New MS Concepts for Synthetic Polymers and Additives Characterization

New ionization processes have been developed for biological mass spectrometry in which the matrix lifts the nonvolatile analyte into the gas phase as ions without any additional energy input. We rationalized that additional fundamental knowledge is needed to assess analytical utility for the field of synthetic polymers and additives. Different mass spectrometers (Thermo Orbitrap (Q-)Exactive (Focus); Waters SYNAPT G2(S)) were employed. The formation of multiply-charged polymer ions upon exposure of the matrix/analyte(/salt) sample to sub-atmospheric pressure directly from the solid state and surfaces facilitates the use of advanced mass spectrometers for detection of polymeric materials including consumer products (e.g., gum). Astonishingly, using nothing more than a small molecule matrix compound (e.g., 2-methyl-2-nitropropane-1,3-diol or 3-nitrobenzonitrile) and a salt (e.g., mono- or divalent cation(s)), such samples upon exposure to sub-atmospheric pressure transfer nonvolatile polymers and nonvolatile salts into the gas phase as multiply-charged ions. These successes contradict the conventional understanding of ionization in MS, because can nonvolatile polymers be lifted in the gas phase as ions not only by as little as a volatile matrix but also by the salt required for ionizing the analyte through noncovalent metal cation adduction(s). Prototype vacuum MAI and automated sources using a contactless approach are demonstrated for direct analyses of synthetic polymers and plasticizers, minimizing risk of contamination using direct sample introduction to the mass spectrometer vacuum. Direct ionization methods from surfaces without the need of high voltage, a laser, or even applied heat are demonstrated for detailed materials characterization using (ultra)high resolution and accurate mass measurements enabled by the multiply-charged ions extending the mass range of high-performance mass spectrometers and use of a split probe. Our vision is that, with further development of fundamentals and dedicated sources, both spatial- and temporal-resolution measurements are within reach if sensitivity is addressed for decreasing sample-size measurements.