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Evaluation of halogen chain-end functionality in 2-bromo-2-methylpropanoate esters of poly(oxyalkylene) polymers by MALDI-TOF spectroscopy

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Abstract

Esters of 2-bromo-2-methylpropanoate of poly(oxyalkylene) polymers such as poly(ethylene glycol) or α-methyl poly(ethylene glycol) were prepared in high yields and characterized by spectroscopic and chromatographic methods (NMR, FT-IR, mass spectroscopy and SEC). The halogen chain-end group in the poly(oxyalkylene) bromine-terminated esters was characterized by MALDI-TOF MS. The effect of the solvents (methanol or tetrahydrofuran) and the cationic agents such as silver trifluoroacetate (AgTFA), silver trifluoromethanesulfonate (AgTFS) and sodium trifluoroacetate (NaTFA) on the mass spectra was studied. Analysis of the mass spectra demonstrated that the analyte was transformed to unsaturated (elimination), alkoxy or hydroxyl end-groups (substitution) molecules when silver cationic agents were used; these results were also supported by 1H NMR study. When sodium salt was used as a cationic agent, well-defined bromine-terminated macromolecules were successfully determined through MALDI-TOF MS. Well-characterized esters of 2-bromo-2-methylpropanoate of poly(oxyalkylene) polymers could be used as ATRP macroinitiators for the synthesis of a variety of polymeric architectures of interest as drug delivery bioconjugates.

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Acknowledgements

The authors wish to thank the National Council of Science and Technology (CONACyT) for the support provided through the Project Number 256727 and the Laboratorio Nacional de Materiales Grafénicos (LNMG) of Centro de Investigación en Química Aplicada (CIQA) for the support with the instrumentation of MALDI-TOF. The authors also thank Dr. Geraldina Rodriguez for her valuable support during MALDI-TOF measurements.

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  1. Centro de Investigación en Química Aplicada (CIQA), Boulevard Enrique Reyna Hermosillo No 140, C.P. 25253, Saltillo, Coahuila, Mexico

    Angélica Velázquez & Luis Ernesto Elizalde

  2. Institut de Chimie Et Des Matériaux Paris-Est (ICMPE), UMR 7182, CNRS-Université Paris-Est Créteil, 2 rue Henri Dunant, 94320, Thiais, France

    Daniel Grande

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  1. Angélica Velázquez
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Correspondence to Luis Ernesto Elizalde.

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Velázquez, A., Grande, D. & Elizalde, L.E. Evaluation of halogen chain-end functionality in 2-bromo-2-methylpropanoate esters of poly(oxyalkylene) polymers by MALDI-TOF spectroscopy. Polym. Bull. 78, 5641–5665 (2021). https://doi.org/10.1007/s00289-020-03391-1

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