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Time‐base modulation for the correction of cyclotron frequency shifts observed in long‐lived transients from fourier‐transform ion‐cyclotron‐resonance mass spectrometry of electrosprayed biopolymers
Author(s) -
Bruce James E.,
Anderson Gordon A.,
Hofstadler Steven A.,
Winger Brian E.,
Smith Richard D.
Publication year - 1993
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.1290070803
Subject(s) - fourier transform ion cyclotron resonance , chemistry , ion cyclotron resonance , mass spectrometry , cyclotron , analytical chemistry (journal) , selected ion monitoring , fourier transform , ion , resolution (logic) , nuclear magnetic resonance , atomic physics , physics , chromatography , artificial intelligence , gas chromatography–mass spectrometry , organic chemistry , quantum mechanics , computer science
The occurrence of small shifts in the cyclotron frequency during the acquisition of very long transients (in excess of 80 s) has been observed to be a limiting factor for ultrahigh‐resolution mass measurements of protein ions performed with electrospray‐ionization Fourier‐transform ion‐cyclotron‐resonance mass spectrometry. Resolution measurements were restricted to values less than 10 6 because of the frequency shifts. Measurements of the frequency shifts, performed by sequentially transforming small segments of the transient, allowed the shift to be characterized and fitted to a 4th‐order equation. The sampling rate of the acquired transient was then modulated (at a rate equal to the reciprocal of the rate for the frequency shift) to allow ultrahigh resolution, greater than 2 × 10 6 , and improved mass measurement and precision to be achieved for a small protein.