Abstract

In the collisionally-activated dissociation of the proton-bound cluster ions of DNA base guanine (G) and cytosine(C), G••H+••C, the abundance of [CH+] ions was found to be higher than that of [GH+] despite the fact that G has a higher protonaffinity than C. This unexpected observation seems to demonstrate another example that the simple kinetic method scheme doesnot work. We suggest that a kinetic factor or detailed dynamics governing the proton transfer and dissociation should be carefullyconsidered in the applications of the kinetic method to the proton affinity measurements.

Highlights

  • The kinetic method has been widely used for the thermochemical determination of gas-phase basicities, gas-phase acidities, proton affinities, electron affinities, ionization potentials, metal ion affinities, and so forrth.[1,2,3,4] In particular, the Cooks’ kinetic method is based on the measurements of relative rates of competitive dissociations of a cluster ion comprised of the compound of interest and a reference compound.[5]

  • We suggest that a kinetic factor or detailed dynamics governing the proton transfer and dissociation should be carefully considered in the applications of the kinetic method to the proton affinity measurements

  • We present another example of an anomalous dissociation of proton-bound complex of DNA guanine (G)-cytosine (C) base-pair

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Summary

Introduction

The kinetic method has been widely used for the thermochemical determination of gas-phase basicities, gas-phase acidities, proton affinities, electron affinities, ionization potentials, metal ion affinities, and so forrth.[1,2,3,4] In particular, the Cooks’ kinetic method is based on the measurements of relative rates of competitive dissociations of a cluster ion comprised of the compound of interest and a reference compound.[5]. Abstract: In the collisionally-activated dissociation of the proton-bound cluster ions of DNA base guanine (G) and cytosine (C), GH+C, the abundance of [CH+] ions was found to be higher than that of [GH+] despite the fact that G has a higher proton affinity than C.

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