Characterization and Isolation of Piperamides from Piper nigrum cultivated in Costa Rica

The piperamides profile of Piper nigrum cultivated in Costa Rica was studied using Ultra Perfor-mance Liquid Chromatography coupled with Electrospray Ionization Quadrupole Time-of-Flight High Resolution Mass Spectrometry (UPLC-ESI-QTOF-HRMS) on enriched-piperamides extracts. A total of 31 different piperamides were identified, 24 of them with a methylenedioxyphenyl moiety, including piperine and nine other compounds with the characteristic piperidine ring, as well as guineensine, retrofractamide B and eight other piperamides with an N-isobutyl group. In addition, piperyline and two other compounds with a pyrrolidine ring as well as piperflaviflorine B, holding a N-2-methylbutyl chain, were characterized. In turn, pellitorine and six other piperamides exhib-iting a long olefinic chain instead of the methylenedioxyphenyl group, were also tentatively iden-tified. In addition, quantification was performed using UPLC coupled with Diode Array Detector (UPLC-DAD), with 15 piperamides being quantified, including piperine, piperyline, piperanine, and piperloguminine with values within the range of previous reports, while results obtained for guineensine (276.5 - 421.0 mg/100 g dry material) and pellitorine (414.4 - 725.0 mg/100 g dry ma-terial) are higher than those reported in the literature. Additionally, preparative and semi-preparative High Performance Liquid Chromatography (HPLC) separations allowed to iso-late, besides piperine, four other piperamides, which were identified through HRMS, 1H and 13C Nuclear Magnetic Resonance (NMR), including retrofractamide B, guineensine, pellitorine, and (2E,4E,12Z)-N-isobutyl-octadeca-2,4,12-trienamide, with yields of 134.0 mg/100 g dry material, 209.7 mg/100 g dry material, 361.8 mg/100 g dry material and 467.0 mg/100 g dry material, re-spectively, with all these values higher than those reported in previous studies in the literature. The findings constitute the first report of such a number and diversity of compounds in P. nigrum cul-tivated in Costa Rica.Universidad de Costa Rica/[115-B6-163]/UCR/Costa RicaUniversidad de Costa Rica/[115-C0-001]/UCR/Costa RicaUniversidad de Costa Rica/[115-C3-005]/UCR/Costa RicaUniversidad de Costa Rica/[ED-2033]/UCR/Costa RicaUCR::Vicerrectoría de Docencia::Ciencias Básicas::Facultad de Ciencias::Escuela de Químic