Adaptive search mass spectrometer spectral analysis

A computer-based method of mass spectroscopy analysis, the method comprising:

• identifying a set of sample peaks in a sample spectrum, wherein the sample spectrum comprises a sample mass spectrometer spectrum and the sample peaks are associated with fragments of a sample, each having sample fragment mass;
• selecting a reference spectrum having a set of reference peaks associated with fragments of a reference, each having a reference fragment mass;
• determining a mass difference between a selected sample peak in the sample spectrum, as compared to a selected reference peak in the reference spectrum;
• selecting a group exchange based on the mass difference, wherein the group exchange represents a change in the sample fragment mass associated with the selected sample peak, as compared with the reference fragment mass associated with the selected reference peak;
• shifting the selected sample peak or the selected reference peak by the mass difference;
• determining a fit value for the sample spectrum with respect to the reference spectrum, wherein the fit value characterizes similarity between the respective sets of sample and reference peak, including the shifted sample or reference peak, responsive to the group exchange;
• outputting one or both of the sample spectrum and the reference spectrum to a user interface;
• selecting one or more additional group exchanges representing one or more additional mass differences between one or more of the sample fragment masses associated with the sample peaks, as compared with one or more of the reference fragment masses associated with the reference peaks;
• and
• shifting one or more additional sample peaks or one or more additional reference peaks by the respective one or more additional mass differences;
• wherein the fit value characterizes similarity between the respective sample and reference spectra, including the one or more additional shifted sample or reference peaks, responsive to the one or more additional group exchanges.

A computer-based mass spectroscopy analysis system, comprising:

• a processor and memory adapted for comparing a sample spectrum from a mass spectrometer with a set of reference spectra from a library thereof, wherein the sample and reference spectra each comprise a plurality of peaks representing fragment masses of respective fragments;
• a user interface in communication with the processor, the user interface configured for:
• displaying the sample spectrum;
• identifying one or more of the reference spectra from the library based on a similarly or fit metric selected to identify same or similar fragment masses in the sample and reference spectra, wherein the similarity or fit metric is further selected to identify a same or similar total mass associated with one or more of the peaks in the respective sample and reference spectra;
• displaying one or more of the identified reference spectra with the sample spectrum;
• shifting one or more of the peaks in the displayed sample or reference spectrum by a change in mass value corresponding to a group exchange in the respective fragment;
• selecting or updating the total mass;
• identifying the one or more reference spectra based on the selected or updated total mass;
• and
• updating the respective similarly or fit metric accordingly, based on the one or more shifted peaks.