Dissociation kinetics of singly protonated leucine enkephalin investigated by time-resolved photodissociation tandem mass spectrometry.

The yields of post-source decay (PSD) and time-resolved photodissociation (PD) at 193 and 266 nm were measured for singly protonated leucine enkephalin ([YGGFL + H](+)), a benchmark in the study of peptide ion dissociation, by using tandem time-of-flight mass spectrometry. The peptide ion was generated by matrix-assisted laser desorption ionization (MALDI) using 2,5-dihydroxybenzoic acid as the matrix. The critical energy (E(0)) and entropy (DeltaS(++) at 1000 K) for the dissociation were determined by Rice-Ramsperger-Kassel-Marcus fit of the experimental data. MALDI was done for a mixture of YGGFL and Y(6) and the plume temperature determined by the kinetic analysis of [Y(6) + H](+) data were used to improve the precision of E(0) and DeltaS(++) for [YGGFL + H](+). E(0) and DeltaS(++) thus determined (E(0) = 0.67 +/- 0.08 eV, DeltaS(++) = -24.4 +/- 3.2 eu with 1 eu = 4.184 J K(-1)mol(-1)) were significantly different from those determined by blackbody infrared radiative dissociation (BIRD) (E(0) = 1.10 eV, DeltaS(++) = -14.9 eu), and by surface-induced dissociation (SID) (E(0) = 1.13 eV, DeltaS(double dagger) = -10.3 eu). Analysis of the present experimental data with the SID kinetics (and BIRD kinetics also) led to an unrealistic situation where not only PSD and PD but also MALDI-TOF signals could not be detected. As an explanation for the discrepancy, it was suggested that transition-state switching occurs from an energy bottleneck (SID/BIRD) to an entropy bottleneck (PSD/PD) as the internal energy increases.