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J Am Soc Mass Spectrom. 2017 Apr;28(4):768-780. doi: 10.1007/s13361-017-1598-y. Epub 2017 Feb 17.

Fourier Transform Ion Cyclotron Resonance Mass Spectrometry at the Cyclotron Frequency.

Author information

1
Spectroswiss Sàrl, EPFL Innovation Park, 1015, Lausanne, Switzerland.
2
Spectroswiss Sàrl, EPFL Innovation Park, 1015, Lausanne, Switzerland. tsybin@spectroswiss.ch.

Abstract

The phenomenon of ion cyclotron resonance allows for determining mass-to-charge ratio, m/z, of an ensemble of ions by means of measurements of their cyclotron frequency, ω c . In Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), the ω c quantity is usually unavailable for direct measurements: the resonant state is located close to the reduced cyclotron frequency (ω+), whereas the ω c and the corresponding m/z values may be calculated via theoretical derivation from an experimental estimate of the ω+ quantity. Here, we describe an experimental observation of a new resonant state, which is located close to the ω c frequency and is established because of azimuthally-dependent trapping electric fields of the recently developed ICR cells with narrow aperture detection electrodes. We show that in mass spectra, peaks close to ω+ frequencies can be reduced to negligible levels relative to peaks close to ω c frequencies. Due to reduced errors with which the ω c quantity is obtained, the new resonance provides a means of cyclotron frequency measurements with precision greater than that achieved when ω+ frequency peaks are employed. The described phenomenon may be considered for a development into an FT-ICR MS technology with increased mass accuracy for applications in basic research, life, and environmental sciences. Graphical Abstract ᅟ.

KEYWORDS:

Cyclotron frequency; FT; FTMS; Fourier transform; Fourier transform mass spectrometry; ICR; Ion cyclotron resonance; Ion motion; Magnetron frequency; Mass accuracy; Reduced cyclotron frequency

PMID:
28213728
DOI:
10.1007/s13361-017-1598-y

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