Fast atom bombardment mass spectrometry of Mycobacterial glycopeptidolipid antigens: Structural characterization by charge remote fragmentation

Mycobacteria contain species- and type-specific antigens. Among them, glycopeptidolipids are present in medically relevant organisms belonging to Mycobacterium avium or M. fortuitum complexes. Fast-a tom bombardment mass spectrometry of glycopeptidolipids has proven to be difficult. In this article the cationization method with a metanitrobenzyl alcohol matrix, doped with sodium iodide, is described for analyzing these molecules. The molecular weight of the intact glycopeptidolipids was successfully determined and, using mass-analyzed ion kinetic energy spectrometry, the complete sequences of the peptide and saccharide moieties were elucidated. Moreover, the two structural variants present in these molecules were clearly differentiated. Application of the method showed that the same structural variant occurs in the glycopeptidolipids from two serologically related species of the M. fortuitum complex.     

Characterization of iridoids by fast atom bombardment mass spectrometry followed by collision-induced dissociation of

Fast atom bombardment mass spectra of a series of naturally occurring and synthetically modified iridoid glycosides were studied using lithium cationization and collision-induced dissociation of the resulting [M+Li]+ ions. Lithium cationization leads to the unambiguous determination of the molecular masses of these compounds. Collision-induced dissociation of the lithiated molecular ions give valuable structural information regarding the nature of the substituent on both the aglycone and the sugar moieties. The characteristic fragmentation pathways identified are (1) elimination of neutral molecules comprising the substituents on either the aglycone or sugar moieties, (2) formation of lithiated aglycone and their fragment ions, (3) formation of lithiated sugar and their fragment ions, (4) fragmentation corresponding to the cleavage of the aglycone or sugar ring and (5) fragmentation characteristic of the substituents present in either the aglycone or sugar parts of the molecule. Elimination of two acyloxy radicals from the lithiated molecular ion is a characteristic fragmentation in the case of acyloxy derivatives.     

Structural determination of saponins extracted from starfish by fast atom bombardment collision-induced dissociation mass spectrometry.

Three saponins were extracted and isolated from starfish by reversed-phase high performance liquid chromatography (HPLC), and analyzed by fast atom bombardment mass spectrometry (FAB-MS). Their molecular weight information could be obtained by the presence of abundant [M+Na]+ ions and weak [M+H]+ ions in FAB-MS spectra. Moreover, high resolution mass measurements of their [M+Na]+ ions were performed at the resolution of 10000 to elucidate the element composition of extracted saponins. The collision-induced dissociation (CID) of sodium-adducted molecules [M+Na]+ yielded diverse product ions via dissociated processes. In the collision-induced dissociation (CID)-MS/MS analysis of [M+Na]+ ion, the sulfate-containing saponins produced characteristic ions such as SO4Na+, [NaHSO4+Na]+, [M+Na-sugar]+ and [M+Na-2sugar]+ ions, whereas the sulfate-free compound showed characteristic ions produced by cleavage of sugar moiety and side chain of aglycone. The fragmentation patterns could provide information on the linkage position of sugar groups in aglycone and sulfate groups.     

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 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.     

暗霉素的快原子轰击(FAB)质谱

快原子轰击(fast atom bombardment,简称 FAR)质谱是八十年代开发的质谱新技术.这种在室温条件下用具有一定能量的中性原子轰击样品进行离子化的技术特别适用予热稳定性差、难挥发、强极性样品的分析.我们用 FAB 对七个暗霉素(nebramycin)抗生素组分进行结构测定,获得了较满意的结果.暗霉素属氨基糖苷类抗生素.我们从我国土壤中分离的菌株发酵液中提取暗霉素复合物及其水解产物,并分离和鉴定了七个单一组分.这七个化合物(1～7)的结构如下:     

Charge-remote fragmentation characteristics of functionalized alkanes in high-energy collision-induced dissociation

In this study we report on high-energy, collision-induced dissociation processes leading to charge-remote fragmentations, using three alkyl cations, namely n-hexadecylpyridinium, n-hexadecyltriphenylphosphonium and n-hexadecyltriethylammonium, each with and without (2)H(2)-labelling at the C(9) position of the hexadecyl chain. The characteristic patterns corresponding to the formal elimination of alkane elements were observed, and the (2)H(2)-labelling at C(9) clearly affected only one charge-remote fragment ion of the homologous series. However, in addition to the expected fragment ion containing only one deuterium atom, a significant ion retaining two deuterium atoms was observed. MS/MS/MS experiments demonstrated clearly that the latter ion showed partial deuteration around the charge site, the level of deuteration depending on the structure of the original precursor cation. These results can be interpreted in terms of two novel, distinct mechanisms, one of which involves an excited state in an aromatic ring. Mixed-site fragmentation (MSF) ions were also observed from the phosphonium and ammonium ion precursors. We believe that the observation of the MSF process occurring at an sp(2)-hybridized center in the phosphonium series has not been reported previously. It thus becomes apparent that high-energy collisions leading to charge-remote reactions in fact lead to a broad range of pathways. Copyright 2000 John Wiley & Sons, Ltd.     

