Structural characterization of "tailed picket-fence porphyrins" by high-energy fast atom bombardment collision-induced dissociation mass spectrometry/mass spectrometry

Toshimichi Shibue, Hisashi Kambe, Hiroyuki Nishide, Satoko Akashi, Naoshi Dohmae, Yoko Ohashi

Research output: Contribution to journal › Article

2 Citations (Scopus)

Abstract

The applicability of high-energy fast atom bombardment (FAB) collision-induced dissociation mass spectrometry/mass spectrometry (CID-MS/MS) to the structural characterization of side-chains of porphyrin derivatives with a "tailed picketfence" structure was examined. These porphyrins showed a molecular ion [M]+• as well as a protonated molecule [M + H]+ and another at [M + 2]+ in the positive ion mode. Doubly-charged ions were observed when the "tail" has an imidazole ring. The linked-scan spectrometry indicated that the "tail" of the porphyrin is eliminated first as a neutral species from the pyrrole-2-position as a β-type cleavage, after which each of the four pivaloyl "picket-fences" are cleaved off in series from the remainder of the molecule-related ions. The spectrum also clearly showed charge-remote product ions in the low mass region, in addition to charge-mediated product ions representing the precise side chain structure of the "tailed picket-fence" porphyrin. FAB CID-MS/MS spectra of [M]+•, [M + 1]+ and [M + 2]+, using the EBEB-type four-sector tandem mass spectrometer, show similar fragmentation patterns to each other with 1 u difference in parallel. The CID-MS/MS of [M + 1]+ and [M + 2]+ showed higher product ion intensities than the corresponding product ion intensities of [M]+•. CID-MS/MS, using an EBEB-type four-sector tandem mass spectrometer, showed charge-remote product ions much more clearly than those observed in B/E-constant linked-scan spectra.

Original languageEnglish
Pages (from-to)291-299
Number of pages9
JournalEuropean Journal of Mass Spectrometry
Volume3
Issue number4
Publication statusPublished - 1997

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fences
Fences
Porphyrins
porphyrins
Mass spectrometry
bombardment
mass spectroscopy
dissociation
Ions
Atoms
collisions
atoms
ions
products
energy
Mass spectrometers
mass spectrometers
sectors
Pyrroles
Molecules

Keywords

  • Charge-remote fragmentation
  • Collision activation
  • Collision-induced dissociation
  • Doubly-charged ion
  • Fast atom bombardment
  • Linked-scanning
  • Picket-fence porphyrin
  • Porphyrins
  • Tailed picket-fence porphyrin
  • Tandem mass spectrometry

ASJC Scopus subject areas

  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Structural characterization of "tailed picket-fence porphyrins" by high-energy fast atom bombardment collision-induced dissociation mass spectrometry/mass spectrometry. / Shibue, Toshimichi; Kambe, Hisashi; Nishide, Hiroyuki; Akashi, Satoko; Dohmae, Naoshi; Ohashi, Yoko.

In: European Journal of Mass Spectrometry, Vol. 3, No. 4, 1997, p. 291-299.

