2000
DOI: 10.1016/s1387-3806(99)00256-0
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Conformations of biopolymers in the gas phase: a new mass spectrometric method

Abstract: A method is developed for measuring collision cross sections of gas-phase biomolecules using a slightly modified commercial triple quadrupele instrument. The modifications allow accurate stopping potentials to be measured for ions exiting the collision region of the instrument. A simple model allows these curves to be converted to cross sections. In order to account for certain poorly defined experimental parameters (exact ion energy, absolute pressure in the collision cell, etc.) variable parameters are inclu… Show more

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Cited by 53 publications
(58 citation statements)
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“…All of the above observations are consistent with the premise that the reaction pathways followed after electron capture, and thus the fragments obtained, reflect the conformational heterogeneity of the trapped ions. It is encouraging that the fragments obtained at 86 K appear to correlate with the structure calculated by Bowers and workers for the gas-phase [M ϩ 2H] 2ϩ ion of Substance P, in which the part of the peptide backbone involved in internal solvation includes the amino acids whose scission leads to the c 7 and c 10 fragments [26]. Intramolecular solvation of the protonated lysine is Ϸ40 kJ mol Ϫ1 more stable (enthalpically) than solvation of the other protonation site (arginine) and the enthalpic contribution increasingly dominates the conformer population at lower temperatures (see personal communications below) (and thus the intramolecular solvation shells that determine which fragments are obtained).…”
Section: Resultssupporting
confidence: 70%
“…All of the above observations are consistent with the premise that the reaction pathways followed after electron capture, and thus the fragments obtained, reflect the conformational heterogeneity of the trapped ions. It is encouraging that the fragments obtained at 86 K appear to correlate with the structure calculated by Bowers and workers for the gas-phase [M ϩ 2H] 2ϩ ion of Substance P, in which the part of the peptide backbone involved in internal solvation includes the amino acids whose scission leads to the c 7 and c 10 fragments [26]. Intramolecular solvation of the protonated lysine is Ϸ40 kJ mol Ϫ1 more stable (enthalpically) than solvation of the other protonation site (arginine) and the enthalpic contribution increasingly dominates the conformer population at lower temperatures (see personal communications below) (and thus the intramolecular solvation shells that determine which fragments are obtained).…”
Section: Resultssupporting
confidence: 70%
“…A quick comparison of the method we used with the experiments for determination of collision cross sections in the collision cell of tandem quadrupole mass spectrometers [17][18][19] shows the following: In the stationary gas of the collision cell the ions with smallest cross sections pass the stopping potential (a low pass filter in terms of cross sections) and are detected, while the collisions with ions of larger cross sections reduce their translational energy so that they cannot reach the analyzer quadrupole. However, in our experiments, where the ions are transported by the gas flow, ions with the largest cross sections pass the barrier (high pass filter) and are detected.…”
Section: Discussionmentioning
confidence: 99%
“…Interesting experiments for measuring collision cross sections of ions were also reported by Covey and Douglas, [17], by Cox et al [18], and by Gill et al [19], who used tandem quadrupole mass spectrometers. In these experiments, ions traveling through the collision cell lost a certain portion of their kinetic energy depending on their cross sections.…”
mentioning
confidence: 91%
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