Consecutive reaction monitoring in a four-sector mass spectrometer: MS4 and one step beyond.
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Mass Spectrometry↗
Biomedical subjects
K B Tomer
Publications and source records attributed to K B Tomer.
FAB and tandem mass spectrometry for endorphin- and ACTH peptides of molecular weight to 2000.
Four beta-endorphins (beta-endorphin 6-17, 2-17, 1-16, and 1-17) and two adrenocorticotropic hormone (ACTH) peptides (ACTH 1-10 and (1-16)-NH2) were studied by using fast atom bombardment coupled with tandem mass spectrometry. The capability to reproduce metastable ion and collisionally activated decomposition spectra on two different commercial sector mass spectrometers in two different laboratories was found to be acceptable (deviations in relative abundance are less than +/- 50%). The endorphin peptides fragment metastably or upon collisional activation to give abundant B-series ions as well as Y-series ions, whereas Y-series ions are the principal ionic species produced upon the desorption by fast atom bombardment. The ACTH peptides also fragment to give Y-series ions, but of relatively low abundance compared to those from the endorphins. For both sets of peptides, high-energy collisionally activated decomposition and metastable ion decomposition daughter ion spectra are precise, structurally informative--even for peptides up to m/z 2000--and complementary to spectra of daughter ions produced by desorption ionization alone.
Adrenocorticotropic Hormone↗
Analysis of glutathione conjugates and related compounds by thermospray mass spectrometry.
A series of 17 cysteine, N-acetyl cysteine, glutathione, and N-trifluoroacetyl glutathione conjugates have been prepared, and their thermospray (TSP) spectra have been recorded in the positive and negative ion modes. The compounds undergo extensive fragmentation, which primarily occurs at the carbon-sulfur bonds. For most of the compounds, positive ion TSP is more sensitive than negative ion thermospray. Probably due to the thermal lability of these adducts, the quality of the spectra obtained are dependent on source conditions, requiring fine control of the vaporization/desolvation process.
Chemical Phenomena↗
Thermospray liquid chromatographic-mass spectrometric method for the analysis of metribuzin and its metabolites.
A thermospray liquid chromatographic-mass spectrometric (TSP LC-MS) method has been developed for the analysis of the herbicide metribuzin and its three major metabolites in plant tissue. Metribuzin and its metabolites exhibited widely varying sensitivities in positive-ion TSP, with metribuzin being the most sensitive and deaminated diketo metribuzin being the least sensitive. All four compounds of interest were detected in an extract of a soybean plant which had been treated with metribuzin.
Biotransformation↗
Fast atom bombardment and tandem mass spectrometry for structure determination: remote site fragmentation of steroid conjugates and bile salts.
A series of 35 steroid conjugates (sulfates and glucuronides) and bile salts were investigated by using fast atom bombardment and tandem mass spectrometry. Collisional activation of the [M - H]- anions of sulfate conjugates and bile salts predominantly yields fragment ions arising by reactions occurring remote from the charge site. These reactions are sometimes sensitive to differences in stereochemistry at positions remote from the charge site and are useful for positional isomer differentiation. On the other hand, collisional activation of the [M - H]- anions of the glucouronide conjugates leads primarily to charge-driven fragementations.
Bile Acids and Salts↗
Applications of fast atom bombardment and tandem mass spectrometry.
The application of fast atom bombardment combined with tandem mass spectrometry to the structure elucidation of carcinogen-modified oligonucleotides, glutathione, cysteine and N-acetyl cysteine conjugates of exogenous toxins and chemically modified peptides is described.
Acetylcysteine↗
Separation and identification of trifluralin metabolites by open-tubular liquid chromatography/negative chemical ionization mass spectrometry.
The utility of combined open-tubular liquid chromatography/negative ion chemical ionization (NCI) mass spectrometry for the separation and analysis of trifluralin, a commonly used pre-emergence herbicide, and seven of its metabolites has been demonstrated. The NCI mass spectra for these compounds are reported. Some of the NCI mass spectra were obtained from as little as 50 pg of analyte.
Chromatography, Liquid↗
Identification and characterization of the major DNA adduct formed chemically and in vitro from the environmental genotoxin 3-nitrofluoranthene.
The genotoxic environmental pollutant 3-nitrofluoranthene (3-NFA) was reduced chemically and allowed to react with calf thymus DNA, yielding one major adduct which was determined to be N-(deoxyguanosin-8-yl)-3-amino-fluoranthene based on Fast Atom Bombardment Mass Spectrometry (FAB-MS), proton nuclear magnetic resonance, ultraviolet-visible wavelength light spectroscopy (UV-VIS), and fluorescence data. Extensive characterization of the isolated adduct by tandem mass spectrometry (MS/MS) was necessary to demonstrate definitively that the adduct isolated was the dG:C8 adduct, and not the isomeric dG:N2 adduct. The extent of modification of the initial calf thymus DNA by chemically reduced 3-NFA was 0.12% (1.2 adducts/10(3) nucleosides), which was sufficient to allow several hundred micrograms of the adduct to be isolated and purified. The chemically synthesized adduct was utilized as a reference standard for comparison to the major adduct isolated from xanthine-oxidase-catalyzed reduction of 3-NFA in vitro. The yield from the in vitro biological system was 2.4 adducts/10(5) nucleosides; the adduct isolated possessed the same mass spectrometric, UV-VIS, and fluorescence characteristics as the purified standard, and co-eluted with the standard on HPLC. No evidence for other adducts was found, either in vitro or in the chemical synthesis, based on FAB-MS examination of whole extracts of the reaction mixture for the presence of ions related to other possible adducts. Therefore, if minor adducts were present they were formed in substantially lesser amounts than N-(deoxyguanosin-8-yl)-3-aminofluoranthene.
