Fast Atom Bombardment Mass Spectra of Some N-α-(t-Butoxycarbonyl)-O-(diorganylphosphono)-L-serines and O-(Diorganylphosphono)seryl-Containing Dipeptides and Tripeptides

1994 ◽  
Vol 47 (2) ◽  
pp. 229 ◽  
Author(s):  
JW Perich ◽  
I Liepa ◽  
AL Chaffee ◽  
RB Johns
Keyword(s):  
Mass Spectrometry ◽  
Mass Spectrum ◽  
High Intensity ◽  
Mass Spectra ◽  
Fast Atom Bombardment ◽  
Molecular Ions ◽  
Operating Conditions ◽  
Negative Ion ◽  
The Matrix ◽  
Positive Ion

Positive and negative ion fast atom bombardment ( f.a.b .) mass spectrometry were found to be useful methods for the analysis and structural characterization of five Nα-(t- butoxycarbonyl )-O-( diorganylphosphono )-L- serines ( organyl = Ph, Et, Me, Bzl , But), especially in the case of the sensitive benzyl and t-butyl phosphono derivatives. Under positive ion operating conditions, high intensity pseudo-molecular ions were obtained in the f.a.b . mass spectra, and the fragmentation pathway of the phenyl, ethyl and methyl derivatives was established by parent/daughter linked scanning studies to involve (a) the two-step loss of the t- butoxycarbonyl group, (b) loss of the amino acid as the neutral fragment from the [MH]+, [MH-56]+, [MH-100]+ and [MH-146]+ ions by a four- centred β-elimination rearrangement, and (c) cleavage of the phosphono phenyl and ethyl groups from only the [(RO)2P(OH)2]+ and [NH=CHCH2PO3R2+H]+ fragments. Parent/daughter linked scanning studies of the benzyl derivative showed that the prominent fragmentation involved loss of the benzyl group as the tropylium ion and that the 'apparent' [MH-90]+ peak observed in its f.a.b. mass spectrum resulted from cleavage of the phosphono benzyl group in the matrix during the bombardment process. In the case of the t-butyl derivative, parent/daughter linked scanning studies showed that the prominent fragmentation involved successive 'in-flight' loss of the phosphono t-butyl groups as isobutene. Negative ion f.a.b. mass spectrometry of the five derivatives gave f.a.b. mass spectra which displayed distinct [M-H]- anions along with high intensity [M-H-R]- and [(RO)2PO2]- fragment anions, the f.a.b . mass spectrum of the t-butyl derivative containing an additional [M-H-But-But]- fragment anion. Parent/daughter linked scanning studies established that the majority of the observed fragment anions resulted from extensive fragmentation of the Boc -Ser(PO3R2)-OH derivatives in the matrix phase followed by sputtering of the resultant fragments into the gas phase. In addition, positive ion f.a.b . mass spectrometry was found to be useful for the analysis of a series of protected O-( diorganylphosphono ) seryl-containing dipeptides and tripeptides ( organyl = Ph, Et, Me, Bzl ). The obtained spectra showed that β-elimination fragmentation of the Ser(PO3R2) residue was more pronounced with the tripeptide series and indicated that there was increased sensitivity of the O-( diorganylphosphono ) seryl residue with replacement of the Boc group by an amino acyl residue at its N-terminus.

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.

Synthesis and fast atom bombardment mass spectrometry of the coordination complexes of the ligand 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane

1989 ◽  
Vol 67 (5) ◽  
pp. 797-803 ◽  
Author(s):  
Cindy Lee MacLaurin ◽  
Jack Martin Miller ◽  
Mary Frances Richardson
Keyword(s):  
Mass Spectrometry ◽  
Mass Spectra ◽  
Fast Atom Bombardment ◽  
Spectroscopic Properties ◽  
Coordination Complexes ◽  
Negative Ion ◽  
Successful Technique ◽  
Negative Ion Mode ◽  
Positive Ion ◽  
Fab Mass Spectra

Metal complexes containing the ligand 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazatetradecane were synthesized and characterized using electron impact (EI) and fast atom bombardment (FAB). The FAB mass spectra were obtained in positive and negative ion mode. FAB in the positive ion mode proved to be the most successful technique for the identification of these compounds. The majority of the FAB spectra obtained were structurally informative, although not all showed molecular (M+) or quasimolecular ([M + H]+) ions. The fragmentations observed were characteristic of the ligands and the metal, and were interpreted based on the chemical and spectroscopic properties of these compounds. Keywords: FAB mass spectroscopy, tetraazacyclotetradecane complexes.

