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Block length determination of the block copolymer mPEG-b-PS using MALDI-TOF MS/MS

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Crecelius, Anna C., Becer, C. Remzi, Knop, Katrin and Schubert, Ulrich S. (2010) Block length determination of the block copolymer mPEG-b-PS using MALDI-TOF MS/MS. Journal of Polymer Science Part A: Polymer Chemistry, Vol.48 (No.20). pp. 4375-4384. doi:10.1002/pola.24223 ISSN 0887-624X.

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Official URL: http://dx.doi.org/10.1002/pola.24223

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Abstract

The molar mass determination of block copolymers, in particular amphiphilic block copolymers, has been challenging with chromatographic techniques. Therefore, methoxy poly(ethylene glycol)-b-poly(styrene) (mPEG-b-PS) was synthesized by atom transfer radical polymerization (ATRP) and characterized in detail not only by conventional chromatographic techniques, such as size exclusion chromatography (SEC), but also by matrix-assisted laser/desorption ionization tandem mass spectrometry (MALDI-TOF MS/MS). As expected, different molar mass values were obtained in the SEC measurements depending on the calibration standards (either PEG or PS). In contrast, MALDI-TOF MS/MS analysis allowed the molar mass determination of each block, by the scission of the weakest point between the PEG and PS block. Thus, fragments of the individual blocks could be obtained. The PEG block showed a depolymerization reaction, while for the PS block fragments were obtained in the monomeric, dimeric, and trimeric regions as a result of multiple chain scissions. The block length of PEG and PS could be calculated from the fragments recorded in the MALDI-TOF MS/MS spectrum. Furthermore, the assignment of the substructures of the individual blocks acquired by MALDI-TOF MS/MS was accomplished with the help of the fragments that were obtained from the corresponding homopolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Block copolymers, Mass spectrometry, Tandem mass spectrometry
Journal or Publication Title: Journal of Polymer Science Part A: Polymer Chemistry
Publisher: John Wiley & Sons Ltd.
ISSN: 0887-624X
Official Date: 2010
Dates:
DateEvent
2010Published
Volume: Vol.48
Number: No.20
Page Range: pp. 4375-4384
DOI: 10.1002/pola.24223
Status: Peer Reviewed
Publication Status: Published
Funder: Dutch Polymer Institute (DPI), Thuringia (Germany). Ministerium für Bildung, Wissenschaft und Kultur
Grant number: B515-07008 (TMBWK)

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