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Issue 31, 2015
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On the structure–control relationship of amide-functionalized SG1-based alkoxyamines for nitroxide-mediated polymerization and conjugation

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Abstract

The functionalization of alkoxyamines prior to nitroxide-mediated polymerization (NMP) induces important structural variations when compared to the parent molecules. This may have important consequences on the design of functionalized materials by pre-functionalization. In this context, a wide range of amide-functionalized alkoxyamines (a functionality often obtained after conjugation from COOH– and N-succinimidyl-containing alkoxyamines) based on the nitroxide SG1 (N-tert-butyl-N-(1-diethyl phosphono-2,2-dimethylpropyl) nitroxide) have been synthesized and their dissociation rate constants (kd) have been determined. To rationalize their reactivity, a multi-parameter procedure was applied and enabled to discriminate disubstituted amide-functionalized alkoxyamines from monosubstituted ones. Monosubstituted alkoxyamines exhibited lower kd than their disubstituted counterparts (Ea increase of ∼7–10 kJ mol−1) because of the occurrence of intramolecular hydrogen bonding (IHB) between the alkyl and the nitroxide fragments. NMP of styrene, n-butyl acrylate and methyl methacrylate with a small amount of acrylonitrile was then successfully performed from two representative secondary SG1-based alkoxyamines employed for conjugation: namely AMA (COOH-containing) and AMA-NHS (N-succinimidyl derivative), and compared to polymerizations initiated with AMA-Gem, an AMA-based alkoxyamine pre-functionalized with the anticancer drug Gemcitabine (Gem) and subjected to IHB. Although AMA-NHS showed the best results due to its lower Ea, the strong polarity of the Gem moiety that counter-balanced the detrimental effect of IHB over its kd still allowed for a reasonable control.

Graphical abstract: On the structure–control relationship of amide-functionalized SG1-based alkoxyamines for nitroxide-mediated polymerization and conjugation

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Publication details

The article was received on 22 Feb 2015, accepted on 19 Mar 2015 and first published on 19 Mar 2015


Article type: Paper
DOI: 10.1039/C5PY00283D
Polym. Chem., 2015,6, 5693-5704
  • Open access: Creative Commons BY-NC license
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    On the structure–control relationship of amide-functionalized SG1-based alkoxyamines for nitroxide-mediated polymerization and conjugation

    E. Guégain, V. Delplace, T. Trimaille, D. Gigmes, D. Siri, S. R. A. Marque, Y. Guillaneuf and J. Nicolas, Polym. Chem., 2015, 6, 5693
    DOI: 10.1039/C5PY00283D

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