Fast Atom Bombardment Mass Spectrometry of the Vitamin B12 Analogues Hydrogenobalamin and Cupribalamin

1984 ◽  
Vol 39 (2) ◽  
pp. 248-251 ◽  
Author(s):  
Lutz Grotjahn ◽  
Volker B. Koppenhagen ◽  
Ludger Ernst
Keyword(s):  
Mass Spectrometry ◽  
Mass Spectrum ◽  
Mass Spectra ◽  
Fast Atom Bombardment ◽  
Metal Clusters ◽  
Cobalt Atom ◽  
Vitamin B ◽  
Metal Free ◽  
Characteristic Fragment ◽  
Fab Mass Spectra

Hydrogenobalam in (metal-free vitamin B12) and cupribalamin are characterized by their fast atom bombardment (FAB) mass spectra which show molecular ion and characteristic fragment ion peaks. These spectra and the high-resolution FAB mass spectrum of cobalamin (vitamin B12) show that the (M+H)+-CN-59 peak for the latter is due to loss of acetamide and not of the central cobalt atom. In the FAB mass spectrum of cupribalamin metal clusters are observed

Electron impact studies. XXXII. Negative-ion mass spectra of aromatic compounds containing the =N-O- substituent

1968 ◽  
Vol 21 (8) ◽  
pp. 2031 ◽  
Author(s):  
JH Bowie ◽  
SO Lawesson ◽  
BS Larse ◽  
GE Lewis ◽  
G Schroll
Keyword(s):  
Electron Impact ◽  
Aromatic Compounds ◽  
Mass Spectra ◽  
Molecular Ions ◽  
Negative Ion ◽  
Skeletal Rearrangement ◽  
Marked Contrast ◽  
Azoxy Compounds ◽  
Positive Ion ◽  
Fragmentation Processes

The negative-ion mass spectra of aromatic azoxy compounds, nitrones, and N-oxides exhibit pronounced molecular ions and simple fragmentation processes. No skeletal-rearrangement fragments are produced upon electron impact, in marked contrast to those exhibited in the positive-ion spectra of these compounds.

A study of the negative ion FABMS of tris(perfluorophenyl)phosphine and related compounds: matrix effects

1995 ◽  
Vol 73 (8) ◽  
pp. 1321-1328
Author(s):  
Mandapati Saraswathi ◽  
Jack M. Miller ◽  
Tim R.B. Jones
Keyword(s):  
Mass Spectra ◽  
Fast Atom Bombardment ◽  
Matrix Effects ◽  
Negative Ion ◽  
The Matrix ◽  
Related Compounds

The mass spectra of tris(perfluorophenyl)phosphine obtained under negative ion Fast Atom Bombardment conditions showed formation of an unusual ion at m/z 397 attributed to ((C6F5)2PO2)−. The matrix effects involved in this reaction are discussed. Negative ion FAB spectra of tris(perfluorophenyl)arsine and tris(perfluorophenyl)stibine are also reported. Keywords: pentafluorophenylphosphine, -arsine, -stibine; negative ion FABMS; matrix effects.

The fast atom bombardment mass spectra of some N-substituted pyrimidinium salts

1987 ◽  
Vol 65 (4) ◽  
pp. 718-721 ◽  
Author(s):  
Clement W. Kazakoff ◽  
Robin T. B. Rye ◽  
Oswald S. Tee
Keyword(s):  
Concentration Dependence ◽  
Mass Spectra ◽  
Fast Atom Bombardment ◽  
Negative Ion ◽  
Cluster Ions ◽  
Solution Equilibria ◽  
Mixed Cluster ◽  
Cluster Ion ◽  
Conventional Solution ◽  
Positive Ion

The fast atom bombardment mass spectra of selected 1,2-dihydro-1,3-disubstituted-2-oxo-pyrimidinium salts are presented. Loss of N-substituents from the solute cation is the principal fragmentation observed in the positive ion spectra. Several concentration dependent features of the spectra are identified; these are thought to result from the interaction of the solute cation with bombardment-induced matrix fragments. Cluster ions are observed in both positive and negative ion spectra. In a mixed solute system cluster ions resulting from extensive cation and anion mixing are observed; the concentration dependence of these mixed cluster ion peaks can be approximately described in terms of conventional solution equilibria.

Electron ionization mass spectrometry of cobalt(III) β-diketonates and monothio-β-diketonates possessing aryl and fluorinated alkyl substituents

1992 ◽  
Vol 70 (3) ◽  
pp. 952-963 ◽  
Author(s):  
Mark L. J. Reimer ◽  
John B. Westmore ◽  
Manoranjan Das
Keyword(s):  
Mass Spectrometry ◽  
Mass Spectra ◽  
Fluorine Content ◽  
Molecular Ions ◽  
Electron Ionization ◽  
Ionization Mass ◽  
Chelate Complexes ◽  
Neutral Species ◽  
Positive Ion ◽  
Marked Dependence

