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1.
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   

2.
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   

3.
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   

4.
Electron impact induced fragmentation of the title compounds obeys a route where the lactam moiety, OCNH, is cleaved first, with the accompanying formation of a cycloalkene ion. This can be verified by low-resolution, high-resolution, B/E and B2/E spectra as well as by collisional activation spectra of, for example, the ions m/z 82 and 67 from 7-azabicyclo[4.2.0]octan-8-one and from cyclohexene. The only, and fairly weak, fragment ions including O and N are [C3H3O]+, [CkH2k-2N]+ (k = 5–8) and [C3H6N]+. The ammonia chemical ionization spectra are also characteristic for all four lactams and show the same dominant ions in all cases, namely [M + 1]+, [M + 1 + NH3]+˙ and [2 M + 1]+˙.  相似文献   

5.
The electron impact mass spectrometric behaviour of a series of macrocyclic-acyclic polyether-ester compounds containing an isoxazole, benzene or pyridine ring is discussed in detail with the aid of exact mass measurements and metastable ions (linked scans B/E and B2/E). The nature of unusual [M+H]+ species, present in the crown moieties only, is elucidated by means of low electron energy measurements and labelling experiments. The field desorption spectra show only intense peaks corresponding to [M+H]+ species and rule out the presence of dimeric moieties.  相似文献   

6.
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   

7.
The aim of this study was to present integrated mass spectrometric methods for the structural characterization and identification of flavonoid glycoconjugates. During the liquid chromatography/mass spectrometry analyses, TriVersa NanoMate chip‐based system with nanoelectrospray ionization and fraction collection was combined to a quadrupole time‐of‐flight mass spectrometer. In the extract samples prepared from green leaves of wheat plantlets, 41 flavonoid derivatives were recognized. Part of the target natural products had the full structure being characterized after the registration of mass spectra, where m/z values for protonated [M + H]+ and deprotonated molecules [M ? H]? were annotated. MS2 and pseudo‐MS3 experiments were performed for [M + H]+ or [M ? H]? and aglycone ions (Y0+/?‐type), respectively. It should be underlined that pseudo‐MS3 mass spectra were registered for aglycone product ions in the mass spectra of O‐glycosides present in the extract samples. In many cases, only tentative structural identification of aglycones was possible, mainly because of the presence of numerous C‐monoglycoside or C‐diglycoside in the samples. Acylation of the sugar moiety and/or methylation of the aglycone in the flavonoid glycosides under study was observed. The existence of isobaric and/or isomeric compounds was demonstrated in the extract studied. The collision‐induced dissociation mass spectra registered for C,O‐diglycosides and C,C‐diglycosides did not permit to draw complete structural conclusions about the compounds studied. For the investigated class of natural products, unambiguous classification of sugar moieties linked to the aglycones from the recorded mass spectra was not possible. Registration of the positive and negative ion mass spectra did not lead to the precise conclusion about the glycosylation position at C‐6 or C‐8, and O‐4′ or O‐7 atoms. It was possible, on the basis of the collected MS2 spectra, to differentiate between O‐glycosides and C‐glycosides present in the samples analyzed. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

8.
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   

9.
A series of new synthetic tetrabenzyl N-glucosidic, N-mannosidic and N-galactosidic isomers were investigated by fast atom bombardment (FAB)/mass-analysed ion kinetic energy (MIKE) spectrometry. The [M + H]+ ions were obtained with high abundance in the FAB spectra when using 3-nitrobenzyl alcohol as the matrix. The FAB/MIKE spectra provide characteristic daughter ions fragmented from selected molecular parent ions, allowing these isomers to be differentiated. In addition, an interesting rearrangement was found from the MIKE spectra, indicating that the benzyl (Bzl) group on the sugar ring is rearranged on to the N atom of the base (R) group to form [R + Bzl + H]+ and [R+ 2Bzl]+ ions.  相似文献   

10.
The tetramethylsilane (TMS) chemical ionization (CI) mass spectra of some geometrical isomers of unsaturated dicarboxylic acids, esters and isomeric phthalic acids reveal explicit differences. The (E)-acids show an abundant [M + 73 ? CH4]+Ion whereas the (Z)-acids exhibit a strong [M + 73 ? H2O]+ ion in their TMS CI spectra. The loss of CH4 from the adduct of fumaric acid has been confirmed by the study of fumaric acid-d2 and B/E linked scan studies. In the case of esters, the TMS CI spectra of (E)-isomers contain abundant [M + 73]+ adduct ions, whereas these are weakly abundant in the TMS CI of the (Z)-isomers.  相似文献   

11.
在对糖苷的FAB分析技术的研究中发现,如果在样品中同时加入适量的NaCl和LiCl水溶液进样时,其FAB谱中会出现[M+Na]^+和[M+Li]^+两个强峰,两峰之质量差为16(Na和Li原子量之差值),并且发现其谱图中找不到明显的碎片离子和Na^+及Li^+的加合离子,而只有糖苷分子和Na^+及Li^+的加合离子。所以很容易在FAB谱中识别它们。因而不需联谱解析而仅凭FAB谱就可准确、快速地定出糖苷的分子量。此技术国内外尚未见报道。  相似文献   

