Fast atom bombardment mass spectrometry of polyglycols

Fast atom bombardment mass spectrometry (FAB-MS) has rapidly become established, after its introduction two years ago, as a method of choice for mass spectral analysis of higher molecular weight polar organic chemicals. In industrial analysis, the technique has been found to be a very effective method for analyzing numerous classes of polar polymeric chemicals, including rubber and plastic additives, organometallics, and polar polymers. Normally applied in conjunction with field desorption (FD-MS), FAB-MS is used to determine chemical structures for both pure compounds and oligomeric mixtures. Fast atom bombardment results for poly(ethylene glycol) and poly(propylene glycol) show that, while oligomer quasimolecular ion distributions give a rough indication of relative oligomer abundances, the data are not quantitative in comparison with that previously described for FD-MS (or electrohydrodynamic ionization, EH-MS) analysis. More specifically, lower mass oligomer intensities tend to be too high in FAB-MS due to fragmentation reactions.     

Fast atom bombardment mass spectrometry of salts

The positive and negative fast atom bombrdment spectra of two groups of simple salts have been recorded. The structures of the major ionic species of eight chlorides and five, complex anion, sodium salts have been interpreted and tabulated.     

Fast atom bombardment mass spectrometry of pertechnetate

Negative Ion Fast Atom Bombardment Mass Spectrometry is conducted on potassium pertechnetate evaporated onto a copper probe. The mass spectra of pertechnetate /TcO ₄ ^– / reveal the presence of mononuclear and polynuclear technetium oxo species which form general series Tc_nO _n+1 ^– ,...Tc_nO_n+4 with n=1 to 5. The polynuclear species are believed to be formed via gas phase reactions.     

Fast atom bombardment mass spectrometry of neutral methanide and ionic carbene platinum(II) derivatives

The fast atom bombardment mass spectra of a series of neutral methanide and ionic carbene platinum(II) complexes of formula dPePtL₂ and [dPePt(LH)₂](BF₄)₂ (dPe = (C₆H₅)₂PCH₂CH₂P(C₆H₅)₂; L = ? C(OCH₃)-NCH₃, ? C(OCH₃) ? NC₆H₁₁, ? C(OCH₃) ? NC₆H₄p ? CH₃), respectively are reported. Glycerol, 3-mercapto-1,2-propanediol, bis (2-hydroxyethyl)sulphide, 3-nitrobenzyl alcohol, and 2,4-di-tert-pentylphenol have been used as matrices. Neutral and ionic derivatives containing the same ligand behave similarly and give the same quasi-molecular [dPePtL(L + H)]⁺ ion by different primary processes. Stepwise breakdown of the ligands L with retention or further loss of atoms or molecules of hydrogen is observed for all these complexes, followed by ejection of radicals from the dPe ligand. Elimination of CH₃OH from [dPePtL(L + H)]⁺ also occurs. The highest ionic yields of both neutral methanide and ionic carbene complexes are observed in 3-mercapto-1,2-propanediol, in bis(2-hydroxyethyl)sulphide, and in 3-nitrobenzyl alcohol with respect to glycerol. The [dPePt(LH)₂]²⁺ doubly charged ions are present in the spectra obtained with 3-nitrobenzyl alcohol and are rather strong when L is ? C(OCH₃) ? NCH₃ and ? C(OCH₃) ? NC₆H₄p ? CH₃. Substitution of ligands L with a molecule or with a fragment of a sulphur containing matrix takes place very seldom with this series of complexes.     

Fast atom bombardment and tandem mass spectrometry of quaternary pyridinium salt-type tryptophan derivatives

Fast atom bombardment and collision-induced dissociation tandem mass spectrometry were used to study the fragmentation of quaternary pyridinium salt-type amides of tryptophan (α-amino-3-indolepropionic acid) esters and their analogs which incorporate the α-nitrogen into the quaternary pyridinium structure. By cleavage directly at the pyridine nitrogen, the 1-alkyl-substituted nicotinamides decompose exclusively to a carbocation, which then becomes the intermediate to further fragments. Rearrangement of the 3-indolepropionate-2-yl carbocations may involve a five- to seven-membered ring expansion, which generates alternative fragmentation pathways; the formation of an even-electron and a radical cation, respectively. In trigonellyl amide-type tryptophan derivatives, fragmentation of the pyridinium ion proceeds on multiple pathways induced by the positive charge which may not be localized on the quaternary nitrogen, and isomerization to a dihydropyridinyl structure is probably involved. Besides the formation of protonated nicotinamide and alkene from tryptophan amides that contain methylene or ethylene units between the amino and the quaternary pyridinium nitrogens, a fragmentation route leading to the carbocation identical with that of the 1-alkyl-substituted nicotinamides has also been revealed.     

Fast atom bombardment mass spectrometry of hydroxybenzoic acids

Summary Ten hydroxybenzoic acids were analysed by positive and negative-ion fast atom bombardment mass spectrometry. FAB-MS of all acids investigated gave intense (M+H)⁺ or (M-H)^– ion peaks. Isomers could be distinguished by the metastabile ion or collisional activation spectra of selected ions, except for m- and p-hydroxybenzoic acid. These compounds could be distinguished, however, by the charge stripping spectra of the (M-H)^– ions.

