TY - JOUR
T1 - Determination of polyethylene glycol end group functionalities by combination of selective reactions and characterization by matrix assisted laser desorption/ionization time-of-flight mass spectrometry
AU - Zhang, Boyu
AU - Zhang, Hong
AU - Myers, Brittany K.
AU - Elupula, Ravinder
AU - Jayawickramarajah, Janarthanan
AU - Grayson, Scott M.
N1 - Funding Information:
The authors acknowledge the financial support of Department of Defense ( W81XWH-10-1-0377 ) and the National Science Foundation under the NSF EPSCoR Cooperative Agreement No. EPS-1003897 with additional support from the Louisiana Board of Regents . JJ and HZ acknowledge NSF for support ( CHE 1112091 ). The authors also acknowledge Aldrich Materials Science, an initiative of Sigma- Aldrich for providing the polymers for analysis.
Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.
PY - 2014/3/13
Y1 - 2014/3/13
N2 - End groups play a critical role in macromolecular coupling reactions for building complex polymer architectures, yet their identity and purity can be difficult to ascertain using traditional analytical technique. Recent advances in mass spectrometry techniques have made matrix-assisted laser desorption/ionization time-of-fight (MALDI-TOF) mass spectrometry a rapid and powerful tool for providing detailed information about the identity and purity of homopolymer end groups. In this work, MALDI-TOF mass spectrometry was used to study end groups of linear polyethylene glycols. In particular, the identifications of alcohol, amine and thiol end groups are investigated because these nucleophilic moieties are among the most common within biological and synthetic macromolecules. Through comparative characterization of alcohol, amine, and thiol end groups, the exact identification of these end groups could be confirmed by selective and quantitative modification. The precision of this technique enables the unambiguous differentiation of primary amino groups relative to hydroxyl groups, which differ by only 1 mass unit. In addition, the quantitative conversion of various polyethylene glycol end groups using highly efficient coupling reactions such as the thiol-ene and azide-alkyne click reactions can be confirmed using MALDI-TOF mass spectrometry.
AB - End groups play a critical role in macromolecular coupling reactions for building complex polymer architectures, yet their identity and purity can be difficult to ascertain using traditional analytical technique. Recent advances in mass spectrometry techniques have made matrix-assisted laser desorption/ionization time-of-fight (MALDI-TOF) mass spectrometry a rapid and powerful tool for providing detailed information about the identity and purity of homopolymer end groups. In this work, MALDI-TOF mass spectrometry was used to study end groups of linear polyethylene glycols. In particular, the identifications of alcohol, amine and thiol end groups are investigated because these nucleophilic moieties are among the most common within biological and synthetic macromolecules. Through comparative characterization of alcohol, amine, and thiol end groups, the exact identification of these end groups could be confirmed by selective and quantitative modification. The precision of this technique enables the unambiguous differentiation of primary amino groups relative to hydroxyl groups, which differ by only 1 mass unit. In addition, the quantitative conversion of various polyethylene glycol end groups using highly efficient coupling reactions such as the thiol-ene and azide-alkyne click reactions can be confirmed using MALDI-TOF mass spectrometry.
KW - Click chemistry
KW - End group determination
KW - Matrix-assisted laser desorption/ionization time-of-fight mass spectrometry
KW - Polyethylene glycol
KW - Polymer characterization
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U2 - 10.1016/j.aca.2014.01.039
DO - 10.1016/j.aca.2014.01.039
M3 - Article
C2 - 24580852
AN - SCOPUS:84894487174
SN - 0003-2670
VL - 816
SP - 28
EP - 40
JO - Analytica Chimica Acta
JF - Analytica Chimica Acta
ER -