Capabilities and limitations of direct analysis in real time orbitrap mass spectrometry and tandem mass spectrometry for the analysis of synthetic and natural polymers

Abstract

DART-MS allowed the direct and rapid analysis (mass spectra and tandem mass spectra of all the polymers were acquired in seconds) based on the exact masses of their [M+H](+) and [M+NH4](+) ions (in the positive mode) or [M](-·) ions (for polymers having a high sensitivity toward electron-capture ionisation such as PFPEs), as well as the exact masses of their product ions, for both synthetic and natural polymers under ambient conditions without any sample pre-treatment.

Detection of polydimethylsiloxanes transferred from silicone‐coated parchment paper to baked goods using direct analysis in real time mass spectrometry

“…The most abundant PDMS ions in positive‐ion DART‐MS are formed as ammonium adducts and correspond to a series of the general formula [(C 2 H 6 SiO) n + NH 4 ] + yielding peaks at nominal m/z = (n × 74) + 18. These ions do not necessarily represent intact PDMS molecules . The isotopic patterns also reveal the presence of multiple Si atoms.…”

“…Positive‐ion DART‐MS is well‐suited for the analysis of polydimethylsiloxane (PDMS) up to about m/z 3000 that can also be employed for mass calibration . Further, positive‐ion DART‐MS can efficiently be applied to analyze PDMS on the surfaces of silicone rubber products of daily use and to track the release of PDMS oligomers from silicone rubber molds into baked goods under the conditions of common kitchen use …”

“…[4] It has, for example, been used to analyze polycyclic aromatic hydrocarbon and polychlorinated biphenyl contaminations in shrimps and fish, [20] to detect aflatoxin in milk, [21] and to observe the formation of acrylamide in biscuits during baking. [22] Positive-ion DART-MS is well-suited for the analysis of polydimethylsiloxane (PDMS) up to about m/z 3000 [23] that can also be employed for mass calibration. [16] Further, positive-ion DART-MS can efficiently be applied to analyze PDMS on the surfaces of silicone rubber products of daily use [19] and to track the release of PDMS oligomers from silicone rubber molds into baked goods under the conditions of common kitchen use.…”

Improving the Resolution of Kendrick Mass Defect Analysis for Polymer Ions with Fractional Base Units

“…5–7) In a favorable case (soluble, low molecular weight and dispersity), soft ionization techniques such as electrospray ionization (ESI) or matrix assisted laser desorption ionization (MALDI) transfer the intact polymer chains into the gas phase with no loss of the molecular information. 8–13) Alternatively, harder ion sources such as laser desorption ionization (LDI), atmospheric solids analysis probe (ASAP) 14,15) or pyrolysis 16) produce satisfactory mass spectra retaining a part of the molecular information from high molecular weight or crosslinked polymers.…”

Characterizing synthetic polymers and additives using new ionization methods for mass spectrometry

“…In the past two decades, developments in ionization methods have significantly increased the applicability of mass spectrometry (MS) for the analysis of synthetic polymeric materials. [1][2][3][4][5][6][7][8][9][10][11] More recently, ambient ionization approaches have provided rapid analysis with little or no sample preparation by methods such as desorption electrospray ionization (DESI), [12][13][14] direct analysis in real time (DART), [15][16][17] and atmospheric solids analysis probe (ASAP). [18][19][20][21] Investigations are ongoing to elucidate the processes responsible for gas-phase ion formation.…”