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MALDI-TOF MS Characterization of Covalent Cationized Polyethylene



Sheng Lin-Gibson, D L. Brunner, David L. VanderHart, Barry J. Bauer, B M. Fanconi, Kathleen M. Flynn, William E. Wallace


MALDI-TOF MS generally uses metal salts to cationize synthetic polymers, such as polystyrene. However, reduced analyte signal often results from complications during the metal ionization processes in the gas phase including competition between the analyte and matrix for cationization, self-clustering of the metal salts, and clustering of metal salts with matrix. One approach to increase the polymer ion signal is to apply more aggressive laser power; however, this may result in fragmentation of the polymer leading to molecular mass distribution (MMD) unrepresentative of the true distribution. We have developed a covalent cationization method in which a phosphonium or an ammonium salt is covalently attached to one of the chain ends. This will assure singly charged analytes and the competition associated with metal ionization will be eliminated. Better spectra can be generated since the undesirable background noise can also be reduced. Furthermore, polyolefins that cannot be cationized using traditional metal approach can be cationized using covalent cationization to produce successful MALDI spectra. This proceeding polyolefins and polystyrenes and compare covalent cationization method to traditional metal cationization for polybutadiene and polystyrene to gain understanding of the mechanisms that govern the desorption ionization processes.
Proceedings Title
American Chemical Society; Division of Polymer Chemistry, National Meeting |224th | 224th ACS National Meeting | American Chemical Society
Conference Dates
August 1, 2002
Conference Title
Polymer Preprints


chemical modification, MALDI-TOF MS, polybutadiene, polyolefin, polystryrene


Lin-Gibson, S. , Brunner, D. , VanderHart, D. , Bauer, B. , Fanconi, B. , Flynn, K. and Wallace, W. (2003), MALDI-TOF MS Characterization of Covalent Cationized Polyethylene, American Chemical Society; Division of Polymer Chemistry, National Meeting |224th | 224th ACS National Meeting | American Chemical Society, [online], (Accessed May 24, 2024)


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Created August 1, 2003, Updated February 19, 2017