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. 2009 Feb;20(2):247-56.
doi: 10.1016/j.jasms.2008.09.028. Epub 2008 Oct 17.

The spontaneous loss of coherence catastrophe in Fourier transform ion cyclotron resonance mass spectrometry

Konstantin Aizikov  1 , Raman Mathur, Peter B O'Connor
Affiliations

The spontaneous loss of coherence catastrophe in Fourier transform ion cyclotron resonance mass spectrometry

Konstantin Aizikov et al. J Am Soc Mass Spectrom. 2009 Feb.

Abstract

The spontaneous loss of coherence catastrophe (SLCC) is a frequently observed, yet poorly studied, space-charge related effect in Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). This manuscript presents an application of the filter diagonalization method (FDM) in the analysis of this phenomenon. The temporal frequency behavior reproduced by frequency shift analysis using the FDM shows the complex nature of the SLCC, which can be explained by a combination of factors occurring concurrently, governed by electrostatics and ion packet trajectories inside the ICR cell.

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Figures

Figure 1
Figure 1
Examples of the transient signals: (a) hypothetical exponentially decaying sinusoidal signal; (b) transient of a high-resolution substance-P spectrum; (c) an example of SLCC where a period of exponential decay is followed by a rapid noncorrelated decay.
Figure 2
Figure 2
An illustration of an effect EPIC has on SLCC: (a) a SLCC during substance-P signal acquisition; (b) complete elimination of SLCC by applying EPIC (all other experimental parameters are kept the same).
Figure 3
Figure 3
(a) A frequency domain spectrum and the transient of an isolated cesium iodide cluster and (b) the frequency shift modulation calculations of the ICR peak at 272.75 kHz.
Figure 4
Figure 4
A Fourier Transform of the frequency shift calculations (see Figure 3b) conducted on the cesium iodide signals acquired without (a) and with (b) application of EPIC.
Figure 5
Figure 5
The results of the frequency shift calculations conducted on (a) the experimental SLCC of angiotensinogen. (I) is the magnification of the region of the time domain transient signal under investigation, (II) its amplitude dk, and (III) frequency fk temporal behaviors calculated using FDM (b) before, and (c) after the nipple.
Figure 6
Figure 6
(a) An illustration of the inhomogeneities in the electric field experienced by a trapped ion packet in a closed, cylindrical ICR cell. When the ions follow the cyclotron orbit close to the middle of the cell (trajectory I), they are subjected to nearly hyperbolic electric potential. As the axial and magnetron components start to contribute ions travel through highly inhomogeneous electric field (for example, trajectory II), which perturbs the motion further increasing the magnetron component. The orbits are not drawn to scale. (b) A schematic representation of the ions being temporally positioned in the center of the cell as consequence of the superimposition the cyclotron and magnetron orbits. The figure is not drawn to scale.
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