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FAB-Massenspektrometrie von Hydroxybenzoesäuren

Zusanunenfassung Zehn Hydroxybenzoesäuren wurden mit Hilfe der FAB-Massenspektrometrie (positive und negative Ionen) analysiert. Alle untersuchten Säuren ergaben intensive (M+H)⁺-oder (M–H)^–-Ionenpeaks. Isomere konnten mit Hilfe der Spektren metastabiler Ionen oder von Kollisions-Aktivierungsspektren ausgewahlter Ionen unterschieden werden, außer m- und p-Hydroxybenzoesäure, die durch Charge-stripping-Spektren der (M-H)^–-Ionen unterschieden wurden.

     

Fast atom bombardment mass spectrometry of coordination compounds

It is shown that fast atom bombardment mass spectrometry is well suited for the study of coordination compounds.     

Applications of fast atom bombardment mass spectrometry (FAB MS) to organometallic and coordination chemistry

This article describes the technique of fast atom bombardment mass spectrometry (FAB MS) and its applications to the analysis of organometallic and coordination complexes. Sections on ion generation and matrices are followed by a Periodic Group-based review of FAB MS results obtained from Transition Metal and Main Group compounds, organometallic cluster carbonyls and their derivatives, and salts of poly-oxo-anions. The literature has been surveyed from 1981 to approximately mid-1986.     

Fast atom bombardment mass spectrometry of butyloxycarbonyl protected (BOC) amino acids

The positive and negative ion mass spectra of a series of BOC-protected amino acids have been obtained using an FAB source. The spectra show characteristic features including a McLafferty type of rearrangement.     

Fast atom bombardment mass spectrometry of two isomeric tripeptides

Fast atom bombardment of solids is presented as the basis of a new ion source for mass spectrometry. This novel technique is particularly useful for obtaining mass spectra from involatile and thermally labile materials. The ion source produces both positive and negative ions with equal facility, and examples of both are presented for two underivatized tripeptides. The normal second field free region metastables are observed in a double focusing mass spectrometer and comprehensive metastable pathways have been traced using Barber-Elliott (V-scan) techniques.     

Fast atom bombardment mass spectrometry of seryl- and O-phosphoseryl-containing peptides

FAB-MS was found to be a mild technique for the rapid identification of O—phosphoseryl residues in peptides and the characterization of O—phosphoseryl—containing peptides.     

Fast atom bombardment mass spectrometry of some alkoxv- and chloro-silanes

The positive and negative FAB mass spectra of a series of alkoxy- and chloro-silanes X_m(CH₃)₃-_mSi(CH₂)_nR [m = 1 or 3, n = 3, 10 or 17, X = Cl or OMe or OEt, R = Me, NH₂, glycidoxy, COOMe, NHCO(CH₂)₇COOMe or NHCO(CH₂)₁₀CH₂OAc] were recorded in NBA and NPOE matrices. The chlorosilanes underwent rapid hydrolysis into silanols which condense to form siloxanes, the process being complete in NBA and partial in NPOE, yielding siloxane-based fragment ions in the positive spectra and silyloxyanions in the negative spectra. The alkoxysilanes were more resistant to hydrolysis, affording abundant [MH – HX]⁺ ions (X = OMe or OEt) in their positive FAB spectra and moderate to high intensity [M – H]^? ions in the negative mode, the latter undergoing characteristic sequential loss of C₂H₄, EtOH and C₂H₄. Significant variations were observed in the positive spectra of all the silanes with change of matrix.     

Fast atom bombardment mass spectrometry of protein and carbohydrate biopolymers

Within the past decade significant advances in the field of biological mass spectrometry have resulted in unique approaches to the structural analysis of biopolymers. This article pinpoints key instrumental developments and outlines strategies based upon high field fast atom bombardment mass spectrometry which are allowing hitherto elusive biopolymer structural data to be obtained.     

Fast atom bombardment in mass spectrometry: Method and applications

The review article is devoted to the mass spectrometry method of ionization of material by fast atom bombardment (FAB). The FAB method extends the possibilities of mass spectrometry by making it possible to obtain the mass spectra of nonvolatile, thermally unstable, and high-polarity compounds, which contain information on the molecular weight and the structure of the compounds studied. The mechanism of ion formation, the apparatus design, and also the main results of FAB mass spectrometric study of different classes of compounds are examined. This method is specially helpful in analysis of natural compounds.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 1, pp. 62–78, January, 1987.     

Optimization of fast atom bombardment (FAB) mass spectra of arsenobetaine and arsenocholine

Optimized FAB mass spectra of arsenobetaine and arsenocholine may be obtained when the matrices glycerol and thioglycerol are used.     

Fast atom bombardment mass spectrometry of carbobenzyloxy-protected amino acids and peptides

The positive fast atom bombardment (FAB) mass spectra of 15 N-carbobenzyloxy derivatives of α-amino acids are presented together with those of some synthetic peptides containing other widely employed protecting groups. The data obtained allow a fragmentation pattern to be established for the N-carbobenzyloxy moiety and to obtain detailed structural information on the main fragment ions. A study of the ion current ratio vs. time pattern shows that important fragments derive from the parent protonated molecule through FAB-induced condensed-phase reactions.