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1.
Fast atom bombardment (FAB), FAB mass-analysed ion kinetic energy (FAB MIKE) and collision-activated dissociation (FAB CAD-MIKE) mass spectra were obtained for two series of unsaturated anomeric aryl C-glycosides. These tandem mass spectrometric techniques allowed the differentiation of the anomers by analysing either the [M + H]+ ion or the [M + met]+ ion (met=Li, Na).  相似文献   

2.
Positive and negative ion fast atom bombardment (FAB) mass spectra of some monosubstituted nitroaromatic isomers are reported. Generally ions carresponding to [M + H]+ and M+ are observed in the positive ion FAB spectra; ions such as [M ? H] ? and M?˙ are observed in the negative ion FAB spectra. The use of FAB mass spectra to distinguish the isomers is discussed. Comparisons of FAB, chemical ionization and electron impact mass spectra of the same isomers (wherever possible) are reported. The structural information obtained in the negative ion FAB spectra complement those obtained in the positive ion FAB spectra.  相似文献   

3.
The unimolecular fragmentations of [M + H]+ and [M – H]? ions from four 2-aryl-2-methyl-1,3-dithianes are described and clarified with the aid of deuterated derivatives. Comparison of the MIKE spectra of [M + H]+ species obtained under chemical ionization and fast atom bombardment (FAB) conditions reveals differences which are attributed to the different energetics involved in the two ionization processes. It is suggested that FAB is a ‘softer’ ionization technique but, at the same time, it provides, for the possibility of solvation, reaction sites not available in gas-phase protonation. [M – H]? species and anionic fragments thereof were generally not obtained under FAB(?) conditions. [M – H]? ions are readily produced in gas-phase reactions with OH? via proton abstraction from C(4) or C(5), and from the 2-methyl substituent; and they fragment according to several reaction pathways.  相似文献   

4.
Positive-ion fast atom bombardment (FAB) and B/E linked scan FAB mass spectra of seven carotenoids are reported. In all cases the M ions are observed, and the [M + H]+ ions are absent in the hydrocarbons and weak in the oxygenated compounds. The usefulness of B/E linked scan FAB mass spectra to distinguish isomers and to attribute the loss of toluene from the M to an ionic fragmentation and not to a thermal process is discussed.  相似文献   

5.
Mechanisms are proposed for the formation of M+, [M + 2H]+ and [M + 3H]+ ions in the fast atom bombardment (FAB) mass spectra of 4-(2,2,6,6-tetramethyl-1-oxyl)-piperidol and its carboxylates. Free radical quenching induced by the fast atom beam has been observed. The effects of temperature on the radical quenching and of acid on the FAB mass spectra are discussed. The experiment showed that the volatile liquid samples with vapour pressures higher than that for glycerol produced M+ even-electron molecular ions, and the FAB mass spectra were similar to the corresponding electron ionization mass spectra. For the solid samples, it was found that the free radicals were quenched during the FAB process so that the mononitroxide and dinitroxide compounds produced [M + 2H]+ and [M + 3H]+ ions, respectively. Further experiments showed that the intensities and stabilities of [M + 2H]+ and [M + 3H]+ ions could be improved by addition of acids.  相似文献   

6.
When mass-analysed ion kinetic energy (MIKE) spectra are required to discriminate between isomeric ions formed under conditons of fast atom bombardment (FAB) in the ion source, severe interference may be observed. The interfering peaks in MIKE spectra obtained with a reversed-geometry instrument can arise from different sources. Moreover, the intensity distribution of the true ions from the selected precursor ion may depend strongly on the instrument being used. This means that the FAB–MIKE or collisionally induced dissociation (CID) spectrum is not an absolute characteristic of a particular ion. The [M + H ? HOAc]+ ion in the spectrum of peracetylated ribopyranose is used as an example to illustrate this and to trace and discuss the origin of the phenomena observed.  相似文献   

