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Keywords:

  • bradykinin;
  • gas-phase basicity;
  • deprotonation reaction;
  • molecular modeling;
  • FT-ICR

Abstract

Apparent gas-phase basicities (GBapps) for [M + H]+ of bradykinin, des-Arg1-bradykinin and des-Arg9-bradykinin have been assigned by deprotonation reactions of [M + 2H]2+ in a Fourier transform ion cyclotron resonance mass spectrometer. With a GBapp of 225.8 ± 4.2 kcal mol−1, bradykinin [M + H]+ is the most basic of the ions studied. Ions from des-Arg1-bradykinin and des-Arg9-bradykinin have GBapp values of 222.8 ± 4.3 kcal mol−1 and 214.9 ± 2.3 kcal mol−1, respectively. One purpose of this work was to determine a suitable reaction efficiency ‘break point’ for assigning GBapp values to peptide ions using the bracketing method. An efficiency value of 0.1 (i.e. approximately 10% of all collisions resulting in a deprotonation reaction) was used to assign GBapps. Support for this criterion is provided by the fact that our GBapp values for des-Arg1-bradykinin and des-Arg9-bradykinin are identical, within experimental error, to literature values obtained using a modified kinetic method. However, the GBapps for bradykinin ions from the two studies differ by 10.3 kcal mol−1. The reason for this is not clear, but may involve conformation differences produced by experimental conditions. The results may be influenced by salt-bridge conformers and/or by conformational changes caused by the use of a proton-bound heterodimer in the kinetic method. Factors affecting the basicities of these peptide ions are also discussed, and molecular modeling is used to provide information on protonation sites and conformations. The presence of two highly basic arginine residues on bradykinin results in its high GBapp, while the basicity of des-Arg1-bradykinin ions is increased by the presence of two proline residues at the N-terminus. The proline residue in the second position folds the peptide chain in a manner that increases intramolecular hydrogen bonding to the protonated N-terminal amino group of the proline at the first position. Copyright © 2001 John Wiley & Sons, Ltd.