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(+)-Silybin, a pharmacologically active constituent of Silybum marianum: fragmentation studies by atmospheric pressure chemical ionization quadrupole time-of-flight tandem mass spectrometry.
Rapid Commun Mass Spectrom. 2007; 21(14):2255-62.RC

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+Show Affiliations

Department of Applied Chemistry, University of Debrecen, H-4010 Debrecen, P.O. Box 1, Hungary. keki@tigris.unideb.huNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

17569099

Citation

Kéki, Sándor, et al. "(+)-Silybin, a Pharmacologically Active Constituent of Silybum Marianum: Fragmentation Studies By Atmospheric Pressure Chemical Ionization Quadrupole Time-of-flight Tandem Mass Spectrometry." Rapid Communications in Mass Spectrometry : RCM, vol. 21, no. 14, 2007, pp. 2255-62.
Kéki S, Tóth K, Zsuga M, et al. (+)-Silybin, a pharmacologically active constituent of Silybum marianum: fragmentation studies by atmospheric pressure chemical ionization quadrupole time-of-flight tandem mass spectrometry. Rapid Commun Mass Spectrom. 2007;21(14):2255-62.
Kéki, S., Tóth, K., Zsuga, M., Ferenczi, R., & Antus, S. (2007). (+)-Silybin, a pharmacologically active constituent of Silybum marianum: fragmentation studies by atmospheric pressure chemical ionization quadrupole time-of-flight tandem mass spectrometry. Rapid Communications in Mass Spectrometry : RCM, 21(14), 2255-62.
Kéki S, et al. (+)-Silybin, a Pharmacologically Active Constituent of Silybum Marianum: Fragmentation Studies By Atmospheric Pressure Chemical Ionization Quadrupole Time-of-flight Tandem Mass Spectrometry. Rapid Commun Mass Spectrom. 2007;21(14):2255-62. PubMed PMID: 17569099.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - (+)-Silybin, a pharmacologically active constituent of Silybum marianum: fragmentation studies by atmospheric pressure chemical ionization quadrupole time-of-flight tandem mass spectrometry. AU - Kéki,Sándor, AU - Tóth,Katalin, AU - Zsuga,Miklós, AU - Ferenczi,Renáta, AU - Antus,Sándor, PY - 2007/6/15/pubmed PY - 2007/8/24/medline PY - 2007/6/15/entrez SP - 2255 EP - 62 JF - Rapid communications in mass spectrometry : RCM JO - Rapid Commun Mass Spectrom VL - 21 IS - 14 N2 - 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. SN - 0951-4198 UR - https://www.unboundmedicine.com/medline/citation/17569099/_+__Silybin_a_pharmacologically_active_constituent_of_Silybum_marianum:_fragmentation_studies_by_atmospheric_pressure_chemical_ionization_quadrupole_time_of_flight_tandem_mass_spectrometry_ L2 - https://doi.org/10.1002/rcm.3081 DB - PRIME DP - Unbound Medicine ER -