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126 264 Assigned Chemical Formulas from an Atmospheric Pressure Photoionization 9.4 T Fourier Transform Positive Ion Cyclotron Resonance Mass Spectrum
Version 2 2017-10-12, 19:43
Version 1 2017-10-11, 18:17
journal contribution
posted on 2017-10-11, 00:00 authored by Logan
C. Krajewski, Ryan P. Rodgers, Alan G. MarshallHere,
we present atmospheric pressure photoionization (APPI) Fourier
transform ion cyclotron resonance (FTICR) mass analysis of a volcanic
asphalt sample by acquiring data for 20 Da wide mass segments across
a 1000 Da range, stitched into a single composite mass spectrum, and
compare to a broad-band mass spectrum for the same sample. The segmented
spectrum contained 170 000 peaks with magnitude greater than
6σ of the root-mean-square (rms) baseline noise, for which 126 264
unique elemental compositions could be assigned. Approximately two-thirds
of those compositions represent monoisotopic (i.e., chemically different)
species. That complexity is higher than that for any previously reported
mass spectrum and almost 3 times greater than that obtained from the
corresponding broad-band spectrum (59 015). For the segmented
mass spectrum, the signal-to-noise ratio (S/N) was significantly higher
throughout the spectrum, but especially at the lower and upper ends
of mass distribution relative to that of the near-Gaussian broad-band
mass distribution. Despite this S/N improvement, mass measurement
accuracy was noticeably improved only at lower masses. The increased
S/N did, however, yield a higher number of peaks and higher dynamic
range throughout the entire segmented spectrum relative to the conventional
broad-band spectrum. The additional assigned peaks include higher
heteroatom species, as well as additional radicals and isotopologues.
Segmenting can require a significant investment in data acquisition
and analysis time over broad-band spectroscopy (∼1775% in this
case) making it best suited for targeted analysis and/or when complete
compositional coverage is important. Finally, the present segmented
spectrum contains, to our knowledge, more assigned peaks than any spectrum of any kind (e.g., UV–vis, infrared,
microwave, magnetic resonance, etc.).
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170 000 peaks126 264 Assigned Chemical Formulasmass spectrummass measurement accuracyion cyclotron resonancenear-Gaussian broad-band mass distributionUV1000 Da rangeAPPIbroad-band mass spectrumAtmospheric Pressure Photoionization 9.4 T Fourier TransformIon Cyclotron Resonance Mass Spectrum126 264FTICR
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