Research output: Contribution to journal › Article

Shibue, T, Kambe, H, Nishide, H, Akashi, S, Dohmae, N & Ohashi, Y 1997, 'Structural characterization of "tailed picket-fence porphyrins" by high-energy fast atom bombardment collision-induced dissociation mass spectrometry/mass spectrometry', European Journal of Mass Spectrometry, vol. 3, no. 4, pp. 291-299.
Shibue T, Kambe H, Nishide H, Akashi S, Dohmae N, Ohashi Y. Structural characterization of "tailed picket-fence porphyrins" by high-energy fast atom bombardment collision-induced dissociation mass spectrometry/mass spectrometry. European Journal of Mass Spectrometry. 1997;3(4):291-299.
Shibue, Toshimichi ; Kambe, Hisashi ; Nishide, Hiroyuki ; Akashi, Satoko ; Dohmae, Naoshi ; Ohashi, Yoko. / Structural characterization of "tailed picket-fence porphyrins" by high-energy fast atom bombardment collision-induced dissociation mass spectrometry/mass spectrometry. In: European Journal of Mass Spectrometry. 1997 ; Vol. 3, No. 4. pp. 291-299.
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abstract = "The applicability of high-energy fast atom bombardment (FAB) collision-induced dissociation mass spectrometry/mass spectrometry (CID-MS/MS) to the structural characterization of side-chains of porphyrin derivatives with a {"}tailed picketfence{"} structure was examined. These porphyrins showed a molecular ion [M]+• as well as a protonated molecule [M + H]+ and another at [M + 2]+ in the positive ion mode. Doubly-charged ions were observed when the {"}tail{"} has an imidazole ring. The linked-scan spectrometry indicated that the {"}tail{"} of the porphyrin is eliminated first as a neutral species from the pyrrole-2-position as a β-type cleavage, after which each of the four pivaloyl {"}picket-fences{"} are cleaved off in series from the remainder of the molecule-related ions. The spectrum also clearly showed charge-remote product ions in the low mass region, in addition to charge-mediated product ions representing the precise side chain structure of the {"}tailed picket-fence{"} porphyrin. FAB CID-MS/MS spectra of [M]+•, [M + 1]+ and [M + 2]+, using the EBEB-type four-sector tandem mass spectrometer, show similar fragmentation patterns to each other with 1 u difference in parallel. The CID-MS/MS of [M + 1]+ and [M + 2]+ showed higher product ion intensities than the corresponding product ion intensities of [M]+•. CID-MS/MS, using an EBEB-type four-sector tandem mass spectrometer, showed charge-remote product ions much more clearly than those observed in B/E-constant linked-scan spectra.",
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AU - Shibue, Toshimichi

AU - Kambe, Hisashi

AU - Nishide, Hiroyuki

AU - Akashi, Satoko

AU - Dohmae, Naoshi

AU - Ohashi, Yoko

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N2 - The applicability of high-energy fast atom bombardment (FAB) collision-induced dissociation mass spectrometry/mass spectrometry (CID-MS/MS) to the structural characterization of side-chains of porphyrin derivatives with a "tailed picketfence" structure was examined. These porphyrins showed a molecular ion [M]+• as well as a protonated molecule [M + H]+ and another at [M + 2]+ in the positive ion mode. Doubly-charged ions were observed when the "tail" has an imidazole ring. The linked-scan spectrometry indicated that the "tail" of the porphyrin is eliminated first as a neutral species from the pyrrole-2-position as a β-type cleavage, after which each of the four pivaloyl "picket-fences" are cleaved off in series from the remainder of the molecule-related ions. The spectrum also clearly showed charge-remote product ions in the low mass region, in addition to charge-mediated product ions representing the precise side chain structure of the "tailed picket-fence" porphyrin. FAB CID-MS/MS spectra of [M]+•, [M + 1]+ and [M + 2]+, using the EBEB-type four-sector tandem mass spectrometer, show similar fragmentation patterns to each other with 1 u difference in parallel. The CID-MS/MS of [M + 1]+ and [M + 2]+ showed higher product ion intensities than the corresponding product ion intensities of [M]+•. CID-MS/MS, using an EBEB-type four-sector tandem mass spectrometer, showed charge-remote product ions much more clearly than those observed in B/E-constant linked-scan spectra.

AB - The applicability of high-energy fast atom bombardment (FAB) collision-induced dissociation mass spectrometry/mass spectrometry (CID-MS/MS) to the structural characterization of side-chains of porphyrin derivatives with a "tailed picketfence" structure was examined. These porphyrins showed a molecular ion [M]+• as well as a protonated molecule [M + H]+ and another at [M + 2]+ in the positive ion mode. Doubly-charged ions were observed when the "tail" has an imidazole ring. The linked-scan spectrometry indicated that the "tail" of the porphyrin is eliminated first as a neutral species from the pyrrole-2-position as a β-type cleavage, after which each of the four pivaloyl "picket-fences" are cleaved off in series from the remainder of the molecule-related ions. The spectrum also clearly showed charge-remote product ions in the low mass region, in addition to charge-mediated product ions representing the precise side chain structure of the "tailed picket-fence" porphyrin. FAB CID-MS/MS spectra of [M]+•, [M + 1]+ and [M + 2]+, using the EBEB-type four-sector tandem mass spectrometer, show similar fragmentation patterns to each other with 1 u difference in parallel. The CID-MS/MS of [M + 1]+ and [M + 2]+ showed higher product ion intensities than the corresponding product ion intensities of [M]+•. CID-MS/MS, using an EBEB-type four-sector tandem mass spectrometer, showed charge-remote product ions much more clearly than those observed in B/E-constant linked-scan spectra.

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