Unusual behavior of gem-diamino peptides in fast atom bombardment and electrospray ionization mass spectrometry

Vivet, B.; Cavelier, Florine; Enjalbal, Christine; Martinez, Jean; Sanchez, Pierre; Aubagnac, Jean‐Louis

doi:10.1051/analusis:2000280268

Cited by 4 publications

(2 citation statements)

References 4 publications

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“…Since primary ESI mass spectra generally contain only molecular species, the presence of a co‐eluting deletion by‐product was first envisaged. Indeed, although in‐source fragmentations have been observed for low molecular weight peptides,8 especially when relatively high cone voltages are used, such a phenomenon was not predicted for high molecular weight peptides exhibiting multiprotonated ions. To confirm such an assumption, two experiments were carried out by modifying the synthetic strategy on one hand and by recording the CAD mass spectra of the [M + 2H] 2+ and [M + 3H] 3+ ions on the other hand.…”

Section: Resultsmentioning

confidence: 99%

New example of proline‐induced fragmentation in electrospray ionization mass spectrometry of peptides

Maux

Enjalbal

Martinez

et al. 2002

Rapid Comm Mass Spectrometry

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The positive ion electrospray ionization (ESI+) mass spectra of peptides usually display only protonated molecules provided that soft ionization conditions are applied (low cone voltage to prevent in-source dissociations). Such ions can be multiply charged depending on the molecular weight of the studied compounds. We have experienced an unexpected behavior during the ESI analysis of a modified peptide of relatively high mass (3079 Da). A specific fragmentation occurred even under soft energetic conditions, leading to a mass spectrum containing multiply charged molecular and fragment ions. The selective rupture involved the amide bond between the glutamic acid and proline residues (E-P sequence). The successive replacement of each amino acid by an alanine residue (positional scanning study) was undertaken to assess which part of the sequence induced such selective and abundant fragmentation on multiply charged species. The succession P-P was evidenced as the minimum unit giving rise to the first peptide bond rupture in the sequence X-P-P. Any acidic amino acid at the X position (X = D, E) favored the fragmentation by an intramolecular interaction. Such proline-induced fragmentation occurring readily in the source differed from the literature data on the specific behavior of proline-containing peptides where bond ruptures occur solely in dissociation conditions.

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Section: Resultsmentioning

confidence: 99%

New example of proline‐induced fragmentation in electrospray ionization mass spectrometry of peptides

Maux

Enjalbal

Martinez

et al. 2002

Rapid Comm Mass Spectrometry

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“…Tandem mass spectrometry (MS/MS) in electrospray ionization (ESI) is an established technique for the structure elucidation of peptides [35][36][37][38][39][40][41][42][43][44][45][46] and peptidomimetics, [47][48][49][50][51][52][53][54][55][56][57] but the characterization of peptides containing a gem-diaminoalkyl moiety has received little attention. [58][59][60][61] This has prompted us to undertake a detailed mass spectrometric study on a series of N-alkoxycarbonyl-N′-formyl-gemdiaminoalkyl derivatives using the ESI technique both in the positive and negative ion mode.…”

Section: Introductionmentioning

confidence: 99%

Characterization of N‐Boc/Fmoc/Z‐N′‐formyl‐gem‐diaminoalkyl derivatives using electrospray ionization multi‐stage mass spectrometry

Verardo

Gorassini

2013

J. Mass Spectrom.

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N-Boc/Fmoc/Z-N'-formyl-gem-diaminoalkyl derivatives, intermediates particularly useful in the synthesis of partially modified retro-inverso peptides, have been characterized by both positive and negative ion electrospray ionization (ESI) ion-trap multi-stage mass spectrometry (MS(n)). The MS(2) collision induced dissociation (CID) spectra of the sodium adduct of the formamides derived from the corresponding N-Fmoc/Z-amino acids, dipeptide and tripeptide acids show the [M + Na-NH2CHO](+) ion, arising from the loss of formamide, as the base peak. Differently, the MS(2) CID spectra of [M + Na](+) ion of all the N-Boc derivatives yield the abundant [M + Na-C4H8](+) and [M + Na-Boc + H](+) ions because of the loss of isobutylene and CO2 from the Boc protecting function. Useful information on the type of amino acids and their sequence in the N-protected dipeptidyl and tripeptidyl-N'-formamides is provided by MS(2) and subsequent MS(n) experiments on the respective precursor ions. The negative ion ESI mass spectra of these oligomers show, in addition to [M-H](-), [M + HCOO](-) and [M + Cl](-) ions, the presence of in-source CID fragment ions deriving from the involvement of the N-protecting group. Furthermore, MS(n) spectra of [M + Cl](-) ion of N-protected dipeptide and tripeptide derivatives show characteristic fragmentations that are useful for determining the nature of the C-terminal gem-diamino residue. The present paper represents an initial attempt to study the ESI-MS behavior of these important intermediates and lays the groundwork for structural-based studies on more complex partially modified retro-inverso peptides.

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Current Awareness

2001

J. Mass Spectrom.

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In order to keep subscribers up‐to‐date with the latest developments in their field, John Wiley & Sons are providing a current awareness service in each issue of the journal. The bibliography contains newly published material in the field of mass spectrometry. Each bibliography is divided into 11 sections: 1 Books, Reviews & Symposia; 2 Instrumental Techniques & Methods; 3 Gas Phase Ion Chemistry; 4 Biology/Biochemistry: Amino Acids, Peptides & Proteins; Carbohydrates; Lipids; Nucleic Acids; 5 Pharmacology/Toxicology; 6 Natural Products; 7 Analysis of Organic Compounds; 8 Analysis of Inorganics/Organometallics; 9 Surface Analysis; 10 Environmental Analysis; 11 Elemental Analysis. Within each section, articles are listed in alphabetical order with respect to author (5 Weeks journals ‐ Search completed at 6th. Dec. 2000)

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Unusual behavior of gem-diamino peptides in fast atom bombardment and electrospray ionization mass spectrometry

Cited by 4 publications

References 4 publications

New example of proline‐induced fragmentation in electrospray ionization mass spectrometry of peptides

New example of proline‐induced fragmentation in electrospray ionization mass spectrometry of peptides

Characterization of N‐Boc/Fmoc/Z‐N′‐formyl‐gem‐diaminoalkyl derivatives using electrospray ionization multi‐stage mass spectrometry

Current Awareness

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