title: High Resolution Mass Spectrometry of Polyfluorinated Polyether-Based Formulation.
abstract: High resolution mass spectrometry (HRMS) was successfully applied to elucidate the structure of a polyfluorinated polyether (PFPE)-based formulation. The mass spectrum generated from direct injection into the MS was examined by identifying the different repeating units manually and with the aid of an instrument data processor. Highly accurate mass spectral data enabled the calculation of higher-order mass defects. The different plots of MW and the nth-order mass defects (up to n = 3) could aid in assessing the structure of the different repeating units and estimating their absolute and relative number per molecule. The three major repeating units were -C2H4O-, -C2F4O-, and -CF2O-. Tandem MS was used to identify the end groups that appeared to be phosphates, as well as the possible distribution of the repeating units. Reversed-phase HPLC separated of the polymer molecules on the basis of number of nonpolar repeating units. The elucidated structure resembles the structure in the published manufacturer technical data. This analytical approach to the characterization of a PFPE-based formulation can serve as a guide in analyzing not just other PFPE-based formulations but also other fluorinated and non-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health. Graphical Abstract ᅟ.
authors.affiliation: Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, Science Park 904, Amsterdam, 1098XH, The Netherlands.|Hochschule Fresenius, Institute for Analytical Research, Limburger St. 2, D-65510, Idstein, Germany.
authors.forename: Ian Ken
authors.initials: IK
authors.lastname: Dimzon
authors.affiliation: The National Food Institute, Mørkhøj Bygade 19, DK-2860, Søborg, Denmark.
authors.forename: Xenia
authors.initials: X
authors.lastname: Trier
authors.affiliation: Hochschule Fresenius, Institute for Analytical Research, Limburger St. 2, D-65510, Idstein, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Frömel
authors.affiliation: Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, Science Park 904, Amsterdam, 1098XH, The Netherlands.
authors.forename: Rick
authors.initials: R
authors.lastname: Helmus
authors.affiliation: Hochschule Fresenius, Institute for Analytical Research, Limburger St. 2, D-65510, Idstein, Germany.
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Knepper
authors.affiliation: Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, Science Park 904, Amsterdam, 1098XH, The Netherlands. W.P.deVoogt@uva.nl.
authors.forename: Pim
authors.initials: P
authors.lastname: de Voogt
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods; D005465:Fluorocarbon Polymers / Q000032:analysis* / Q000737:chemistry*; D013058:Mass Spectrometry / Q000379:methods*; D015394:Molecular Structure; D053719:Tandem Mass Spectrometry / Q000379:methods
chemical_list: D005465:Fluorocarbon Polymers
keywords: HRMS; Higher-order mass defect; PFPE