Determination of structure and properties of modified chlorophylls by using fast atom bombardment combined with tandem mass spectrometry

Richard P. Grese, Ronald Cerny, Michael L. Gross, Mathias Senge

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

Tandem mass spectrometry (MS/MS) was used to investigate and compare the decompositions of radical cations (M+.), radical anions (M-.), [M + H]+ ions, and [M + Cat]+ ions (Cat = alkali metal ions) of chlorophylls. Included in this study are chlorophyll a, chlorophyll b, bacteriochlorophyll a, chlorophyll a allomers, and the corresponding pheophytins. Fast atom bombardment of chlorophyll a produces abundant M+. ions, which decompose metastably and upon collisional activation to give fragment ions from losses of the phytyl chain and the β-keto group of ring V. In addition, previously unreported charge-remote fragmentations are useful for identification of branch points on the phytyl chain. Collisional activation of [M + Cat]+ ions produces fragment ions that are complementary to those of the M+ and are used to examine the intrinsic gas-phase reactivity of metal ions and chlorophylls. Peripheral metal ion attachment in chlorophyll a in the gas phase is suggested to be at C-9, and the β-keto ester group at C-10, of ring V. Examination of decompositions of chlorophyll dimers suggests that in the gas phase the interaction between monomers involves bonding of the Mg atom of one chlorophyll a molecule and the C-9 carbonyl oxygen of the other, which was also suggested for chlorophyll a dimers in solution.

Original languageEnglish (US)
Pages (from-to)72-84
Number of pages13
JournalJournal of the American Society for Mass Spectrometry
Volume1
Issue number1
DOIs
StatePublished - Feb 1990

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Chlorophyll
Tandem Mass Spectrometry
Mass spectrometry
Ions
Atoms
Metal ions
Gases
Dimers
Cats
Pheophytins
Chemical activation
Bacteriochlorophylls
Alkali Metals
Decomposition
Metals
Anions
chlorophyll a
Cations
Esters
Monomers

ASJC Scopus subject areas

  • Structural Biology
  • Spectroscopy

Cite this

Determination of structure and properties of modified chlorophylls by using fast atom bombardment combined with tandem mass spectrometry. / Grese, Richard P.; Cerny, Ronald; Gross, Michael L.; Senge, Mathias.

In: Journal of the American Society for Mass Spectrometry, Vol. 1, No. 1, 02.1990, p. 72-84.

Research output: Contribution to journalArticle

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