Determination of cross sections by overtone mobility spectrometry: evidence for loss of unstable structures at higher overtones.

Determination of cross sections by overtone mobility spectrometry: evidence for loss of unstable structures at higher overtones.
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DOI:
10.1021/jp1060123
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发表时间:
2010-09-30
影响因子:
3.3
通讯作者:
Clemmer, David E.
Clemmer, David E.
中科院分区:
化学3区
文献类型:
--
作者:
Lee, Sunyoung;Ewing, Michael A.;Nachtigall, Fabiane M.;Kurulugama, Ruwan T.;Valentine, Stephen J.;Clemmer, David E.

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Overtone mobility spectrometry (OMS) is examined as a means of determining the collision cross sections for multiply-charged ubiquitin and substance P ions, as well as for singly-charged rafinose and melezitose ions. Overall, values of collision cross section measured by OMS for stable ion conformations are found to be in agreement with values determined by conventional ion mobility spectrometry (IMS) measurements to within ~1%, relative uncertainty. The OMS spectra for ubiquitin ions appear to favor different conformations at higher overtones. We propose that the changes in the distributions as a function of the overtone region in which they are measured arise from the elimination of ions that undergo structural transitions in the drift regions. Kinetics simulations suggest that structural transitions occurring on the order of a few ms and resulting in a ~4% change in ion collision cross sections are detected by OMS measurements. The unique method of distinguishing ion mobilities with OMS reveals these structural transitions which are not readily apparent from traditional IMS measurements.
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