Chemical Phenomena↗
Direct coupling of open-tubular liquid chromatography with mass spectrometry.
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Chromatography, Liquid↗
Fast atom bombardment combined with tandem mass spectrometry for determining structures of small oligonucleotides.
A study of small (n = 3 to 6) oligonucleotide and the metastable and collisionally activated decompositions of their (M-H)- species desorbed by using fast atom bombardment (FAB) is reported. Data were obtained for both ribo- and 2'-deoxyribotrinucleotides and for 2'-deoxyribotetra-, penta-, and hexanucleotides. The favored metastable decompositions of all of the oligonucleotides studied are eliminations of neutral CONH and loss of BH, where B is the base moiety. The BH elimination, however, provides little sequence information in the higher oligonucleotides and the process is more indicative of the different bases present in the oligomer. The chemistry observed upon collisional activation changes as one goes from trinucleotides to hexanucleotides. The formation of sequence ions is more facile for processes involving the 3' terminus, allowing the sequence to be determined. As one goes to the higher oligonucleotides, however, several different competitive fragmentation processes become as facile as or more facile than the reactions giving the sequence ions. This hinders proper ion assignments and makes sequence determination difficult.
Gas Chromatography-Mass Spectrometry↗
Applications of fast atom bombardment mass spectrometry and fast atom bombardment mass spectrometry-mass spectrometry to the maduramicins and other polyether antibiotics.
Fast atom bombardment mass spectrometry (FAB MS) and fast atom bombardment mass spectrometry-mass spectrometry (FAB MS/MS) were used to study the monovalent glycoside polyether antibiotics maduramicin alpha, beta and delta and the maduramicin alpha salts, their derivatives and degradation products. Also, representative compounds from three major classes of polyether antibiotics were studied: the monovalent polyethers, nigericin and monensin A, the divalent polyether lasalocid A and the monovalent glycoside polyethers septamycin, BL580 delta, etheromycin and carriomycin. The respective FAB fragment and decomposition ions were correlated with the known structures. The FAB spectra of all the polyethers contained metal-adduct molecular ions. Protonated molecular ions were absent. All the polyethers having a beta-hemiketal carboxylic acid group produced an abundant ion, often the base peak of the spectra, 62 daltons less than the corresponding metal-adduct molecular ion. The gas phase mechanism proposed for the formation of this fragment ion is an unusual unimolecular reaction which is initiated by an intramolecular proton transfer from the carboxylic acid to the hydroxy group of the beta-hemiketal, and, then followed by the concerted losses of water and carbon dioxide to produce the corresponding polyether olefin.
Anti-Bacterial Agents↗
Analyses of carcinogen-modified oligonucleotides by fast atom bombardment/tandem mass spectrometry.
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7,8-Dihydro-7,8-dihydroxybenzo(a)pyrene 9,10-oxide↗
FAB MS/MS for phosphatidylinositol, -glycerol, -ethanolamine and other complex phospholipids.
Fast atom bombardment (FAB) of phosphatidylinositol, phosphatidylethanolamine, cardiolipin, phosphatidic acid and phosphatidylglycerol produces a limited number of very informative negative ions. Especially significant is the formation of (M-H)-ions and ions that correspond to the carboxylate portions of these molecules. FAB desorption in combination with collisional activation allows for characterization of fragmentation and determination of structural features. Collisional activation of the carboxylate anion from complex lipids is especially informative. Structural characterization of the fatty acids can be achieved as the released saturated carboxylate anions undergo highly specific charge remote fragmentations that are entirely consistent with the chemistry of carboxylate anions desorbed from free fatty acids. This permits both identification of the modification and assignment of its location on the acid chain. FAB-desorbed alkyl acetyl glycerophosphocholines (platelet-activating factor) do not produce (M-H)-ions. However, significant high mass ions are formed, and these can be collisionally activated for structural characterization.
Mass Spectrometry↗
High performance liquid chromatography and fast atom bombardment mass spectrometry of unusual branched and unsaturated phospholipid molecular species.
The unusual symmetrical molecular species 1,2-di-3,7,11,15-tetramethylhexadecanoyl-sn-glycero-3-phosphoglyce rol, 1,2-di-5,8,11,14-docosatetraenoyl-sn-glycero-3-phosphocholine, 1,2-di-5,9,19-octacosatrienoyl-sn-glycero-3-phosphoethanolamine, and 1,2-di-5,9,23-triacontatrienoyl-sn-glycero-3-phosphoethanolamine were isolated from the marine sponges Axinella verrucosa, Higginsia tethyoides, Tethya aurantia and Aplysina fistularis by HPLC and studied by fast atom bombardment (FAB) mass spectrometry. In addition to molecular weights, branching and double bonds were located in the fatty acyl chains of the intact phospholipid molecules, using FAB either in a positive or negative mode. Some mass spectral results were obtained on enriched phospholipid fractions rather than pure molecular species using MS/MS.
