Polymer Analysis in the Second Dimension: Preliminary Studies for the Characterization of Polymers with 2D MS

Abstract

Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry (2D FTICR MS or 2D MS) allows direct correlation between precursor and fragment ions without isolation prior to fragmentation. The method has been optimized for the analysis of complex mixtures and used so far for the analysis of small molecules and peptides obtained by tryptic digestion of proteins and entire proteins. In this work, a 2D MS method is developed to characterize complex mixtures of polymers using infrared multiphoton decay (IRMPD) and electron capture dissociation (ECD) as fragmentation techniques, and D-α-tocopheryl polyethylene glycol 1000 succinate (TPGS), Polysorbate 80, and poly(methyl methacrylate) (PMMA) as analytes. The use of 2D MS allowed generation of fragment m/z values for all the compounds in the mixture at once and allowed tandem mass spectrometry of species very close in m/z that would have been difficult to isolate with a quadrupole for standard MS/MS. Furthermore, the use of unique features of 2D MS such as the extraction of neutral-loss lines allowed the successful assignment of peaks from low abundant species that would have been more difficult with standard MS/MS. For all the samples, the amount of information obtained with 2D MS was comparable with what obtained with multiple 1D MS/MS experiments targeted on each individual component within each mixture but required a single experiment of about 20-40 min.

Two-dimensional mass spectrometry: new perspectives for tandem mass spectrometry

“…Two-dimensional mass spectrometry was first introduced in 1987, but it has only seen significant development since 2010, because of the computational demands to store and process datasets and the impact of scintillation noise on the spectra. Since then, the development of 2D MS and the urQRd algorithm have enabled applications in the analysis of small molecules, proteomics (both top-down and bottom-up), and polymers (Floris et al 2016 , 2017 , 2018c ; Simon et al 2016 ; van Agthoven et al 2015 ; van Agthoven et al 2016 ). 2D MS has also been applied for MS 3 experiments on proteins without ion isolation (Floris et al 2018a , b ).…”

Phase relationships in two-dimensional mass spectrometry

“…Denoising algorithms have been proposed in order to decrease the amount of scintillation noise in 2D mass spectra and the pulse sequence was optimized [15][16][17]. 2D MS has been applied to small molecules and bottom-up and top-down proteomics, as well as polymer analysis [18][19][20][21][22][23][24][25]. Automated peak-assignment algorithms are being developed for routine analysis [26].…”

Electrospray Ionization of Polypropylene Glycol: Rayleigh-Charged Droplets, Competing Pathways, and Charge State-Dependent Conformations

“…3−6 ESI-MS is commonly used for studying polymers that are soluble in organic, aqueous, or mixed solvent systems. 7,8 Many of these investigations have benefited from the incorporation of ion mobility spectrometry (IMS) for ESI-IMS/MS workflows. 9,10 The question how gaseous analyte ions are produced during the ESI process has captivated the analytical research community for decades.…”