside |
| 80 | 10.09 | C23H22O13 | 505.3 | 445.1[M − H − CH3COOH]−, 301.1[M − H − acetyl-Glc]− | Quercetin-acylated-glucoside |
| 81 | 10.10 | C22H22O12 | 477.3 | 315.0[M − H − Gal]− | Isorhamnetin-3-O-galactoside |
| 82 | 10.14 | C28H32O15 | 607.4 | 299.1[M − H − Nhe]− | Chrysoeriol-7-neohesperidoside |
| 83 | 10.21 | C25H24O12 | 515.5 | 353.2[M − H − caffeoyl]−, 191.0[M − H − 2caffeoyl]−, 178.9[M − H − caffeoyl-quinoyl]− | 3,5-O-Dicaffeoylquinic acid (Isochlorogenic acid A) a |
| 84 | 10.22 | C30H24O12 | 575.3 | 406.9[M − H − CO2 − C7H8O2]− | A-type procyanidin dimer |
| 85 | 10.27 | C21H22O9 | 417.2 | 307.3[M − H − C6H6O2]−, 163.0[M − H − arbutin]−, 145.1[M − H − arbutin − H2O]− | p-Coumaroylarbutin |
| 86 | 10.28 | C22H22O12 | 477.3 | 315.0[M − H − Glc]− | Isorhamnetin-3-O-glucoside |
| 87 | 10.31 | C21H20O11 | 447.3 | 285.0[M − H − hexose]− | Kaempferol-3-O-glucoside |
| 88 | 10.34 | C21H20O10 | 431.2 | 269.1[M − H − hexose]− | Apigenin-O-hexoside |
| 89 | 10.38 | C25H24O11 | 499.4 | 353. 0[M − H − p-coumaroyl]−, 337.0[M − H − caffeoyl]−, 191.0[M − H − caffeoyl − p-coumaroyl]− | p-Coumaroylcaffeoylquinic acid |
| 90 | 10.58 | C22H22O11 | 461.4 | 298.9[M − H − Gal]− | Chrysoeriol-7-O-galactoside |
| 91 | 10.60 | C45H34O18 | 861.3 | 735.0[M − H − C6H6O3]−, 693.1[M − H − CO2 − C7H8O2]−, 571.1[M − H − C15H14O6]−, 288.9[M − H − 2C15H10O6]− | A-type procyanidin trimer |
| 92 | 10.71 | C25H24O12 | 515.5 | 353.1[M − H − caffeoyl]−, 191.1[M − H − 2caffeoyl]−, 179.0[M − H − caffeoyl-quinoyl]− | 4,5-O-Dicaffeoylquinic acid (Isochlorogenic acid C) a |
| 93 | 10.75 | C22H22O11 | 461.4 | 299.2[M − H − Glc]− | Chrysoeriol-7-O-glucoside |
| 94 | 10.80 | C23H22O12 | 489.1 | 285.1[M − H − acetyl-Gal]− | Kaempferol-acylated-galactoside |
| 95 | 10.85 | C24H24O13 | 519.4 | 315.3[M − H − acetyl-Gal]−, 299.2[M − H − acetyl-Gal − CH4]− | Isorhamnetin-acylated-galactoside |
| 96 | 11.05 | C24H24O13 | 519.5 | 315.0[M − H − acetyl-Glc]−, 299.2[M − H − acetyl-Glc − CH4]−, 271.2[M − H − acetyl-Glc − CH4 − H2O]− | Isorhamnetin-acylated-glucoside |
| 97 | 11.30 | C25H24O11 | 499.4 | 353. 0[M − H − p-coumaroyl]−, 337.1[M − H − caffeoyl]−, 190.9[M − H − caffeoyl − p-coumaroyl]−, 163.0[p−coumaroyl − H]− | p-Coumaroylcaffeoylquinic acid |
| 98 | 11.78 | C23H22O12 | 489.1 | 285.1[M − H − acetyl-Glc]− | Kaempferol-acylated-glucoside |
| 99 | 11.80 | C17H20O9 | 367.4 | 205.1[M − H − caffeoyl]−, 190.9[M − H − caffeoyl-methyl]−, 147.0[M − H − caffeoyl-methyl − CO2]− | 1-O-Caffeoylquinic acid methyl ester |
| 100 | 12.13 | C21H20O11 | 447.3 | 295.4[M − H − Galloyl]− | Galloyl-coumaric acid pentoside |
| 101 | 12.15 | C22H22O12 | 477.3 | 273.1[M − H − acetyl-hexose]− | Phloretin-acylated-hexoside |
| 102 | 12.38 | C21H20O11 | 447.3 | 295.1[M − H − Galloyl]− | Galloyl-coumaric acid pentoside |
| Triterpenoid | |||||
| 1′ | 1.21 | C30H48O5 | 487.3 | 469.1[M − H − H2O]−, 425.0[M − H − H2O − CO2]− | Euscaphic acid |
| 2′ | 1.40 | C30H48O5 | 487.3 | 469.3[M − H − H2O]−, 425.2[M − H − H2O − CO2]− | Tormentic acid |
| 3′ | 1.59 | C30H46O5 | 485.3 | 467.1[M − H − H2O]−, 423.2[M − H − H2O − CO2]− | Anmurcoic acid |
| 4′ | 1.95 | C30H48O4 | 471.3 | 453.2[M − H − H2O]−, 407.0[M − H − H2O − CH2O]− | Pomolic acid isomer |
| 5′ | 2.47 | C30H46O4 | 469.3 | 425.1[M − H − CO2]−, 407.0[M − H − H2O − CO2]− | 1-Hydroxy-3-oxours-12-en-28-oic acid or isomer |
| 6′ | 2.63 | C30H48O4 | 471.3 | 453.3[M − H − H2O]−, 407.1[M − H − H2O − CH2O]− | Pomolic acid a |
| 7′ | 2.89 | - | 701.5 | 641.2, 555.1, 540.1, 481.1 | Unknown |
| 8′ | 3.11 | C30H48O4 | 471.3 | 453.2[M − H − H2O]−, 407.1[M − H − H2O − CH2O]− | Alphitolic acid a |
| 9′ | 3.45 | C30H48O4 | 471.3 | 453.0[M − H − H2O]−, 407.1[M − H − H2O − CH2O]− | Maslinic acid a |
| 10′ | 3.79 | C30H48O4 | 471.3 | 453.2[M − H − H2O]−, 407.3[M − H − H2O − CH2O]− | Corosolic acid |
| 11′ | 4.38 | C30H46O4 | 469.3 | 425.2[M − H − CO2]−, 407.1[M − H − CO2 − H2O]− | 1-Hydroxy-3-oxours-12-en-28-oic acid or isomer |
| 12′ | 4.79 | C30H46O4 | 469.3 | 425.1[M − H − CO2]−, 407.3[M − H − CO2 − H2O]− | 1-Hydroxy-3-oxours-12-en-28-oic acid or isomer |
| 13′ | 6.89 | C30H48O3 | 455.3 | 407.4[M − H − H2O − CH2O]− | Betulinic acid a |
| 14′ | 7.44 | C30H48O3 | 455.3 | 407.4[M − H − H2O − CH2O]− | Oleanolic acid a |
| 15′ | 7.95 | C30H48O3 | 455.3 | 407.2[M − H − H2O − CH2O]− | Ursolic acid a |
| 16′ | 8.37 | - | 687.4 | 627.1, 541.2, 526.2, 467.0 | Unknown |
Note: # the proposal ion was [M − H + HCOOH]−; a identification confirmed by authentic standards.