Animals↗
Plasticizers as contaminants in commercial ethanol.
A batch of 95% ethanol caused unusually strong disordering of biomembranes, which could be detected either by fluorescence anisotropy in synaptosomal membranes or by electron paramagnetic resonance spectroscopy in erythrocyte membranes. The contaminated batches of ethanol were visibly fluorescent when evaporated on filter paper. The adulterants were separated by capillary gas chromatography and the ubiquitous pollutant dioctylphthalate was identified by its low resolution electron impact mass spectrum. The remaining peaks, which were not recognized by any of the available mass spectral libraries, were identified by high resolution electron impact and chemical ionization mass spectrometry and low resolution tandem mass spectrometry using fast atom bombardment ionization; they were triethylene glycol esters and aryl phosphates. All the contaminants are industrial plasticizers. Distillation resulted in loss of the strong disordering properties of the alcohol.
Animals↗
Transfer of glycerol by Endo-beta-N-acetylglucosaminidase F to oligosaccharides during chitobiose core cleavage.
N-Linked oligosaccharides, when hydrolyzed by glycerol-containing preparations of endo-beta-N-acetylglucosaminidase (Endo) F from Flavobacterium meningosepticum were found to have glycerol attached to their reducing ends. The absence of a reducing end was confirmed by high-field 1H NMR spectroscopy, and the incorporated glycerol was verified through mass spectrometry and collisionally activated decomposition fast atom bombardment/mass spectrometry/mass spectrometry techniques. Periodate oxidation of [1(3)-14C]glycerol-labeled oligosaccharides indicated glycerol was glycosidically linked via its 1(3) carbon to the C1 of the reducing end N-acetylglucosamine. In a second, less favored reaction, the glycerol glycoside was hydrolyzed by Endo F using water as the terminal nucleophile, thus regenerating the N-acetylglucosamine reducing end. Glycerol could be removed from Endo F preparations without affecting enzyme stability, and chitobiosyl core hydrolysis in its absence provided intact oligosaccharides with normal N-acetylglucosamine reducing ends. The incorporation of labeled glycerol may provide a useful method for monitoring of Endo F release of oligosaccharides.
Acetylglucosamine↗
Fast atom bombardment combined with tandem mass spectrometry for determination of bile salts and their conjugates.
Fast atom bombardment desorption of bile salts produces negative ions which show little fragmentation. The lack of fragmentation limits the utility of the method for resolving questions regarding specific structural features. This paper is a report of negative ion fast atom bombardment mass spectra and collision-activated decomposition spectra of cholate, chenodeoxycholate, lithocholate, taurocholate, taurochenodeoxycholate, taurolithocholate, 3 beta-ol-5-cholenate, taurolithocholate-3-sulfate and glycolithocholate-3-sulfate. The collision-activated decomposition spectra are useful for distinguishing bile salt structural features and for quantifying relative amounts of isomeric ions in a mixture. The negative ion mode is well suited for generating anions of bile salts and, when coupled with collisional activation, provides complementary information to the positive ion mode. The collision-activated fragmentation is also unusual as it appears to be an example of reactions occurring remote from the charge site. Furthermore, on the basis of the fragmentations, the charge site can be located in the amphiprotic form of some gas-phase diprotic bile acids such as taurolithocholate-3-sulfate and glycolithocholate-3-sulfate.
Bile Acids and Salts↗
Fast atom bombardment and tandem mass spectrometry of phosphatidylserine and phosphatidylcholine.
Fast atom bombardment (FAB) desorption of phosphatidylserine and various phosphatidylcholines produces a limited number of very informative negative ions. Especially significant is the formation of (M-H)- ions for phosphatidylserine, a compound which does not yield informative high mass ions by other ionization methods. Phosphatidylcholines do not yield (M-H)- ions but instead produce three characteristic high mass ions, (M-CH+3)-, [M-HN(CH3)+3]- and [M-HN(CH3)+3-C2H2]-. Both classes of lipids also yield anions attributed to the carboxylate components of these complex lipids. FAB desorption in combination with collisional activation allows for characterization of fragmentation and determination of structural features. Collisional activation of the carboxylate anion fragments from the complex lipids is especially informative. Structural characterization of the fatty acid chain can be achieved as the released saturated carboxylate anions undergo a highly specific 1,4-elimination of H2, which results in the losses of the elements of CH4, C2H6, C3H8 . . . in a fashion entirely consistent with the chemistry of carboxylate anions desorbed from free fatty acids. These CnH2n + 2 losses begin at the alkyl terminus and progress along the entire alkyl chain. Modified fatty acids undergo a similar fragmentation; however, the modification affects the series of CnH2n + 2 losses in a manner which permits determining the type of modification and its location on the fatty acid chain.
Mass Spectrometry↗