7.
Positive-ion fast atom bombardment mass spectrometry appears to be a useful method for the differentiation of anomeric C-glycosides. The mass-analysed ion kinetic energy (MIKE) and collision-activated dissociation (CAD) MIKE spectra of selected positive ions can be used as fingerprints of the α- or β-anomers. The main fragmentation routes and particularly the formation of the [M ? H]+ ion and the [M + H ? PhCH2OH]+ ion were traced for each anomer.  相似文献   

8.
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.  相似文献   

9.
Analyses of a series of nitroaromatic compounds using fast atom bombardment (FAB) mass spectrometry are discussed. An interesting ion-molecule reaction leading to [M + O ? H]? ions is observed in the negative ion FAB spectra. Evidence from linked-scan and collision-induced dissociation spectra proved that [M + O ? H]? ions are produced by the following reaction: M + NO2? → [M + NO2]? → [M + O ? H]?. These experiments also showed that M ions are produced in part by the exchange of an electron between M and NO2? species. All samples showed M, [M ? H]? or both ions in their negative ion FAB spectra. Not all analytes studied showed either [M + H]+ and/or M+˙ in the positive ion FAB spectra. No M+˙ ions were observed for ions having ionization energies above ~9 eV.  相似文献   

10.
Electron impact mass spectra were measured for five isomers of pyridinobenzanthrones and three isomers of benzobenzanthrones. The fragmentation pattern and intensity of M2+, [M – H]+, [M – CO]i+, [M – CO – H(or 2H)]i+ and [M – CO – HCN]i+ (i = 1, 2) ions indicated remarkable differences and very interesting features according to the isomers with or without nitrogen and condensation positions of a pyridino or benzo ring to the benzanthrone skeleton. Further, the competition of decompositions through [M – H]+, [M – CO] or [M – HCN] ions was confirmed by the observation of metastable ions and the appearance energies of fragment ions. Interesting observations from these results were expulsion of an H atom in close proximity to the area around an O?C group, a weak bonding interaction between sp2 C? H and an O?C group, inducing specific hydrogen rearrangement, and characteristic charge localization on heteroatoms.  相似文献   

11.
The positive ion field desorption (FD) spectrum of arginine taken at the best anode temperature only contains a peak due to [M+H]+ ions. At higher emitter temperatures a considerable amount of fragmentation is induced and the [M+H NH3]+ ions become most abundant. Specific 15N labelling reveals that the eliminated ammonia molecule, exclusively, contains one of the terminal nitrogen atoms of the guanidyl group. This also applies to the ammonia loss from metastably decomposing [M+H]+ ions. The positive ion fast atom bombardment (FAB) spectrum shows more fragmentation than the FD spectrum. In contrast with the FD results, the [M+H]+ ions generated upon FAB with ion lifetimes <10−6 s eliminate both ammonia containing one of the terminal nitrogen atoms of the guanidyl group and ammonia containing the α-amino group in the ratio of 1.35, as found by 15N labelling. The metastably decomposing [M+H]+ ions, however, eliminate only the former ammonia molecule. In the negative ion FD and FAB spectra no other peak than that corresponding to the [M H] ion is observed. Some attention has been paid to the thermal degradation of arginine on the basis of a few Curie-point pyrolysis experiments.  相似文献   

12.
Five glucosylceramides (GlcCers) were isolated by reversed phase high‐performance liquid chromatography from the MeOH extracts of a marine sponge, Haliclona (Reniera) sp., collected from the coast of Ulleung Island, Korea, and analyzed by fast atom bombardment mass spectrometry (FAB–MS) in positive‐ion mode. FAB‐mass spectra of these compounds included protonated molecules [M + H]+ and abundant sodiated molecules [M + Na]+ from a mixture of m‐NBA and NaI. The structures of these GlcCers, which were similar, were elucidated by FAB‐linked scan at constant B/E. To find diagnostic ions for their characterization, the GlcCers were analyzed by collision‐induced dissociation (CID) linked scan at constant B/E. The CID‐linked scan at constant B/E of [M + H]+ and [M + Na]+ precursor ions resulted in the formation of numerous characteristic product ions via a series of dissociative processes. The product ions formed by charge‐remote fragmentation provided important information for the characterization of the fatty N‐acyl chain moiety and the sphingoid base, commonly referred to as the long‐chain base. The product ions at m/z 203 and 502 were diagnostic for the presence of a sodiated sugar ring and β‐D ‐glucosylsphinganine, respectively. For further confirmation of the structure of the fatty N‐acyl chain moiety in each GlcCer, fatty acid methyl esters were obtained from the five GlcCers by methanolysis and analyzed by FAB–MS in positive‐ion mode. On the basis of these dissociation patterns, the structures of the five GlcCers from marine sponge were elucidated. In addition, the accurate mass measurement was performed to obtain the elemental composition of the GlcCers isolated from marine sponge. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

