Dependence of collision‐induced dissociation energy on molecular degrees of freedom as a means to assess relative binding affinity in multivalent complexes

Abstract

In collision-induced dissociation mass spectrometry experiments, the collision energy required for dissociation linearly depends on the degrees of freedom in the precursor ion. The magnitude of the slope of this relationship previously has been shown to qualitatively correlate to the relative binding strength of a noncovalently bound, monovalent complex. The goal of the work presented here is to determine if a similar methodology can be applied for assessing relative binding strengths in multivalent species. We have tested the method on complexes formed from 18-crown-6 and a variety of protonated, primary alkylamines, [C(n)H(2n+1)NH(3)](+) (n=9, 12, 14, 16 and 18) and alkyldiamines, [H(3)NC(n)H(2n)NH(3)](2+) (n=3, 5, 6, 9 and 12), and compared our results with dissociation energies calculated using density functional theory at the B3LYP/6-31G* level. We found that the method correctly assessed the stronger crown ether/headgroup interaction in the two divalent species (1:1 and 2:1 complexes formed from the diaminoalkanes) compared with the weaker interaction in the monovalent species (1:1 complexes formed from mono-aminoalkanes). However, the experimental method could not distinguish between the binding strengths of the two divalent complexes, perhaps because their calculated dissociation energies were quite similar. Our preliminary results suggest that this method could potentially be used for a quick and simple analysis of binding strengths in multivalent species if the binding strengths of the species are significantly different from one another.

Anion−π Interactions of Hexaaryl[3]radialenes

“…Comparison of NCE values, although qualitative, has been used to infer the stability of other complexes. 46 As expected, it was observed that the complexes fragment at a much lower NCE value than the ion of the initial hexaaryl [3]radialene owing to the weaker noncovalent forces involved.…”

“…The stability of the complexes were probed through comparison of the signal intensities for a particular ion with increasing normalized collision energy (NCE) relative to the signal intensities that are observed with an NCE of zero. Comparison of NCE values, although qualitative, has been used to infer the stability of other complexes . As expected, it was observed that the complexes fragment at a much lower NCE value than the ion of the initial hexaaryl[3]radialene owing to the weaker noncovalent forces involved.…”

Factors that Influence Competitive Intermolecular Solvation of Protonated Groups in Peptides and Proteins in the Gas Phase

“…Evaluation of identical samples with time-of-flight MS, which does not activate ions during detection (see Supporting Information), yields masses and isotope patterns that agree well with predicted values. In Figure 1b, the precursor ion survival yields are shown as a function of activation voltage normalized by the number of vibrational degrees of freedom [24, 19]. The trends in peptide complex stability are nearly identical to those observed by mass shifting in Figure 1a (a quantitative comparison is shown in the Supporting Information).…”