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.

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.

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.

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.

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