Study of formation and fragmentation of ionic complexes of polydentate ligands with Al(III) and glycerol by fast atom bombardment mass spectrometry. Part 1: Polydentate ligands

1996 ◽  
Vol 74 (11) ◽  
pp. 2221-2228
Author(s):  
Mandapati Saraswathi ◽  
Jack M. Miller
Keyword(s):  
Mass Spectrometry ◽  
Fast Atom Bombardment ◽  
Polyethylene Glycols ◽  
Metal Chelation ◽  
Ionic Complexes ◽  
Polydentate Ligands ◽  
Fragment Ions ◽  
Fab Mass Spectrometry ◽  
Aluminum Ions ◽  
Complexation Reactions

The complexation reactions of aluminum ions with polydentate ligands such as 12-crown-4,15-crown-5,18-crown-6, 1,10-dithia-18-crown-6, dicyclohexyl-18-crown-6, dibenzo-18-crown-6, and dibenzo-24-crown-8 and acyclic analogs mono-, di-, tri-, tetra-, penta-, and hexaethylene glycols were studied using FAB mass spectrometry. These cyclic ligands form (M + 117)+, (M + 157)+, (M + 231)+, and (M + 253)+ ions with different aluminum-containing species. Collisionally activated dissociations of these adduct ions gave fragment ions, initially due to the loss of ligands directly attached to aluminum, followed by insertion of aluminum into the remaining ligand skeleton. Further fragmentation of the metal-containing species gave ions corresponding to consecutive losses of C2H4O units. Fragmentations of deuterium-labelled ions were used to help in establishing fragmentation pathways. Selectivity towards metal chelation is observed in this order: 12-crown-4 < 15-crown-5 < 18-crown-6. The elemental compositions of adduct ions were confirmed by high-resolution measurements. The formation of (M + Al − 2H)+ ion, obtained by the displacement of two hydroxy protons, is more favored for tetra- and pentaethylene glycols. Key words: crown ethers, polyethylene glycols, aluminum(III)–glycerol, ionic complexes and ion dissociations.

Differentiation of the Isomeric o-(m- and p-) Nitro-(Chloro- and Bromo-)Benzyl-2,4-(and 2,1-) Disubstituted 2-Thiocytosinium Halides by Electron Impact Ionisation and Fast Atom Bombardment Mass Spectrometry

2009 ◽  
Vol 15 (4) ◽  
pp. 497-506 ◽  
Author(s):  
Tomasz Pospieszny ◽  
Elżbieta Wyrzykiewicz
Keyword(s):  
Mass Spectrometry ◽  
Mass Spectra ◽  
Fast Atom Bombardment ◽  
Collision Induced Dissociation ◽  
Mass Measurements ◽  
Fragmentation Pathways ◽  
Mass Spectral ◽  
Fragment Ions ◽  
Accurate Mass Measurements ◽  
Impact Ionisation

Electron ionisation (EI) and fast atom bombardment (FAB) mass spectral fragmentations of nine 2,4-(and 2,1-) disubstituted o-( m- and p-)nitro-(chloro- and bromo-)-2-thiocytosinium halides are investigated. Fragmentation pathways, whose elucidation is assisted by accurate mass measurements and metastable transitions [EI-mass spectrometry (MS)], as well as FAB/collision-induced dissociation (CID) mass spectra measurements are discussed. The correlations between the abundances of the (C11H10N4SO2)+1–3; (C11H10N3SCl)+4–6 and (C11H10N3SBr)+7–9 ions and the selected fragment ions (EI-MS), as well as (C18H16N5SO4)+1–3; (C18H16N3SCl2)+4–6 and (C18H16N3SBr2) + 7–9 ions and the selected ions (C7H6NO2)+1–3; (C7H6Cl)+ 4–6; (C7H6Br)+ 7–9 (FAB-MS) are discussed. The data obtained can be used for distinguishing isomers.

