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Polymer analysis in the second dimension: preliminary studies for the characterisation of polymers with 2D MS Federico Floris, Claudio Vallotto, Lionel Chiron, Alice Lynch, Mark P. Barrow, Marc-André Delsuc, and Peter B O'Connor Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.7b02086 • Publication Date (Web): 08 Aug 2017 Downloaded from http://pubs.acs.org on August 10, 2017
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Analytical Chemistry
Polymer analysis in the second dimension: preliminary studies for the characterisation of polymers with 2D MS Federico Floris,1 Claudio Vallotto,1 Lionel Chiron,2 Alice M. Lynch,1 Mark P. Barrow,1 Marc-André Delsuc,2,3 Peter B. O’Connor.1,* 1
University of Warwick, Department of Chemistry, Coventry, CV4 7AL, United Kingdom CASC4DE, 20 Avenue du Neuhof, 67100, Strasbourg, France 3 Institut de Génétique et de Biologie Moléculaire et Cellulaire, Institut National de la Santé et de la Recherche, U596; Centre National de la Recherche Scientifique, Unité Mixte de Recherche 7104; Université de Strasbourg, 67404 Illkirch-Graffenstaden, France 2
*
Corresponding Author: Peter B. O’Connor, University of Warwick, Department of Chemistry, Coventry, CV4 7AL, United Kingdom. Email:
[email protected]. Tel: +44 (0) 2476 151 008.
Keywords: FT-ICR MS, 2D MS, polymers
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Analytical Chemistry
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Abstract Two-Dimensional Fourier transform ion cyclotron resonance mass spectrometry (2D FT-ICR MS or 2D MS) allows direct correlation between precursor and fragment ions without isolation prior to fragmentation. The method has been optimised for the analysis of complex mixtures, and used so far for the analysis of small molecules, peptides obtained by tryptic digestion of proteins, and entire proteins. In this work, a 2D MS method is developed to characterise complex mixtures of polymers using IRMPD and ECD as fragmentation techniques, and TPGS, Polysorbate 80, and 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 to 40 minutes.
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Analytical Chemistry
Introduction The increasing diversity and complexity of polymeric structures requires the use of progressively more accurate techniques for their structural investigation. Most polymeric materials consist in fact of complex mixtures of oligomers, whose physical properties are the result of the combined effects of the individual components and are usually characterized through NMR, FTIR and UV spectroscopy, or chromatography. Although these methods have proven their reliability on the studies of polymeric mixtures such as TPGS,1–3 they struggle to provide a complete profile of the components in the mixture; a difficulty aggravated by the presence of low abundant species. On the other hand, mass spectrometry (MS) is able to characterise the different components of a polymer mixture based on the mass-to-charge ratio (m/z) of their ions, through which the number average molecular weight Mn and the weight average molecular weight Mw are calculated. The interest in investigating synthetic polymers structures with ultra-high resolution MS strongly increased in the last decade.4 Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry5,6 has proven to be the highest performance MS technique in terms of resolving power (RP) and mass measurement accuracy (MMA), reaching routinely RP of >106 and MMA
