Commercial formaldehyde standard for mass calibration in mass spectrometry

  1. Get@NRC: Commercial formaldehyde standard for mass calibration in mass spectrometry (Opens in a new window)
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Journal titleJournal of Mass Spectrometry
Pages463469; # of pages: 7
SubjectAcetal resins; calibration; Ionization; Mass spectrometry; Oligomers; Polymers; Spectrometry; Environmental contaminant; External calibration; Formaldehyde solutions; Quadrupole-time of flights; Tandem mass spectrometry; Electrospray ionization; carbene; formaldehyde; polyoxymethylene; chemical reaction; chemical structure; depolymerization; electrospray; fragmentation reaction; hydrogen bond; low temperature; nucleophilicity; polymerization; proton transport; quadrupole mass spectrometry; time of flight mass spectrometry
AbstractCommon calibration standards for mass spectrometry can be a source of many problems including instrument contamination, ionization suppression and formation of unidentified ions during subsequent analysis. In this article, we present a new approach for the calibration of mass analyzers such as a quadrupole-time-of-flight mass spectrometry using a diluted solution of commercial formaldehyde. Formaldehyde is an inexpensive and commonly used solvent, and its intrinsic polymerization leads to the formation of polyoxymethylene (POM) oligomers, which are excellent multiple calibration standards for a low-mass spectral region (up to m/z 400) in the positive and negative mode of electrospray ionization. We explore the nature and origin of these polymeric species and attributed them to chemical reactions of formaldehyde and stabilizing agents in commercial formaldehyde solutions and during electrospray ionization. In contrast to other calibrants, POM oligomers do not contaminate the instrument and can easily be removed from the sample delivery system. Using tandem mass spectrometry, we elucidate the structures of the detected POM oligomers and report their reference masses, which are tightly spaced by 30 mass units. In our calibration method, mass errors of <5ppm can be obtained from m/z 20-400 using external calibration with a simple one-point zero-order correction of spectral data and without the need for operation of a dual spray or internal calibrants. Our approach will be particularly useful for those interested in the analysis of fragile ions with low m/z values and can function at instrumental conditions required for analysis of the most labile metabolites and environmental contaminants.
Publication date
AffiliationNational Research Council Canada (NRC-CNRC); Measurement Science and Standards
Peer reviewedYes
NPARC number21275711
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Record identifier3caf807a-205a-417b-a6e0-f3bddf3ff706
Record created2015-07-14
Record modified2016-05-09
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