Structural characterization of mono‐ and bisphosphonium salts by fast atom bombardment mass spectrometry and tandem mass spectrometry

Claereboudt, J.; Baeten, W.; Geise, H. J.; Claeys, Magda

doi:10.1002/oms.1210280204

Cited by 29 publications

(25 citation statements)

References 28 publications

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“…CRF reactions were first reported in high‐energy collision‐induced and surface‐induced dissociation for functionalized alkanes which were generated by fast atom bombardment 2, 5–7. It was shown in later studies that the same reactions can also be observed in fast atom bombardment8–10 and during post‐source decay of ions produced by matrix‐assisted laser desorption 11. In previous work, we have argued that in high‐energy CID cleavage of a C–H bond at different positions in the aliphatic chain is the initial step which triggers the CRF process 6, 12, 13.…”

Section: Introductionmentioning

confidence: 83%

Resonant electron capture mass spectrometry of free fatty acids: examination of ion structures using deuterium‐labeled fatty acids and collisional activation

2002

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The structures of [M-H](-) ions generated from free fatty acids in resonant electron capture at energies of 1.2 and 7.2 eV were investigated using deuterium-labeled isotopomers and collision-induced dissociation. The [M-H](- small middle dot) ions occur in both a carboxylate anion and a carbanion form. While the formation of the carboxylate anion at 1.2 eV involves the loss of a carboxylic hydrogen, that at 7.2 eV involves the loss of a hydrogen from different positions in the aliphatic chain followed by a rearrangement of a carboxylic hydrogen on to the radical site in the chain. The [M-H-H(2)O](-) ion which is a minor ion in the resonant electron capture spectrum at 7.2 eV is shown to be a precursor for the charge-remote fragment ions corresponding to formal losses of a hydrogen and elements of alkanes. The [M-H-H(2)O](-) ion corresponding to the second major ion in the resonant electron capture spectrum at 7.2 eV is demonstrated to be consistent with a cyclopentanone anion structure. On the basis of new insights obtained in the present study and taking into account previous results, an updated proposal is presented for the mechanism of charge-remote fragmentation which operates in resonant electron capture of free fatty acids at 7.2 eV.

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Section: Introductionmentioning

confidence: 83%

Resonant electron capture mass spectrometry of free fatty acids: examination of ion structures using deuterium‐labeled fatty acids and collisional activation

2002

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“…Hypervalent radical formation from quaternary ammonium (and phosphonium) salts by one‐electron reduction is known since 198012 and is extensively documented 13–18. Aromatic ammonium hypervalent radicals are stabilized by partial delocalization of the electronic density throughout the macrocycle and are relatively stable species, contrary to aliphatic ammonium hypervalent radicals that are transient 19…”

Section: Introductionmentioning

confidence: 99%

Reduction and adduct formation from electrosprayed solutions of porphyrin salts

et al. 2008

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The solutions of four meso-tetrakis(N-alkylpyridinium-4-yl)porphyrin salts and of the p-toluenesulfonate salt of meso-tetrakis(4-trimethylammoniumphenyl)porphyrin, in methanol, were studied by electrospray mass spectrometry, in order to investigate the influence of the type of counter ion, the length of the substituent N-alkyl groups of the four (N-alkylpyridinium-4-yl)porphyrins and the presence of an aromatic (alkylpyridinium) or aliphatic (trimethylammonium) nitrogen, in ion formation. In our experimental conditions, adducts with the counter ions were formed only for the meso-tetrakis(4-trimethylammoniumphenyl)porphyrin and were not observed for the other porphyrins, even when the counter ion was the same. In contrast, formation of reduced species, such as the [M(4+) + e(-)]3+, [M(4+) + 2e(-)]2+, [M(4+) + 4e(-) + 2H(+)]2+, and [M(4+) + 5e(-) + 2H(+)]+ ions was observed only for the (N-alkylpyridinium-4-yl)porphyrins and the appearance of these species is apparently solvent related and may occur via counter ion/solvent adducts.

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“…Fragmentation of the compounds was not reported. FAB has also been used for the structural characterization of mono‐ and bisphosphonium halides derived from triphenylphosphine 18. In a study by Auriola et al, 19 negative ion electrospray ionization tandem mass spectrometry (ESI‐MS/MS) with ion‐pair LC was applied to adenine nucleotide‐containing metabolites of bisphosphonates, including the metabolite of clodronate.…”

Section: Introductionmentioning

confidence: 99%

Electrospray ionization mass spectrometry and tandem mass spectrometry of clodronate and related bisphosphonate and phosphonate compounds

et al. 2002

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The bisphosphonate family with a P-C-P structure is a broad class of drugs, widely investigated as potential inhibitors in bone diseases and calcium metabolic disorders. In this study, the mass spectrometric (MS) behavior and fragmentation of clodronate and related bisphosphonate and phosphonate compounds was studied by using negative ion electrospray ionization (ESI) with triple quadrupole and ion trap instruments. The effect of pH on the degree of deprotonation of the polyprotic bisphosphonic and phosphonic acids in negative ion ESI-MS was investigated, and the degree of deprotonation in the ESI mass spectra and the dissociation in the liquid phase were compared. The results provide evidence that the measured ESI mass spectra do not correlate with the chemistry in the liquid phase owing to the decrease in the pH of the solvent droplets during the ion evaporation process and the charge state neutralization in the gas phase. Ion trap MS(n) provided useful information on the fragmentation study of clodronate and related bisphosphonate and phosphonate compounds, in which interesting fragmentation pathways including the direct elimination of carbon monoxide from deprotonated bisphosphonates and formation of a P-P bond were observed. Reactions between the product ions with a -PO(2) group and residual water in the ion trap or in the high-pressure region of the triple quadrupole instrument formed other unexpected fragmentation paths for all the bisphosphonates studied.

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Structural characterization of mono‐ and bisphosphonium salts by fast atom bombardment mass spectrometry and tandem mass spectrometry

Abstract: Positive-ion fast atom bombardment (FAB) mass spectra are reported for a representative series of mono-and bisphosphonium halides derived from triphenylphosphine. The mass spectra of the monoalkyltriphenylphosphonium

Cited by 29 publications

References 28 publications

Resonant electron capture mass spectrometry of free fatty acids: examination of ion structures using deuterium‐labeled fatty acids and collisional activation

Resonant electron capture mass spectrometry of free fatty acids: examination of ion structures using deuterium‐labeled fatty acids and collisional activation

Reduction and adduct formation from electrosprayed solutions of porphyrin salts

Electrospray ionization mass spectrometry and tandem mass spectrometry of clodronate and related bisphosphonate and phosphonate compounds

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