13.
The mass spectrometric behaviour of a series of 2-aryl substituted 4,7-dioxo-4,5,6,7-tetrahydroindoles has been studied in different ionization conditions (Electron Ionization and Fast Atom Bombardment), with the aid of the metastable ion studies. In electron ionization conditions all the compounds exhibit a highly favoured, primary H2 loss giving rise to the corresponding indole-4,7-diones; in the usual spectra no evidence for the molecular ions in the enolic form was found, while the OH* loss observed in the MIKE (mass analyzed ion kinetic energy) spectra of molecular ions suggests that species at low internal energy content isomerize to the corresponding tautomeric enolic form. FAB mass spectra show easy formation of an unusual [M + 2H]+ species, together with abundant [M + H]+ and M+ cations.  相似文献   

14.
The ammonia chemical ionization (CI/[NH4+]) mass spectra of a series of diastereomeric methyl and benzyl ethers derived from 3-hydroxy steroids (unsaturated in position 5 and saturated) have been studied. The adduct ions [M+NH4]+ and [MH]+ and the substitution product ions [M+NH4? ROH]+ (thereafter called [MsH]+) are characterized by an inversion in their relative stabilites in relation to their initial configuration. [M+NH4]α+ and [MH]α+ formed from the α-Δ5-steroid isomers are stabilized by the presence of a hydrogen bond which is not possible for the β-isomers. This stereochemical effect has also been observed in the mass analysed ion kinetic energy (MIKE) spectra of [M+NH4]+ and [MH]+. The MIKE spectra of [MsH]+ indicate that those issued from the β-isomers are more stable than the one originating from the α-isomers. This behavior is also observed in the first field free region (HV scan spectra) for [MH]+, [MsH]+ and [M+NH4]+ which are precursors of the ethylenic carbocations (base peak in the conventional CI/[NH4]+ spectra). Mechanisms, such as SN1 and SNi, have been ruled out for the formation of [MsH]+, but instead the data support an SN2 mechanism during the ion-molecule reaction between [M+NH4]+ and NH3.  相似文献   

15.
The competitive formation of molecular ions M and protonated molecules [M + H]+ under fast atom bombardment (FAB) conditions was examined using various kinds of organic compounds. The use of protic/hydrophilic matrices such as thioglycerol and glycerol resulted in relatively large values of the peak intensity ratio I([M + H]+)/I(M) compared with the use of relatively aprotic/hydrophobic matrices such as m-nitrobenzyl alcohol and o-nitrophenyl octyl ether. The change of matrix from thiol-containing such as thioglycerol and dithiothreitol to alcoholic such as glycerol and pentamethylene glycol increased the I([M + H]+)/I(M) ratio. Furthermore, the change of matrix increased the peak intensity ratio of the doubly charged ion [M + 2H]2+ to [M + H]+ in the FAB mass spectra of angiotensin I and gramicidin S. The addition of acids to the matrix solution increased the I([M + H]+)/I(M) ratio, although such an effect did not always occur. The acetylation of simple aniline compounds markedly increased the I([M + H]+)/I(M) ratio. It was concluded from these results that the hydrogen bonding interaction between hydroxyl groups(s) of the matrix and basic site(s) of analyte molecules in solution acts advantageously as a quasi-preformed state for [M + H]+ formation, and that the presence of significant proton acceptor(s) such as carbonyl group in analytes hinder the M formation which may generally occur under FAB conditions. The formation of M and [M + H]+ ions seemed to occur competitively, reflecting or according to the interaction or solvation states between the analyte and matrix molecules in solution and the structural characteristics of the analytes.  相似文献   

