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Elimination of isocyanate and isothiocyanate molecules at the electrospray ionization ion trap, electrospray ionization quadrupole time-of-flight and matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry fragmentation of sodium cationized brassitin, brassinin and their glycosides.
Eur J Mass Spectrom (Chichester). 2007; 13(2):147-54.EJ

Abstract

Fragmentation mechanisms of phytoalexin analogs, including brassitin and brassinin and their glucosylated analogs, have been studied by electrospray (ESI) ion trap (IT) multistage (MS(n), n = 1-4) mass spectrometry, matrix-assisted laser desorption/ionization time-of-flight (MALDI ToF/ToF) and ESI-Q/ToF tandem mass spectrometry techniques. At the fragmentation of sodium adducts a hitherto not described process has been elucidated The proposed mechanism of this process includes cyclization of the brassitin and brassinin cationized adducts through a six-membered cycle of the molecules and the elimination of isocyanate or isothiocyanate from the thio- or dithiocarbamate moiety, giving rise to [M + Na - 43](+) or [M + Na - 59](+) adducts. The elimination of NH=C=O or NH=C=S molecules has been confirmed by the high resolution measurement of the elemental composition of the ions produced and quantum-chemical calculations of the six-membered transition state. Other fragmentation routes include cleavage of an alkane linker, while numerous characteristic hexopyranose pathways are taking place in the glucosylated compounds. The presented theoretical data on the ESI and MALDI behavior of the saccharidic, as well as of the indole aglycon parts, can facilitate structural elucidation of the analogous compounds.

Authors+Show Affiliations

Institute of Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 845 38 Bratislava, Slovakia.No affiliation info availableNo 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

17881781

Citation

Bekesová, Slávka, et al. "Elimination of Isocyanate and Isothiocyanate Molecules at the Electrospray Ionization Ion Trap, Electrospray Ionization Quadrupole Time-of-flight and Matrix-assisted Laser Desorption/ionization Time-of-flight Tandem Mass Spectrometry Fragmentation of Sodium Cationized Brassitin, Brassinin and Their Glycosides." European Journal of Mass Spectrometry (Chichester, England), vol. 13, no. 2, 2007, pp. 147-54.
Bekesová S, Kovácik V, Tvaroska I, et al. Elimination of isocyanate and isothiocyanate molecules at the electrospray ionization ion trap, electrospray ionization quadrupole time-of-flight and matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry fragmentation of sodium cationized brassitin, brassinin and their glycosides. Eur J Mass Spectrom (Chichester). 2007;13(2):147-54.
Bekesová, S., Kovácik, V., Tvaroska, I., Curillová, Z., Skultéty, L., & Rehulka, P. (2007). Elimination of isocyanate and isothiocyanate molecules at the electrospray ionization ion trap, electrospray ionization quadrupole time-of-flight and matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry fragmentation of sodium cationized brassitin, brassinin and their glycosides. European Journal of Mass Spectrometry (Chichester, England), 13(2), 147-54.
Bekesová S, et al. Elimination of Isocyanate and Isothiocyanate Molecules at the Electrospray Ionization Ion Trap, Electrospray Ionization Quadrupole Time-of-flight and Matrix-assisted Laser Desorption/ionization Time-of-flight Tandem Mass Spectrometry Fragmentation of Sodium Cationized Brassitin, Brassinin and Their Glycosides. Eur J Mass Spectrom (Chichester). 2007;13(2):147-54. PubMed PMID: 17881781.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Elimination of isocyanate and isothiocyanate molecules at the electrospray ionization ion trap, electrospray ionization quadrupole time-of-flight and matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry fragmentation of sodium cationized brassitin, brassinin and their glycosides. AU - Bekesová,Slávka, AU - Kovácik,Vladimír, AU - Tvaroska,Igor, AU - Curillová,Zuzana, AU - Skultéty,L'udovít, AU - Rehulka,Pavel, PY - 2007/9/21/pubmed PY - 2007/11/8/medline PY - 2007/9/21/entrez SP - 147 EP - 54 JF - European journal of mass spectrometry (Chichester, England) JO - Eur J Mass Spectrom (Chichester) VL - 13 IS - 2 N2 - Fragmentation mechanisms of phytoalexin analogs, including brassitin and brassinin and their glucosylated analogs, have been studied by electrospray (ESI) ion trap (IT) multistage (MS(n), n = 1-4) mass spectrometry, matrix-assisted laser desorption/ionization time-of-flight (MALDI ToF/ToF) and ESI-Q/ToF tandem mass spectrometry techniques. At the fragmentation of sodium adducts a hitherto not described process has been elucidated The proposed mechanism of this process includes cyclization of the brassitin and brassinin cationized adducts through a six-membered cycle of the molecules and the elimination of isocyanate or isothiocyanate from the thio- or dithiocarbamate moiety, giving rise to [M + Na - 43](+) or [M + Na - 59](+) adducts. The elimination of NH=C=O or NH=C=S molecules has been confirmed by the high resolution measurement of the elemental composition of the ions produced and quantum-chemical calculations of the six-membered transition state. Other fragmentation routes include cleavage of an alkane linker, while numerous characteristic hexopyranose pathways are taking place in the glucosylated compounds. The presented theoretical data on the ESI and MALDI behavior of the saccharidic, as well as of the indole aglycon parts, can facilitate structural elucidation of the analogous compounds. SN - 1469-0667 UR - https://www.unboundmedicine.com/medline/citation/17881781/Elimination_of_isocyanate_and_isothiocyanate_molecules_at_the_electrospray_ionization_ion_trap_electrospray_ionization_quadrupole_time_of_flight_and_matrix_assisted_laser_desorption/ionization_time_of_flight_tandem_mass_spectrometry_fragmentation_of_sodium_cationized_brassitin_brassinin_and_their_glycosides_ L2 - https://journals.sagepub.com/doi/10.1255/ejms.847?url_ver=Z39.88-2003&rfr_id=ori:rid:crossref.org&rfr_dat=cr_pub=pubmed DB - PRIME DP - Unbound Medicine ER -