Mass spectrometric studies on gibberellins

Based on the element maps of twenty-two gibberellin methyl esters fragmentations are discussed, which are characteristic of the common structural features as well as structural modification in gibberellin homologues.     

Mass spectrometric studies of 2-nitrosophenols

The mass spectra of 2-nitrosophenols are independent of the insertion temperature, suggesting that the compounds either do not exhibit tautomerism in the vapour phase or that the enthalpy of isomerization is low. However, their fragmentation patterns suggest tautomerism in the molecular ion.     

Mass spectrometric studies of phenoxarsine derivatives

Nine phenoxarsine derivatives with arsenic in the trivalent state and the pentavalent state are synthesized and studied by mass spectrometry. Their characteristic fragmentation modes and the fragment ions with common structures are discussed. Phenoxarsinic acids are found to be unstable in the gaseous phase at the temperatures studied and tend to form their corresponding anhydrides.     

Mass spectrometric studies of benzoxazine resorcarenes

Eleven differently substituted 3,4-dihydro-2H-1,3-benzoxazine resorcarenes were studied by electrospray ionisation (ESI) and matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry, using Fourier transform ion cyclotron resonance (FT-ICR) and time-of-flight (TOF) mass spectrometers, respectively. Under ESI conditions it was possible to transfer the intact resorcarenes from solution to the gas phase, yielding [M + H](+) and [M + 2H](+) ions as the main ions observed. Energy increase of the ions induced ready decomposition through successive eliminations of four CH(2)NR groups. Ion-molecule reactions showed that the ionising proton was situated somewhere inside the molecule and could not be reached with neutral reagent gases. In the host-guest complexation experiments, the benzoxazine resorcarenes studied turned out to be poor hosts for alkali metal and ammonium ions. In MALDI experiments, 2,5-dihydroxybenzoic acid proved to be the best matrix for these compounds. However, the intensity of the [M + H](+) ions was low for all compounds, and extensive fragmentation with consecutive elimination of CH(2)NR groups was observed.     

Liquid chromatographic-mass spectrometric studies on rifamycin antibiotics

The use of a direct liquid introduction type liquid chromatographic-mass spectrometric interface to study highly thermally labile rifamycin antibiotics is described. Using negative ionization, abundant molecular ions were observed, and the spectra, also contained structurally significant fragments. Variation of the high-performance liquid chromatographic parameters did not change the spectra, thus making it easy to change chromatographic conditions. In quantitative studies, a surprising correlation was found, indicating that the mass spectrometric signal was proportional to the square of the sample concentration.     

Mass spectrometric studies of peptides—VI:. Applications of metastable ion and collisional activation spectra

An unambiguous differentiation between leucine and isoleucine residues in peptides is possible with unimolecular metastable ion (MI) and collisional activation (CA) spectra. The immonium ion \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm [Y}\!\mathop {\rm N}\limits^{\rm + } {\rm H = CHC}_{\rm 4} {\rm H}_{\rm 9} {\rm ]} $\end{document}, which is present in the normal mass spectra of all leucine or isoleucine containing peptides, yields MI spectra with which this differentiation can be made with high sensitivity. The MI and CA spectra of other peptide fragments are also applicable in particular cases. MI and CA spectra can also be used to obtain information on the amino acide sequences of individual ions. In general more extensive sequece information is available from CA than from MI spectra. This information appears to be particularly promising for the sequencing of oligopeptide mixtures or of ions produced by field or chemical ionization.     

Mass spectrometric studies on azidomorphine derivatives

The mass spectrometric behaviour of nine azidomorphine derivatives have been studied. These compounds proved to have surprisingly specific and selective fragmentation under electron-impact. For 6-deoxy-6-azido-dihydro-isomorphine derivatives (I to V) the main decomposition pathway involves the loss of an N₂ molecule followed by a very rapid and selective fragmentation process. On the other hand, the molecular ions of 6-deoxy-8-azido-pseudomorphine derivatives (VI to VIII) and 6-deoxy-6-azido-14-hydroxy-isocodein (IX) primarily decompose by loss of the N₃ radical. This is due to the allylic effect of the double bond in ring C, corresponding to the chemical behaviour of these compounds.     