12.
N-Acetylcysteine and nine N-acetylcysteine conjugates of synthetic origin were characterized by positive- and negative-ion plasma desorption mass Spectrometry. For sample preparation the electrospray technique and the nitrocellulose spin deposition technique were applied. The fragmentation of these compounds, which are best seen as S-substituted desaminoglycylcysteine dipeptides, shows a similar behaviour to that of linear peptides. In the positive-ion mass spectra intense protonated molecular ion peaks are observed. In addition, several sequence-specific fragment ions (A+, B+, [Y + 2H]+, Z+), immonium ions (I+) and a diagnostic fragment ion for mercap-turic acids (RM+) are detected. The negative-ion mass spectra exhibit deprotonated molecular ions and in contrast only one fragment ion corresponding to side-chain specific cleavage ([RXS]?) representing the xenobiotic moiety. In the case of a low alkali metal concentration on the target, cluster molecular ions of the [nM + H]+ or [nM - H]? ion type (n = 1-3) are observed. The analysis of an equimolar mixture of eight N-acetylcysteine conjugates shows different quasi-molecular ion yields for the positive- and negative-ion spectra.  相似文献   

13.
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   

14.
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   

15.
In the fast atom bombardment mass spectra of tetracyclines, ammonia elimination fragment ions, [M + H – NH3]+ and [M + H – NH3 – H2O]+, appeared with considerable abundances. A plausible mechanism for the loss of ammonia from [M + H]+ was discussed based on results by measurements on various types of tetracyclines and benzamides as the model compounds and B/E linked scanning. The results indicated that the loss of ammonia occurred in the carboxyamide moiety in the A ring and was accelerated by an ortho-hydroxy group. The same fragmentations were observed in the electrospray mass spectra of tetracyclines with a skimmer-capillary voltage differential of 150 V.  相似文献   

16.
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   

17.
Some ion-formation processes during fast atom bombardment (FAB) are discussed, especially the possibility of reactions in the gas phase. Divided (two halves) FAB probe tips were used for introducing two different samples into the source at the same time. Our results showed [M + A]+ ions (where M = crown ethers and A = alkali metal ions), can be produced, at least in part, in the gas phase when crown ethers and sources of alkali metal ion are placed on two halves of the FAB probe tip. The extent of this ion formation depends on the volatility of the crown ether and on steric factors. Cluster ions such as (M + LiCl)Li+, (2M + LiCl)Li+, [2M + K]+ and [2M + Na]+ are also observed to form in the gas phase. Unimolecular decompositions contribute to some ions detected in FAB. When the alkali ion salt and the crown ether are mixed together the probability of [M + A]+ ion formation increases significantly, regardless of the volatility of the crown ether.  相似文献   

18.
In the field desorption mass spectrometry of oligosaccharides, traces of contaminating salts in polar solvents decrease the detection sensitivity, and in some cases no ion could be detected in the molecular range. The present work shows that the addition of alkaline salts (NaI or KI) greatly increases the sensitivity, and cationized molecular ions are obtained. The influence of the molar ratio sugar/salt on the nature and relative intensity of the desorbed species has been studied on mixtures of α-D -trehalose and NaI. At the low salt ratio (100:1), high molecular weight clusters [X M + Na]+ are preferentially formed. At the high salt ratio (1:10), mixed clusters [M + NaI + Na]+, doubly charged ions [M + 2Na]2+ and monomeric cationized ions [M + Na]+ are observed along with salt clusters [NaI + Na]+ and [2NaI + Na]+. In the range of molar ratios sugar/salt of 10:1 to 1:1, the field desorption mass spectra exhibit a cationized ion [M + Na]+, which contributes more than 80% of Σ100. This cationization technique has been applied to the field desorption mass spectrometry of several oligosaccharides. In all cases, the salt effect causes the replacement of the [M + H]+ ion by a [M + C]+ ion. (Note: the term [M + C]+ and similar ones mean an association between the whole molecule studied (M) and an alkaline cation [C]+ ([K)]+, [Na]+, [Li]+).) Thus, di, tri- and tetrasaccharides exhibit intense [M + Na]+ ions in the presence of NaI and only a few fragment peaks are observed in their field desorption mass spectra. This technique has been applied successfully to the detection of the hexasaccharide ajugose in a natural sample of pentasaccharide, and has also allowed the unambiguous determination of the composition of a mixture of partially methylated trehaloses. The salt effects are dicussed in terms of selective adsorption on the emitter, pre-existing soluble complexes sugar-salt, interactions between these species in the electric field and dissociative desorption of ionic complexes.  相似文献   

19.
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   

20.
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   

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