title: (+)-Silybin, a pharmacologically active constituent of Silybum marianum: fragmentation studies by atmospheric pressure chemical ionization quadrupole time-of-flight tandem mass spectrometry.
abstract: The fragmentation behavior of (+)-silybin (1) and (+)-deuterosilybin (2), as well as of their flavanone-3-ol-type building blocks, such as 3,5,7-trihydroxy-2-phenyl-4-chromanone (3) and 2-(1,4-benzodioxolanyl)-3,5,7-trihydroxy-4-chromanone (4), were investigated by atmospheric pressure chemical ionization quadropole time-of-flight tandem mass spectrometry in the positive ion mode (APCI(+)-QqTOF MS/MS). The product ion spectra of the protonated molecules of 1 revealed a rather complicated fragmentation pattern with product ions originating from consecutive and competitive loss of small molecules such as H2O, CO, CH2O, CH3OH and 2-methoxyphenol, along with the A+- and B+-type ions arising from the cleavage of the C-ring of the flavanone-3-ol moiety. The elucidation of the fragmentation behavior of 1 was facilitated by acquiring information on the fragmentation characteristics of the flavanone-3-ol moieties and 2. The capability of the accurate mass measurement on the quadrupole time-of-flight mass spectrometer allowed us to determine the elemental composition of each major product ion. Second-generation product ion spectra obtained by combination of in-source collision induced dissociation (CID) with selective CID (pseudo-MS(3)) was also helpful in elaborating the fragmentation pathways and mechanism. Based on the experimental results, a fragmentation mechanism as well as fragmentation pathways for 1 and its flavanone-3-ol building blocks (3, 4) are proposed and discussed.
authors.affiliation: Department of Applied Chemistry, University of Debrecen, H-4010 Debrecen, P.O. Box 1, Hungary. keki@tigris.unideb.hu
authors.forename: Sándor
authors.initials: S
authors.lastname: Kéki
authors.forename: Katalin
authors.initials: K
authors.lastname: Tóth
authors.forename: Miklós
authors.initials: M
authors.lastname: Zsuga
authors.forename: Renáta
authors.initials: R
authors.lastname: Ferenczi
authors.forename: Sándor
authors.initials: S
authors.lastname: Antus
mesh_terms: D001274:Atmospheric Pressure; D004353:Drug Evaluation, Preclinical; D020944:Silybum marianum / Q000378:metabolism*; D010936:Plant Extracts / Q000737:chemistry*; D000077385:Silybin; D012838:Silymarin / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods*
chemical_list: D010936:Plant Extracts; D012838:Silymarin; D000077385:Silybin