Reduction processes in fast atom bombardment mass spectrometry: Methylene blue in glycerol‐thioglycerol and glycerol‐nitrobenzyl alcohol matrices

Kazakoff, Clement W.; Rye, Robin T. B.

doi:10.1002/oms.1210260309

Cited by 16 publications

(5 citation statements)

References 13 publications

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“…The reduction/protonation process requires lower laser energy (over 5 µJ/pulse) than direct desorption of MB + (over 13 µJ/pulse). Previously, the reduction/protonation of the methylene blue was observed in FAB MS, [19] in LDI MS from nanocrystalline TiO 2 support [18] and in MALDI and DIOS MS. [20] As it was shown in Kazakoff et al, [19] the reduction/protonation of MB + may occur via the electron transfer and protonation (Eqns 3 and 4) or via the direct addition of H…”

Section: Desorption/ionization Mechanismsmentioning

confidence: 95%

Chemically modified porous silicon for laser desorption/ionization mass spectrometry of ionic dyes

et al. 2009

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Desorption/ionization on silicon (DIOS) mass spectra of model ionic dyes methylene blue (MB+Cl-) and methyl orange (Na+MO-) were studied using p+ type-derived porous silicon (PS) free layers. As-prepared PS (PS-H), the PS thermally oxidized at 300 degrees C (PS-OX), PS with chemically grafted cation-exchanging alkylsulfonic acid (PS-SO(3)H) and anion-exchanging propyl-octadecyldimethylammonium chloride (PS-ODMA+Cl-) groups was tested as ionization platforms. Two mechanisms of the methylene blue desorption/ionization were found: (1) the formation of [MB + H]+* ion due to the reduction/protonation of MB+, which is predominant for PS-H and PS-OX platforms and (2) direct thermal desorption of the MB+ cation, prevailing for PS-SO3H. The fragmentation of the cation is significantly suppressed in the latter case. The samples of PS-SO3H and PS-ODMA+ Cl- efficiently adsorb the dyes of the opposite charge from their solutions via the ion-exchange. Consequent DIOS MS studies allow to detect only low fragmented ions (MB+ and MO-, respectively), demonstrating the potential of the ion-exchange adsorption combined with DIOS MS for the analysis of ionic organic compounds in solutions.

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Section: Desorption/ionization Mechanismsmentioning

confidence: 95%

Chemically modified porous silicon for laser desorption/ionization mass spectrometry of ionic dyes

et al. 2009

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“…As mentioned above, the electron‐scavenging properties of a matrix solvent, that is, its ability to compete with the analyte for bombardment‐generated electrons or hydrogen radicals, affects the extent of reduction under FAB/SIMS 7, 23–26. Some agents that suppress the reduction, such as transition metals (Fe, Mn, Cu) chlorides,24 Cu(II) salts,7 SnCl 2 ,24 4‐hydroxybenzenesulfonic acid,25 nitrobenzyl alcohol (NOBA)26 have been reported, while reduction‐enhancing agents were not looked for.…”

Section: Introductionmentioning

confidence: 99%

Sensitivity of redox reactions of dyes to variations of conditions created in mass spectrometric experiments

et al. 2008

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Redox behaviour of four imidazophenazine dye derivatives under mass spectrometric conditions of matrix-assisted laser desorption/ionization (MALDI), laser desorption/ionization (LDI) from metal and graphite surface, electrospray, low temperature secondary ion mass spectrometry (LT SIMS) and fast atom bombardment (FAB) was studied and distinctions in the reduction-dependent spectral patterns were analyzed from the point of view of different quantities of protons and electrons available for reduction in different techniques. The reduction products [M + 2H](+*), [M + 3H](+) and M(-*), [M + H](-) were observed in the positive and negative ion modes, respectively, which permitted to suggest independent occurrence of reduction and protonation/deprotonation processes. LDI from graphite substrate was the only technique that allowed us to obtain abundant negative ions of all dye derivatives. The yield of field ionization (FI) or field desorption (FD) mechanism to ion formation under LDI from rough graphite surface has been addressed. The sensitivity of reduction of the dyes to variation of reduction-initiating agents confirms high redox activity of the dyes essential for their functioning in natural and artificial systems.

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“…The concomitant formation of one‐electron reduction products [M 2+ + e − ] +· and of [M +· +H · ] + species has been observed in the FAB‐MS spectra of porphyrins and in other compounds, including organic dye molecules and nucleosides 5g, 7a, 16, 17b,c. However, the redox potential and the availability of low‐energy unoccupied molecular orbitals (LUMOs) of the analyte under investigation, as well as the proton and electron affinity characteristics of the matrix used, seem to be controlling parameters for the formation of [M +· + H · ] + ions.…”

Section: Resultsmentioning

confidence: 97%

“…2(a) and (b)]. In the case of SGLY as a FAB‐matrix the efficient H · scavenger properties of thiols have to be considered:16 …”

Section: Resultsmentioning

confidence: 99%

A fast atom bombardment and matrix‐assisted laser desorption/ionization mass spectrometry study of doubly charged porphyrins

Schäfer

Budzikiewicz

2001

J. Mass Spectrom.

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In this mass spectrometry (MS) study of doubly charged porphyrin salts, fast atom bombardment (FAB) and matrix-assisted laser desorption/ionization (MALDI) MS techniques are utilized to examine several unique ionic species. The predominant transformation of preformed doubly charged ions in the desorption/ionization mechanism of FAB and MALDI is the result of deprotonation reactions to form singly charged ions of the type [M(2+) - H(+)](+) and of one-electron reductions to form radical cations [M(2+) + e(-)](+.). The dependence of this phenomenon and the formation of a number of additional ionic species on the different matrices and the FAB-matrix additive benzoquinone is examined. The significant analogous behavior of doubly charged porphyrins in FAB- and MALDI-MS leads to the conclusion that one-electron reductions are of distinct relevance in the desorption/ionization mechanism of MALDI.

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Reduction processes in fast atom bombardment mass spectrometry: Methylene blue in glycerol‐thioglycerol and glycerol‐nitrobenzyl alcohol matrices

Cited by 16 publications

References 13 publications

Chemically modified porous silicon for laser desorption/ionization mass spectrometry of ionic dyes

Chemically modified porous silicon for laser desorption/ionization mass spectrometry of ionic dyes

Sensitivity of redox reactions of dyes to variations of conditions created in mass spectrometric experiments

A fast atom bombardment and matrix‐assisted laser desorption/ionization mass spectrometry study of doubly charged porphyrins

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