Electron ionization positive ion mass spectra of 15 substituted cobalt(III) β-diketonates and monothio-β-diketonates, CoIIIL3, where L = RCXCHCOR′, R = phenyl, 2-thienyl, or 2-naphthyl; X = O or S; and R′ = CHF2, CF3, C2F5, or n-C3F7, show a marked dependence on the ligand. Molecular ions, [CoIIIL3]+•, are observed only for some of the more highly fluorinated complexes (R′ = C2F5 or n-C3F7). The [CoIIIL2]+• ion, possibly generated by ionization of CoIIL2 formed by thermal degradation, or by electron ionization of CoIIIL3, typically decomposes by elimination of a radical, i.e., L• or R′•, to yield ions containing Co(II); subsequent decompositions proceed preferentially by loss of even-electron neutral species, also to yield ions containing Co(II). Cobalt-containing ions in which fluorine has rearranged to the metal decrease in variety and abundance for the ligands with higher fluorine content. When metal-bonded oxygen is replaced by sulfur, fluorine migration to Co(III), rather than to Co(II), is preferred. These trends are consistent with a combination of several different concepts including the ability of the metal to undergo valency change, the principle of Hard and Soft Acids and Bases, and the inductive capabilities of the ligand donor atoms and of the R and R′ groups. Ion decomposition pathways are proposed. Keywords: mass spectrometry, cobalt complexes, β-diketonates, fluorinated chelate complexes.

Natural Waxes Investigated by Soft Ionization Mass Spectrometry

1987 ◽  
Vol 42 (3) ◽  
pp. 178-190 ◽  
Author(s):  
H .-R . Schulten ◽  
K. E. Murray ◽  
N. Simmleit
Keyword(s):  
Mass Spectrometry ◽  
Mass Spectra ◽  
Molecular Ions ◽  
Negative Ion ◽  
High Mass ◽  
Forest Damage ◽  
Field Ionization ◽  
Ionization Mass ◽  
Field Desorption ◽  
Long Chain

Field ionization (FI) and field desorption (FD) mass spectra of 35 aliphatic long-chain and branched long-chain compounds, representing the major six classes of constituents of natural waxes, are examined. In the FI mode the molecular ions are usually formed at comparatively low levels, while in FD such species are almost exclusively generated. In addition, some fast atom bombardment mass spectra, in the positive and negative ion mode, of selected lipids are recorded for comparison. In general, field ionization and field desorption techniques are found to be superior for mass spectrometric studies of low-polarity compounds. Examination of several natural waxes, such as Jojoba wax, preen gland wax of goose, beeswax and epicuticular wax of Norway spruce, shows that field desorption mass spectrometry has a most promising role in the characterization of wax components. The intense molecular ions allow the identification of the constituents of complex lipid mixtures without the need for derivatization. Thus, for the first time, the carbon number distribution, especially of the high-mass wax con­stituents can be established for the natural waxes investigated. For identification of high-mass wax constituents the present results suggest that field desorption mass spectra could be best employed in conjunction with class and individual separation of constituents by chromatographic proce­dures. The analysis of natural waxes is nowadays of major concern because of its importance in the problem of forest damage.

Electron impact studies. XL. Negative-ion mass spectra of organosulphur compounds : Thioglycollic acids and arylsulphinylamines

1969 ◽  
Vol 22 (1) ◽  
pp. 153 ◽  
Author(s):  
JH Bowie ◽  
F Duus ◽  
S Lawesson ◽  
FCV Larsson ◽  
J+ Madsen
Keyword(s):  
Electron Impact ◽  
Mass Spectra ◽  
Molecular Ions ◽  
Negative Ion ◽  
Skeletal Rearrangement ◽  
Marked Contrast ◽  
Impact Studies ◽  
Positive Ion ◽  
Hydrogen Rearrangement

The negative-ion mass spectra of thioglycollic esters and S- alkylthioglycollic acids exhibit ions produced by simple cleavage and/or cleavage with hydrogen rearrangement. Similar spectra of arylsulphinylamines show pronounced molecular ions together with simple cleavage fragments. No skeletal-rearrangement fragments are present in the negative-ion spectra, in marked contrast with those observed in the corresponding positive-ion spectra.

Electron impact studies. XCVI. Negative ion mass spectra of naturally occurring compounds. Nitrophenyl esters derived from long-chain acids andalcohols

1975 ◽  
Vol 28 (5) ◽  
pp. 1011 ◽  
Author(s):  
JH Bowie ◽  
BJ Stapleton
Keyword(s):  
Electron Impact ◽  
Analytical Method ◽  
Mass Spectra ◽  
Molecular Ions ◽  
Negative Ion ◽  
Impact Studies ◽  
Naturally Occurring ◽  
Molecular Anions ◽  
Positive Ion ◽  
Long Chain

The positive ion mass spectra of long-chain alcohols and acids are either devoid of molecular ions or contain such species in low abundance. The negative ion spectra of p-nitrophenyl esters of these compounds exhibit pronounced molecular anions, showing the technique to be a useful analytical method for these classes of compounds.

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