Fast-Atom Bombardment Mass Spectrometry in Heterogeneous Atmospheric Chemistry

2002 ◽  
Vol 8 (2) ◽  
pp. 131-138 ◽  
Author(s):  
G.B. Pronchev ◽  
I.A. Korobeinikova ◽  
A.N. Yermakov
Keyword(s):  
Mass Spectrometry ◽  
Atmospheric Aerosols ◽  
Atmospheric Chemistry ◽  
Fast Atom Bombardment ◽  
Atmospheric Water ◽  
Ferric Ions ◽  
Fab Mass Spectrometry ◽  
Essential Components ◽  
The Given ◽  
Heterogeneous Atmospheric Chemistry

The application of fast-atom bombardment (FAB) mass spectrometry to solving the problems of heterogeneous atmospheric chemistry is briefly reviewed. The method is useful in studying the state of surfaces and molecules adsorbed thereon and looks appropriate in investigations of the dynamics and mechanisms of chemical reactions occurring both on a surface and in a volume of moving particulate matter suspended in a gas. It was shown that composition of atmospheric aerosols and components dissolved in atmospheric water (clouds, fogs, mists etc.) can be determined by the FAB technique. The given method, as was found in our investigations, allows the discrimination of ferrous and ferric ions. Detection limits for concentrations of H2SO4 and Fe(II / III) ions as essential components of atmospheric water determined in model experiments are established at the level of 10−6 M.

Continuous flow fast atom bombardment mass spectrometry of mononucleotides and their metal complexes

1989 ◽  
Vol 67 (5) ◽  
pp. 910-920 ◽  
Author(s):  
M. J. Bertrand ◽  
V. Benham ◽  
R. St-Louis ◽  
M. J. Evans
Keyword(s):  
Mass Spectrometry ◽  
Continuous Flow ◽  
Fast Atom Bombardment ◽  
Aqueous Media ◽  
Molecular Ions ◽  
Fragment Ions ◽  
Low Concentrations ◽  
Metal Adducts ◽  
Matrix Concentration

The mass spectra of mononucleotides and their metal adducts Na, K, Mg, Ca, Ni, Co, Cu, and Zn of guanosine 5′-monophosphate (5′-GMP) as well as H, Na, and Mg of adenosine 5′-monophosphate (5′-AMP) and H and Ni of inosine 5′-monophosphate (5′-IMP) have been obtained in low concentrations of matrix in water using continuous-flow fast atom bombardment. The results indicate that this technique is suitable for the analysis of these complexes in aqueous media and yields spectra that are highly characteristic of the compounds analyzed. Parent-molecular ions and structurally significant fragment ions are observed for all compounds studied and the different binding sites for the metal on the nucleotides can be isolated from the fragment ions. Experimental parameters influencing the quality of the spectra such as flow rate, matrix concentration, matrix nature, and analyte concentration have been studied and optimized. For the thirteen compounds studied, it appears that continuous-flow FAB is superior to conventional FAB and that good quality spectra can be obtained with as little as 0.5% of added matrix thus minimizing spectral interferences. Keywords: continuous flow FAB, FAB MS, mass spectrometry, nucleotides, metal-nucleotides.

Isolation and structural identification of 9hydroxy-9desmethyl-cyclosporine

1990 ◽  
Vol 36 (11) ◽  
pp. 1875-1879 ◽  
Author(s):  
L D Bowers ◽  
D D Norman ◽  
X X Yan ◽  
D Scheeler ◽  
K L Carlson
Keyword(s):  
Mass Spectrometry ◽  
Fast Atom Bombardment ◽  
Structural Identification ◽  
Collision Induced Dissociation ◽  
Tandem Mass ◽  
Hplc Fraction ◽  
Nomenclature System ◽  
Fragment Ions ◽  
Tandem Mass Spectroscopy ◽  
The Difference

