A rapid analytical method for characterization and simultaneous quantitative determination of phytoconstituents in Piper betle landraces using UPLC-ESI-MS/MS

Abstract

A rapid ultra performance liquid chromatography electrospray ionisation tandem mass spectrometry (UPLC-ESI-MS/MS) method was developed and validated for identification and characterization of phytoconstituents with simultaneous quantitative determination of three major bioactive phenolics namely allylpyrocatechol-3,4-diacetate, eugenyl acetate and eugenol from thirteen landraces of Piper betle leaf extracts. Among the 29 phytoconstituents detected, 19 were identified and characterized based on their fragmentation pattern obtained via MS/MS by means of collision-induced-dissociation (CID) and by comparison of their retention time with authentic standards or by previously reported literature. The proposed method was fully validated in terms of linearity, LOD, LOQ, precision, stability and recovery. All calibration curves showed a good linear relationship (r 2 $ 0.9981). The precision evaluated by an intra-and inter-day study showed RSD # 1.0% and good accuracy with overall recovery in the range from 96.14-98.46% (RSD # 1.6%) for all analytes. The quantitative results showed that there were remarkable differences in the contents of the major bioactive phenolics in all the thirteen landraces of P. betle. The developed UPLC-ESI-MS/MS method was found to be simple, precise, sensitive and accurate. Hence, it can be reliably utilized as a quality control method for P. betle or derived herbal formulations. In vitro antimicrobial activity of the crude extract of P. betle landraces was also evaluated, and all extracts tested exhibited antifungal activity but none of the extracts were found to be active against bacteria even at 500 mg mL À1 concentration.

Top‐down lignomic matrix‐assisted laser desorption/ionization time‐of‐flight tandem mass spectrometry analysis of lignin oligomers extracted from date palm wood

“…The product ion scan of m/z 752.2 affords the ion at m/z 709.24, [C 37 H 40 O 14 + H] + , formed by the loss of one molecule of acetylene eliminated by a RDA reaction and one hydroxyl radical.…”

“…In addition, this latter secondary product can eliminate simultaneously a molecule of carbon monoxide following aromatic ring contraction and a molecule of water, to afford the tertiary product ion at m/z 645.26 (supporting information, SM1). The precursor distonic cation 2 affords the primary product ions at m/z 675.23 and 668.20 by the respective consecutive losses of either a molecule of carbon dioxide, a hydrogen radical and a molecule of methanol, or two molecules of acetylene by RDA rearrangements and a molecule of methanol (supporting information, SM1). For the sake of brevity, further information on the remaining product ions at m/z 621.19, 575.18, 278.07, 184.07 and 163.03 formed from the precursor ion at m/z 752.2 is shown in Schemes and and in Scheme SM1 (supporting information).…”

“…The high‐energy product ion spectrum of the m/z 780.2 ion affords a major ion (base peak) at m/z 737.23, [C 38 H 40 O 15 + H] + , created by the loss of a molecule of acetylene (via RDA reaction) and a hydroxyl radical. Furthermore, cleavage of the S(8‐O‐4''')G bond of cation 3 yields the [C 9 H 6 O 3 + H] + ion at m/z 163.03 ( Scheme ).…”

“…In addition, the product ion scan of the protonated molecule at m/z 1039.3 yields the primary [C 56 H 52 O 18 + H] + product ion at m/z 1013.31 by the loss of a molecule of acetylene by a RDA mechanism (supporting information, SM3A). This primary product ion loses a molecule of carbon monoxide by an aromatic ring contraction of the first H residue, to afford the secondary [C 55 H 52 O 17 + H] + product ion at m/z 985.32 (supporting information, SM3A). Additional information and details of the remaining low mass product ions are provided in the supporting information.…”

“…Cleavage of the protonated molecule between the contiguous two sinapyl residues yields the secondary product ion [C 24 H 30 O 11 + H] + at m/z 495.18 (Scheme ). This latter secondary product ion affords the [C 22 H 28 O 11 + H] + tertiary product ion at m/z 469.16 by loss of acetylene through an RDA mechanism (Scheme ) …”