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 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.     

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.     

Fast atom bombardment mass spectra of telluronium salts

The fast atom bombardment (FAB) mass spectra of telluronium salts were studied. The spectra exhibit the intact cation (C⁺) and cluster ions ([M + C]⁺). The principal fragment ions in the FAB mass spectra of telluronium salts are [RTe]⁺, [R₂Te]⁺˙, [R₂Te − H]⁺, [RTeR′]⁺˙, and [RTeR′ + H]⁺. When the anion was [BPh₄]⁻, interesting cluster ions such as [M + C − BPh₃]⁺ appeared.     

Fast atom bombardment mass spectra of iodonium salts

Positive-ion fast atom bombardment mass spectra and linked-scan tandem mass spectra were measured for aromatic iodonium salts. The mass spectra usually contain the intact cation of the iodonium salt as the base peak, fragment ions of lower abundance resulting from simple cleavages or rearrangements, and a characteristic loss of atomic iodine. High-level semi-empirical calculations suggest that an obtuse ring? I⁺? ring angle facilitates loss of atomic iodine through concomitant ring? to? ring bond formation.     

Identification of cyclic nucleotide derivatives synthesized for radioimmunoassay development by fast atom bombardment with collision-induced dissociation and mass-analysed ion kinetic energy spectroscopy

The syntheses of 2′-O-succinyl, 2′-O-succinyltyrosinyl methyl ester and 2′-O-succinyliodotyrosinyl methyl ester derivatives of a cyclic nucleotide, derivatives necessary for the successful development of a specific radioimmuno-assay, are described. Fast atom bombardment with collision-induced dissociation and mass-analysed ion kinetic energy spectroscopy were used to verify the positions of substitution and the retention of the 3′,5′-cyclic phosphate moiety. Comparison of spectra produced after different iodination times permitted the optimization of the reaction conditions.     

Fast atom bombardment induced ring rupture of silatranes

During a comparison study of the fast atom bombardment (FAB) and electron impact mass spectra of 1-organyl-2,9,10-trioxa-6-aza-1-silatricyclo[4.3.3.0^1,6]dodecanes, an unusual ion peak at m/z 164 was noticed in the FAB spectra. Accurate mass measurement indicated that m/z 164 corresponds to protonated 1-[N,N-bis(2-hydroxyethyl)amino]-1-propanol (BHAP), which is produced by a ring-rupture reaction. Further experiment showed that the intensity of the [BHAP + H]⁺ ion peak increased markedly as the 7keV Ar⁰ bombardment proceeded, suggesting a FAB-induced reaction. The possible mechanism is also discussed.     

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.

     

Analyses of anandamide and endocannabinoid-like compounds using collision-induced dissociation in fast atom bombardment ionization-mass spectrometry and gas chromatography/chemical ionization-mass spectrometry.

The utility of the collision-induced dissociation (CID) of two different forms of precursor cations generated by the fast atom bombardment (FAB) ionization of N-arachidonylethanolamine (anandamide) and a series of endocannabinoid-like compounds, such as N-oleoylethanolamine, N-palmitoylethanolamine, N-stearoylethanolamine, N-linoleoylethanolamine, N-oleoylpropanolamine, and N-palmitoylpropanolamine, as a method of providing general information on their characterizations was examined. The CID spectra of lithium-adduct [M+Li]+ ions of the amines with unsaturated hydrocarbon chains were rich in structurally informative charge-site-remote (CSR) fragmentation patterns that provide information on the locations of double bonds in hydrocarbon chains. On the other hand, the CID reactions of [M+H]+ ions produced acylium ions that are derived from the cleavage of amide bonds, thus providing information on the size of the hydrocarbon chains, although CSR fragmentations were not observed. These compounds without derivatization were analyzed using gas chromatography/chemical ionization-mass spectrometry (GC/CI-MS) with a polyethylene glycol phased column with fused silica capillary pre-tubing. Identifiable molecular-related [M+H]+ ions were observed.     

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.