Abstract A metabolite of cyclosporine has been isolated and its structure identified through use of HPLC and tandem mass spectroscopy. Fast atom bombardment mass spectrometry of an HPLC fraction co-eluting with 1 eta hydroxy-cyclosporine (M17) indicated that the mass of this metabolite was 2 Da greater than that of cyclosporine. Further isolation by HPLC yielded a pure fraction, which we analyzed with tandem mass spectrometry. Linear acyl fragment ions originating from the metabolite under collision-induced dissociation were consistent with the difference in mass being associated with amino acid 9 in the cyclosporine backbone. We propose a nomenclature system for future discussion of cyclosporine metabolites.

scholarly journals Analysis of the Core Oligosaccharide ofAeromonas hydrophila(Chemotype III) Lipopolysaccharide Using Fast Atom Bombardment, Electrospray and Low Energy Tandem Mass Spectrometry

1994 ◽  
Vol 12 (2) ◽  
pp. 55-68 ◽  
Author(s):  
Joseph Banoub ◽  
Emmanuel Gentip ◽  
Derek H. Shaw
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Fast Atom Bombardment ◽  
Low Energy ◽  
Tandem Mass ◽  
Core Oligosaccharide ◽  
Molecular Ion ◽  
The Core ◽  
Fragment Ions ◽  
Positive Ion

Fast-atom bombardment mass spectrometry (FAB-MS) was employed for the structural analysis of the core oligosaccharide ofAeromonas hydrophila(Chemotype III) lipopolysaccharide. Positive ion FAB-MS of the underivatized core oligosaccharide gave the protonated molecular ion, confrrming the correct composition in terms of hexoses, heptoses and Kdo which was present as a bicyclic furanosidic lactone. Negative ion FAB-MS gave the deprotonated molecular ion and fragment ions which were derived from more than two cleavage events with charge retention at the reducing and non-reducing terminals. Positive ion F AB-MS of the permethylated core oligosaccharide afforded fragment ions consistent with the defined sequence and branching patterns of the sugar constituents. The electrospray mass spectrum (ESMS) in the positive ion mode of the underivatized core oligosaccharide afforded the protonated molecular ion in the singly and doubly charged forms. Low energy collision-activated dissociation tandem mass spectrometry (CAD MS/MS) analysis of the protonated molecular ion [M+2H]+2provided additional structural data. ESMS of the permethylated and N-acetylated permethylated core oligosaccharides provided useful structural indices and afforded a characteristic pattern for fragmentions resulting from the opening of the methylated bicyclic Kdo furanosidic 1,7- lactone, which was similar to that obtained in the corresponding FAB-MS.

Ligand Exchange in FAB Mass Spectrometry of Monomerie and Dimeric Corrinoids

1984 ◽  
Vol 39 (11) ◽  
pp. 1548-1552 ◽  
Author(s):  
Lutz Grotjahn ◽  
Ludger Ernst
Keyword(s):  
Mass Spectrometry ◽  
Ligand Exchange ◽  
Mass Spectra ◽  
Fast Atom Bombardment ◽  
Molecular Ions ◽  
Negative Ion ◽  
Fab Mass Spectrometry ◽  
Fab Mass Spectra

Abstract In the Fast Atom Bombardment (FAB) mass spectra of monomeric and dimeric corrinoids, exchange of metal-bound ligands against matrix particles is observed which leads to pseudo molecular ions. Negative ion FAB mass spectra in particular, give distinct information on the intact molecular units.

Characterization of metal complexes of 1,10-phenanthroline, 2,2′-bipyridine, and their derivatives by fast atom bombardment mass spectrometry

1989 ◽  
Vol 67 (9) ◽  
pp. 1496-1500 ◽  
Author(s):  
Jack M. Miller ◽  
Kesagapillai Balasanmugam
Keyword(s):  
Mass Spectrometry ◽  
Metal Complexes ◽  
Metal Ion ◽  
Fast Atom Bombardment ◽  
Laser Mass Spectrometry ◽  
Laser Desorption Mass Spectrometry ◽  
Fragment Ions ◽  
Intact Cation ◽  
Singly Charged ◽  
Positive Ion

