On the Kendrick Mass Defect Plots of Multiply Charged Polymer Ions: Splits, Misalignments, and How to Correct Them

Journal of the American Society for Mass Spectrometry
Thierry FouquetHiroaki Sato

Abstract

The Kendrick mass defect (KMD) analysis of multiply charged polymeric distributions has recently revealed a surprising isotopic split in their KMD plots-namely a 1/z difference between KMDs of isotopes of an oligomer at charge state z. Relying on the KMD analysis of actual and simulated distributions of poly(ethylene oxide) (PEO), the isotopic split is mathematically accounted for and found to go with an isotopic misalignment in certain cases. It is demonstrated that the divisibility (resp. indivisibility) of the nominal mass of the repeating unit (R) by z is the condition for homolog ions to line up horizontally (resp. misaligned obliquely) in a KMD plot. Computing KMDs using a fractional base unit R/z eventually corrects the misalignments for the associated charge state while using the least common multiple of all the charge states as the divisor realigns all the points at once. The isotopic split itself can be removed by using either a new charge-dependent KMD plot compatible with any fractional base unit or the remainders of KM (RKM) recently developed for low-resolution data all found to be linked in a unified theory. These original applications of the fractional base units and the RKM plots are of importance theoretically...Continue Reading

References

Jan 21, 2004·Accounts of Chemical Research·Alan G Marshall, Ryan P Rodgers
Mar 4, 2006·Analytical and Bioanalytical Chemistry·Juris Meija
Feb 24, 2012·Journal of Mass Spectrometry : JMS·Lekha Sleno
Nov 29, 2013·Mass Spectrometry Reviews·Laurence Charles
May 23, 2014·Journal of the American Society for Mass Spectrometry·Hiroaki SatoTakafumi Sato
Mar 10, 2017·Food Chemistry·Anna Vallverdú-QueraltVéronique Cheynier
Apr 4, 2017·Rapid Communications in Mass Spectrometry : RCM·Thierry Fouquet, Hiroaki Sato
Jun 24, 2017·ChemistryOpen·Anna Vallverdú-QueraltVéronique Cheynier
Jul 25, 2017·Journal of the American Society for Mass Spectrometry·Soheil Pourshahian

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Citations

Oct 30, 2019·Journal of the American Society for Mass Spectrometry·Mickaël ChevalierChristophe Flahaut
Nov 24, 2019·Journal of Mass Spectrometry : JMS·Thierry N J Fouquet
Nov 13, 2019·Rapid Communications in Mass Spectrometry : RCM·Jessica S DesportLuc Patiny
Jun 5, 2019·Rapid Communications in Mass Spectrometry : RCM·Thierry N J FouquetRobert B Cody
May 1, 2021·Nature Communications·Bridget B McGivernKelly C Wrighton
Jul 16, 2021·Journal of the American Society for Mass Spectrometry·Tomos E MorganPeter B O'Connor

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