Mass Spectrometry in Structural and Stereochemical Problems. XLV.1The Mass Spectrometric Fragmentation Behavior of Isohexyl Cyanide and Its Deuterium Analogs2

1964 ◽  
Vol 86 (7) ◽  
pp. 1386-1389 ◽  
Author(s):  
R. Beugelmans ◽  
D. H. Williams ◽  
H. Budzikiewicz ◽  
Carl. Djerassi
Keyword(s):  
Mass Spectrometry ◽  
Mass Spectrometric ◽  
Fragmentation Behavior ◽  
Mass Spectrometric Fragmentation

Identification of Phosphorylcholine-Substituted Peptides by Their Characteristic Mass Spectrometric Fragmentation

2005 ◽  
Vol 11 (3) ◽  
pp. 335-344 ◽  
Author(s):  
Julia Grabitzki ◽  
Volker Sauerland ◽  
Rudolf Geyer ◽  
Günter Lochnit
Keyword(s):  
Mass Spectrometry ◽  
Ion Trap ◽  
Neutral Loss ◽  
Structural Data ◽  
Mass Spectrometric ◽  
Peptide Backbone ◽  
Fragmentation Behavior ◽  
Flight Mass Spectrometry ◽  
Characteristic Fragmentation ◽  
Fragmentation Patterns

Phosphorylcholine (PC)-substituted biomolecules are wide-spread, highly relevant antigens of parasites, since this small hapten has been found to be a potent immunomodulatory component which allows the establishment of long lasting infections of the host. Structural data, especially of protein bound PC-substituents, are still rare due to the observation that mass spectrometric analyses are mostly hampered by this zwitterionic substituent resulting in low sensitivities and unusual but characteristic fragmentation patterns. Here, we investigated the fragmentation behavior of synthetic PC-substituted peptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and electrospray ionization ion-trap mass spectrometry. We could show that the predominant neutral loss of a trimethylamine unit (Hoffmann elimination) leads to cyclic phosphate derivatives which prevent further fragmentation of the peptide backbone by stabilizing the positive charge at this particular side chain. Knowledge of this PC-specific fragmentation might help to identify PC-substituted biomolecules and facilitate their structural analysis.

Formation of Organometallic Species, [M – H]+ Ions and Radical Cations upon Mass Spectrometric Fragmentation of Mercury–Crown Ether Complexes

2009 ◽  
Vol 15 (4) ◽  
pp. 479-486 ◽  
Author(s):  
Rafał Frański ◽  
Błażej Gierczyk
Keyword(s):  
Mass Spectrometry ◽  
Crown Ether ◽  
Radical Cations ◽  
Mass Spectrometric ◽  
Tandem Mass ◽  
Fragmentation Pathways ◽  
Factors Influencing ◽  
Crown Ether Complexes ◽  
Mass Spectrometric Fragmentation ◽  
Ether Molecule

Mass spectrometric fragmentation pathways of [M + HgClO4]+ (M – crown ether molecule), determined by tandem mass spectrometry experiments, are discussed in detail. The decomposition of [M + HgClO4]+ proceeds along three fragmentation pathways: formation of [M – H]+ ions, formation of organometallic species, namely [M – H + Hg]+ ions, and formation of radical cations [M]+•. The factors influencing these processes, namely crown ether cavities and the presence of electron withdrawing/electron donor groups, have been discussed.

Mass Spectrometric Investigation of Protonated and Cationized Molecules of Oxaalkyl Phosphates

2002 ◽  
Vol 8 (6) ◽  
pp. 451-460 ◽  
Author(s):  
Natalya Lyapchenko ◽  
Rafał Frański ◽  
Grzegorz Schroeder
Keyword(s):  
Mass Spectrometry ◽  
Alkali Metal ◽  
Secondary Ion Mass Spectrometry ◽  
Metal Cations ◽  
Mass Spectrometric ◽  
Alkali Metal Cations ◽  
Ionisation Mass Spectrometry ◽  
Mass Spectrometric Fragmentation ◽  
Protonated Molecules ◽  
Secondary Ion

Mass spectrometric fragmentation pathways of protonated molecules of oxaalkyl phosphates and their complexes with alkali metal cations are discussed in this paper. Liquid secondary ion mass spectrometry (LSIMS) was used as the ionisation technique and mass spectra from B/E linked scans were registered to elucidate the mass spectrometric decomposition of the studied ions. Mainly loss of the ether molecules H2C=HCOCH3 and HOH2C–H2COCH3 was observed. The elimination of neutrals containing metal, for example, K-CH2CH2OCH3 or KOCH2CH2OCH3 also occurred. In the case of phosphate (III) an unusual loss of two CH3CH2OCH3 molecules and a Li or Na atom was observed. Electrospray ionisation mass spectrometry (ESIMS) was applied in order to check the ability of the studied tripodands to form complexes with alkali metal cations.

Sign in / Sign up

Export Citation Format

Share Document