title: Matrix normalized MALDI-TOF quantification of a fluorotelomer-based acrylate polymer.
abstract: The degradation of fluorotelomer-based acrylate polymers (FTACPs) has been hypothesized to serve as a source of the environmental contaminants, perfluoroalkyl carboxylates (PFCAs). Studies have relied on indirect measurement of presumed degradation products to evaluate the environmental fate of FTACPs; however, this approach leaves a degree of uncertainty. The present study describes the development of a quantitative matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry method as the first direct analysis method for FTACPs. The model FTACP used in this study was poly(8:2 FTAC-co-HDA), a copolymer of 8:2 fluorotelomer acrylate (8:2 FTAC) and hexadecyl acrylate (HDA). Instead of relying on an internal standard polymer, the intensities of 40 poly(8:2 FTAC-co-HDA) signals (911-4612 Da) were normalized to the signal intensity of a matrix-sodium cluster (659 Da). We termed this value the normalized polymer response (P(N)). By using the same dithranol solution for the sample preparation of poly(8:2 FTAC-co-HDA) standards, calibration curves with coefficient of determinations (R(2)) typically >0.98 were produced. When poly(8:2 FTAC-co-HDA) samples were prepared with the same dithranol solution as the poly(8:2 FTAC-co-HDA) standards, quantification to within 25% of the theoretical concentration was achieved. This approach minimized the sample-to-sample variability that typically plagues MALDI-TOF, and is the first method developed to directly quantify FTACPs.
authors: Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario Canada, M5S 3H6.
authors: Keegan
authors: K
authors: Rankin
authors: Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario Canada, M5S 3H6.
authors: Scott A
authors: SA
authors: Mabury
mesh_terms: D000179:Acrylates / Q000032:analysis* / Q000737:chemistry; D004785:Environmental Pollutants / Q000032:analysis*; D005465:Fluorocarbon Polymers; D006845:Hydrocarbons, Fluorinated / Q000032:analysis* / Q000737:chemistry; D011108:Polymers / Q000032:analysis* / Q000737:chemistry; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods*
chemical_list: D000179:Acrylates; D004785:Environmental Pollutants; D005465:Fluorocarbon Polymers; D006845:Hydrocarbons, Fluorinated; D011108:Polymers; C540553:fluorotelomer acrylate polymers