Enhanced ionization in electrospray ionization mass spectrometry of labile end-group-containing polystyrenes using silver(I) tetrafluoroborate as doping salt

Gruendling, T., Hart-Smith, G., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2008) Enhanced ionization in electrospray ionization mass spectrometry of labile end-group-containing polystyrenes using silver(I) tetrafluoroborate as doping salt. Macromolecules, 41(6).

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Abstract

The use of silver tetrafluoroborate as a doping salt to achieve efficient and soft desorption/ionization of labile end-group-carrying polystyrene during electrospray ionization is demonstrated. Polystyrene carrying a dithioester end group prepared via reversible addition fragmentation chain transfer (RAFT) chemistry (using the RAFT agent cumyl phenyldithioacetate) as well as a commercial polymer standard prepared by anionic polymerization serve as model compounds. By employing silver tetrafluoroborate as ionization agent, an increase in ion count of more than one order of magnitude was achieved compared to ionization with sodium iodide. Little loss of the end group occurred via elimination of the dithioacid to yield vinyl-terminated polymer. A possible mechanism is given for catalysis of the cleavage reaction in the presence of silver salts. Side-product formation due to thermal or collision induced loss of the dithioester was kept at a minimum under optimized source conditions. Thus, we introduce a novel soft ionization protocol for polystyrenes, which are often difficult to ionize. © 2008 American Chemical Society.

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ID Code: 99176
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :33
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, University of New South Wales, Sydney, NSW 2052, Australia; email: c.barner-kowollik@unsw.edu.au
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Keywords: Anionic polymerization, Electrospray ionization, Mass spectrometry, Polymers, Sodium compounds, Commercial polymers, Silver tetrafluoroborate, Polystyrenes
DOI: 10.1021/ma702163v
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 10 Oct 2016 02:58

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