16.
The characteristics of the in-beam electron impact mass spectra of six isomers of undecanol as well as several 1-alkanols have been examined. In addition to the characteristic ions observed in the conventional electron impact spectra, the [2M+1]+, [2M+1-H2O]+, [2M+1-2H2O]+, [2M-R or R′]+, [2M-H2O? R or R′]+, [2M? 2H2O? R or R′]+ and [M+1? H2O]+ peaks are common in the in-beam electron impact mass spectra of the undecanol isomers of structure RCH(OH)R′. Deuterium labelling experiments have shown that the extra proton in the protonated dimer ions, [2M+1]+, originates from the hydroxy group. The processes which produce the important peaks in the high m/e regions are discussed.  相似文献   

17.
Positive-ion fast atom bombardment (FAB) mass spectra of flavonol and steroid glycosides with sodium chloride added showed well known characteristic features; of the appearance of [M + Na]+ peaks, disappearance of [M + H]+ peaks and a significant decrease in the peak heights of fragment ions. Compared with the features in the FAB mass spectra of crown ethers with addition of salt, and above features suggest a complexation between Na+ and the glycosides in matrix solution. The B/E-constant linked scanning technique was used to obtain structural information of the [M + Na]+ ion of the glycosides. The B/E spectra gave the daughter-ion peaks, suggesting that coordination of Na+ with the biosides and triosides occurs at the sugar moiety, whereas the coordination with the monoglycosides occurs at the aglycone moiety, except for monoglycosides in which the aglycone moiety does not contain significant oxygen functional groups such as OH and CO.  相似文献   

18.
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[4.3.3.01,6]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.  相似文献   

19.
The collision-induced dissociation (CID) spectra of glycoside–alkali metal adduct ions [M + C]+ (C = Li, Na, K and Rb) produced under fast atom bombardment (FAB) conditions are reported. The results obtained suggested that the CID spectra of the [M + C]+ ions of some flavonoid glycosides reflect the coordination structures because the CID patterns generally changed with the metal cation size. In diglycosides, the CID spectra showed that the relatively small cations Li+ and Na+ rather bind to the sugar moiety, whereas the large cations K+ and Rb+ rather bind to the aglycone moiety. In monoglycosides, the cations C+ rather bind to the aglycone moiety. It was concluded that the CID technique combined with FAB is useful for the structural elucidation of [M + C]+ ions and, in principle, the CID spectra reflect the coordination structures in the gas phase.  相似文献   

20.
Ion/molecule reactions of saturated hydrocarbons (n‐hexane, cyclohexane, n‐heptane, n‐octane and isooctane) in 28‐Torr N2 plasma generated by a hollow cathode discharge ion source were investigated using an Orbitrap mass spectrometer. It was found that the ions with [M+14]+ were observed as the major ions (M: sample molecule). The exact mass analysis revealed that the ions are nitrogenated molecules, [M+N]+ formed by the reactions of N3+ with M. The reaction, N3+ + M → [M+N]+ + N2, were examined by the density functional theory calculations. It was found that N3+ abstracts the H atom from hydrocarbon molecules leading to the formation of protonated imines in the forms of R′R″C?NH2+ (i.e. C–H bond nitrogenation). This result is in accord with the fact that elimination of NH3 is the major channel for MS/MS of [M+N]+. That is, nitrogen is incorporated in the C–H bonds of saturated hydrocarbons. No nitrogenation was observed for benzene and acetone, which was ascribed to the formation of stable charge‐transfer complexes benzene????N3+ and acetone????N3+ revealed by density functional theory calculations. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

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