Determination of the activation energy for unimolecular dissociation of a non-covalent gas-phase peptide: substrate complex by infrared multiphoton dissociation fourier transform ion cyclotron resonance mass spectrometry

Journal of the American Society for Mass Spectrometry
Mathias SchäferA G Marshall

Abstract

The activation energy for the unimolecular dissociation of a non-covalent supramolecular complex between an Artificial Cationic Receptor A ([Gua-Val-Val-Val-Amide]+, in which Gua is guanidiniocarbonyl pyrrole) and an Anionic Tetrapeptide B ([N-Acetyl-Val-Val-Ile-Ala]-) has been determined by measurement of the dissociation rate constant as a function of infrared CO2 laser power density. Singly-charged quasimolecular [A + B + H]+ ions are isolated, stored in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, and irradiated by IR photons. The rate constant for dissociation of the non-covalent complex is determined at five different laser power densities. A plot of the natural logarithm of the first-order rate constant versus the natural logarithm of the laser power density yields a straight line, the slope of which provides an approximate measure of the activation energy (Ea(laser)) for dissociation. Ea(laser) is calculated by a relationship derived earlier by Dunbar and with a newly proposed equation by Paech et al. The results of the two approaches deliver significantly different activation energy values for the unimolecular dissociation of the non-covalent complex. We obtain EaI(laser) = 0.67 eV (Dunbar ap...Continue Reading

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Citations

Dec 17, 2009·Journal of the American Society for Mass Spectrometry·Malgorzata A KaczorowskaHelen J Cooper
Feb 21, 2004·Proceedings of the National Academy of Sciences of the United States of America·Andrew J ForbesNeil L Kelleher
Nov 15, 2006·Journal of Mass Spectrometry : JMS·Alice DelvolvéFrançoise Fournier
Sep 10, 2014·Physical Chemistry Chemical Physics : PCCP·Josephine Abi-Ghanem, Valérie Gabelica
May 16, 2020·ChemPlusChem·Michael GieseJens Voskuhl
Jul 27, 2010·Rapid Communications in Mass Spectrometry : RCM·Antony MemboeufGyörgy Lendvay
Jul 27, 2018·Journal of the Royal Society, Interface·Doron LancetOmer Markovitch

Related Concepts

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Fourier Transform
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