A series of 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (5-NO2-phen), 2,9-dimethyl- 1,10-phenanthroline (dmp), 2,2′-bipyridine (bpy), and 4,4′-dimethy-2,2′-bipyridine (dmb) metal complexes has been characterized using fast atom bombardment mass spectrometry (FAB MS). Intact cations are observed in the positive ion FAB mass spectra of all tetracoordinated complexes, [Ag(L)2]NO3, [Cu(L)2]2 SO4•5H2O, [Cu(L)2]SO4, and [Tl(L)2](ClO4), where L=bpy, phen, or dmp. Structurally significant fragment ions (ML2+, ML+, M+, and (L+H)+, where M+=metal ion) are also observed. Species such as Ag[Ag(L)2]NO3+, where L=bpy or phen, and Tl[Tl(phen)2](ClO4)+ are also seen. The hexacoordinate complexes, [Co(phen)3]Cl2, [Ru(bpy)Cl2], [Fe(phen)2(CN)2], [Fe(L)3](ClO4), where L=5-NO2-phen, dmb, or bpy, and [Fe(L)3]SO4, where L=bpy or phen, show intact cations in the positive ion spectra; [Ni(bpy)3]X2, where X=Cl−,Br−, NO3−, ClO4−, SCN−, and tartrate2−, and [Co(bpy)3](ClO4) do not. Generally, fragment ions such as ML3+, ML2X+, ML2+, MLX+, and (L+H)+ are observed, where X=singly charged intact anion or HSO4−. Comparison of FAB results with those of laser mass spectrometry (LMS) show that they are comparable, through reduction processes are more important for FAB. LMS always gave the intact cation while FAB was not consistent. Keywords: FAB mass spectrometry, phenanthroline complexes, bipyridine complexes, laser desorption mass spectrometry.

scholarly journals A study of formation and fragmentation of ionic metal complexes of substituted benzoic and cinnamic acids with Al(III)–glycerol by fast atom bombardment mass spectrometry

1997 ◽  
Vol 75 (4) ◽  
pp. 398-404
Author(s):  
Mandapati Saraswathi ◽  
Jack M. Miller
Keyword(s):  
Mass Spectrometry ◽  
Carboxylic Acid ◽  
Metal Complexes ◽  
Spectral Data ◽  
Fast Atom Bombardment ◽  
Complex Ions ◽  
Cinnamic Acids ◽  
Collisionally Activated Dissociation ◽  
Fab Mass Spectrometry

Substituted benzoic and cinnamic acids were studied by FAB mass spectrometry using matrix-based Al(III) ions. Complex ions derived from these acids, such as ( M + 117 )+ ( 117 = (Al + glycerol − 2H)+ ), ( M + 159 )+ ( 159 = [2Al + 2glycerol − 5H − 74(epoxypropanol)]+), and ( M + 233)+ ( 233 = (2Al + 2glycerol − 5H)+), when subjected to collisionally activated dissociation (CAD), gave an ion corresponding to ( M − OH)+. Formation of this ion was explained by the transfer of the carboxylic -OH group to the ( Al + glycerol − 2H)+, ( 2Al + 2glycerol − 5H − 74 )+, and ( 2Al + 2glycerol − 5H )+ portion of the complexes. This transfer is more pronounced in the case of meta- and para-substituted acids. The CAD of the ( M + 117 )+ ions yielded ( M + Al(III) )+ ions resulting from the insertion of Al(III) into the carboxylic acid, which was followed by the elimination of CO to produce ( M + Al(III) − CO)+ ions. Interpretation of spectral data was clarified by study of the formation and fragmentation of ions produced from deuterated benzoic and cinnamic acids. Keywords: substituted benzoic and trans-cinnamic acids, Al(III)–glycerol, FAB mass spectrometry, ionic metal complexes, collisionally induced dissociation, Al(III) insertion, carbonyl cations.

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