Mass spectrometric studies of anomeric glycopyranosyl azides

We studied the mass spectrometric behaviour of peracetylated and underivatized anomeric hexopyranosyl azides and 5-thioglucopyranosyl azides by means of different mass spectrometric techniques. The unstable molecular ions fragment predominantly by losing either N3 radical or N2 molecule. Loss of N2 molecule and the protonation of the derived nitrene were characteristic of the studied compounds. The presence of BF3.Et2O in the ion source is favorable for producing the protonated nitrene form. The protonated nitrene shows a new type of ring expansion rearrangement. The abundances of the [M + H - N2]+ ion makes it possible to identify the anomeric configuration of the azido group.     

Mass spectrometric studies of the pterocarpan skeleton

The mass spectrometric characteristics of the pterocarpan skeleton have been studied with the aid of metastable decomposition (CAD-MIKES), high resolution mass measurements and specific deuterium labeling. New structural rotations have been postulated for the [M - H](+) ions which can explain the fragmentation routes for the pterocarpan skeleton.     

Mass spectrometric studies of some novel sulfonamides

A recent paper described the overall 5-endo cyclisation of homoallylic sulfonamides to give pyrrolidines. This reaction was also used to prepare polycyclic systems. Mass spectrometric analysis using classical electron ionisation spectra and accurate mass measurement played a vital role in confirming the proposed structures for the products. These materials were not amenable to newer mass spectrometric methods and this study shows the continuing importance of older techniques.     

Mass spectrometric studies of dithiophosphinato metal complexes

Electron impact induced fragmentation reactions of planar, tetrahedral, octahedral and oligomeric metal dithiophosphinates Me(II)L₂ (L=Et₂PS₂^?; Me(II)=Zn, Cd, Hg, Pb, Co, Mn, Ni, Pd, Pt), Me(III)L₃ (Me(III) = Sb, Bi, In, Rh, Ir) and (Me(I)I)_n (Me(I)/n=Tl/1, Au/2, Cu/4) have been studied. Fragmentation patterns, which are in accordance with metastable peak determinations by linked scans, are reported. In the case of the transition metals the spectra of the complexes show abundant [M]^+· predominantly metal containing ions and, the former being weak and the intensities of the latter being considerably reduced in the case of metal complexes with filled d shells. With planar or tetrahedral transition metal complexes no dependence of fragmentation on the coordination geometry can be observed. The dependence of fragmentation on d configuration, ionization energy of the metal and metal ligand π bonding is discussed. In the case of the oligomeric complexes strong metal-metal interaction is observed even under electron impact.     

Mass spectrometric study to characterize thioisoindole derivatives of aminoglycoside antibiotics

Aminoglycoside antibiotics are widely used to treat serious Gram-negative and Gram-positive bacterial infections. The lack of a UV chromophore presents a problem in the analysis of aminoglycosides. Derivatization with 1,2-phthalic dicarboxaldehyde (OPA) in the presence of a thiol made it possible to introduce a UV chromophoric thioisoindole moiety. A qualitative mass spectrometry study was carried out to confirm the molecular identity of the products formed. The conditions described earlier to derivatize gentamicin and kanamycin yielded products in which all primary amino groups are fully derivatized. On the other hand, with tobramycin and amikacin, there was also formation of incompletely derivatized products that contained one thioisoindole group less than the fully derivatized product. This study has therefore brought an additional insight into the nature of the OPA-aminoglycoside derivatives studied.     

Mass spectrometric studies—II: Mass spectrometric studies of maleimides and benzaldazine adducts. Identification of solid mixtues

It has been found by mass spectrometric studies that the so-called ‘1:1-adduct’ formed by N-( nbutyl)maleimide and benzaldazine, is in fact a solid mixture of one part bis-imide L and one part benzaldazine. Bis-imide L is one of the three stereoisomeric products obtained by the addition of two mole of N-( n-butyl)malemide and one mole of benzaldazine. The three stereoisomeric bis-imides gave identical mass spectra. Mass spectra of bis-imide M and bis-imide M- d2 are discussed, and confirm the proposed structures of perhydroprazolo-pyrazole derivatives for these 1:2-adducts.