Average activation energies of low-energy fragmentation processes of protonated peptides determined by a new approach

Rapid Communications in Mass Spectrometry

Volumn 10, Issue 8, 1996, Pages 911-918

  Vékey, Károly ^a   Somogyi, Árpád ^b   Wysocki, Vicki H ^b  

^a CTRL RES INSTITUTE FOR CHEMISTRY   (Hungary)

^b VIRGINIA COMMONWEALTH UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINO ACIDS; ELECTROSPRAY IONIZATION; PEPTIDES; PROTONATION;

ELECTROSPRAY SOURCE; ENERGY FRAGMENTATION; FRAGMENTATION PROCESS; INTERNAL ENERGIES; LOWER ENERGIES; NEW APPROACHES; PROTONATED; PROTONATED PEPTIDES; RRKM THEORY; SURFACE-INDUCED DISSOCIATION;

ACTIVATION ENERGY;

ENKEPHALIN; OLIGOPEPTIDE; PROTON;

AMINO ACID SEQUENCE; ARTICLE; CHEMISTRY; MASS SPECTROMETRY; MOLECULAR GENETICS; PHYSICAL CHEMISTRY;

AMINO ACID SEQUENCE; CHEMISTRY, PHYSICAL; ENKEPHALINS; MASS SPECTROMETRY; MOLECULAR SEQUENCE DATA; OLIGOPEPTIDES; PROTONS;

EID: 0029716520     PISSN: 09514198     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1097-0231(19960610)10:8<911::AID-RCM593>3.0.CO;2-7     Document Type: Article

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36. + by a low energy rearrangement process, the activation energy of which was reported to be ca. 1 eV (K. L. Busch, G. L. Glish and S. A. McLuckey, Mass Spectrometry/Mass Spectrometry: Techniques and Applications of Tandem Mass Spectrometry, VCH Publishers, New York, 1988). We were not able to detect this low-energy process so we concluded that the internal energy provided by thermal and capillary/ skimmer activation must be high enough to drive a fragmentation with 1 eV activation energy and the appropriate kinetic shift associated with the instrument (in the microsecond time scale). From this, we estimate that in the capillary skimmer region, at 30V capillary/skimmer voltage difference, singly charged ions gain an energy of ca. 0.5-1.0 eV. It should also be noted that the supersonic cooling cannot be a dominant process. By this process, it is mainly the translational energy that is reduced (but this can be overcome by the applied 30 V potential difference in this region). The internal energy provided by thermal excitation in the capillary region can be reduced in two ways: collisional cooling and infrared radiation. Infrared radiation requires more time than several microseconds, so this is an unlikely process.
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