title: Mass spectral characterization of phloroglucinol derivatives hyperforin and adhyperforin.
abstract: Active phloroglucinol constituents of Hypericum perforatum (St. John's wort) extracts, hyperforin and adhyperforin, have been studied following ion activation using tandem mass spectrometry (MS/MS) and complemented by accurate mass measurements. These two compounds were readily analyzed as protonated and deprotonated molecules with electrospray ionization. MS/MS and MS3 data from a quadrupole-linear ion trap tandem mass spectrometer were employed to elucidate fragmentation pathways. Fourier transform ion cyclotron resonance measurements afforded excellent mass accuracies for the confirmation of elemental formulae of product ions formed via infrared multiphoton dissociation and sustained off-resonance irradiation collision-induced dissociation. Fragmentation schemes have been devised for the dissociation of hyperforin and adhyperforin in negative and positive ion modes. This information is expected to be especially valuable for the characterization of related compounds, such as degradation products, metabolites and novel synthetic analogs of hyperforin.
authors.affiliation: Institute for Marine Biosciences, 1411 Oxford Street, Halifax, Nova Scotia B3H 3Z1, Canada.
authors.forename: Lekha
authors.initials: L
authors.lastname: Sleno
authors.forename: Rambod
authors.initials: R
authors.lastname: Daneshfar
authors.forename: Gunter P
authors.initials: GP
authors.lastname: Eckert
authors.forename: Walter E
authors.initials: WE
authors.lastname: Müller
authors.forename: Dietrich A
authors.initials: DA
authors.lastname: Volmer
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000737:chemistry; D020902:Hypericum / Q000737:chemistry*; D015394:Molecular Structure; D010696:Phloroglucinol / Q000031:analogs & derivatives* / Q000737:chemistry; D010936:Plant Extracts / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D013729:Terpenes / Q000737:chemistry*
chemical_list: D001643:Bridged Bicyclo Compounds; D010936:Plant Extracts; D013729:Terpenes; C423123:adhyperforin; D010696:Phloroglucinol; C001654:hyperforin