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Adamantane functionalized poly(2-oxazoline)s with broadly tunable LCST-behavior by molecular recognition

(2021) POLYMERS. 13(3).
Author
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Abstract
Smart or adaptive materials often utilize stimuli-responsive polymers, which undergo a phase transition in response to a given stimulus. So far, various stimuli have been used to enable the modulation of drug release profiles, cell-interactive behavior, and optical and mechanical properties. In this respect, molecular recognition is a powerful tool to fine-tune the stimuli-responsive behavior due to its high specificity. Within this contribution, a poly(2-oxazoline) copolymer bearing adamantane side chains was synthesized via triazabicyclodecene-catalyzed amidation of the ester side chains of a poly(2-ethyl-2-oxazoline-stat-2-methoxycarbonylpropyl-2-oxazoline) statistical copolymer. Subsequent complexation of the pendant adamantane groups with sub-stoichiometric amounts (0-1 equivalents) of hydroxypropyl beta-cyclodextrin or beta-cyclodextrin enabled accurate tuning of its lower critical solution temperature (LCST) over an exceptionally wide temperature range, spanning from 30 degrees C to 56 degrees C. Furthermore, the sharp thermal transitions display minimal hysteresis, suggesting a reversible phase transition of the complexed polymer chains (i.e., the beta-cyclodextrin host collapses together with the polymers) and a minimal influence by the temperature on the supramolecular association. Analysis of the association constant of the polymer with hydroxypropyl beta-cyclodextrin via H-1 NMR spectroscopy suggests that the selection of the macrocyclic host and rational polymer design can have a profound influence on the observed thermal transitions.
Keywords
CRITICAL SOLUTION TEMPERATURE, CYCLODEXTRIN INCLUSION COMPLEXES, RESPONSIVE POLYMERS SYNTHESIS, HOST-GUEST COMPLEXATION, THERMORESPONSIVE, POLYMERS, SUPRAMOLECULAR CONTROL, BETA-CYCLODEXTRIN, AQUEOUS-SOLUTIONS, COPOLYMERS, AMIDATION, stimuli-responsive polymer, post-polymerization modification, supramolecular association, poly(2-oxazoline)s, cyclodextrin

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Citation

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MLA
Van Guyse, Joachim, et al. “Adamantane Functionalized Poly(2-Oxazoline)s with Broadly Tunable LCST-Behavior by Molecular Recognition.” POLYMERS, vol. 13, no. 3, 2021, doi:10.3390/polym13030374.
APA
Van Guyse, J., Bera, D., & Hoogenboom, R. (2021). Adamantane functionalized poly(2-oxazoline)s with broadly tunable LCST-behavior by molecular recognition. POLYMERS, 13(3). https://doi.org/10.3390/polym13030374
Chicago author-date
Van Guyse, Joachim, Debaditya Bera, and Richard Hoogenboom. 2021. “Adamantane Functionalized Poly(2-Oxazoline)s with Broadly Tunable LCST-Behavior by Molecular Recognition.” POLYMERS 13 (3). https://doi.org/10.3390/polym13030374.
Chicago author-date (all authors)
Van Guyse, Joachim, Debaditya Bera, and Richard Hoogenboom. 2021. “Adamantane Functionalized Poly(2-Oxazoline)s with Broadly Tunable LCST-Behavior by Molecular Recognition.” POLYMERS 13 (3). doi:10.3390/polym13030374.
Vancouver
1.
Van Guyse J, Bera D, Hoogenboom R. Adamantane functionalized poly(2-oxazoline)s with broadly tunable LCST-behavior by molecular recognition. POLYMERS. 2021;13(3).
IEEE
[1]
J. Van Guyse, D. Bera, and R. Hoogenboom, “Adamantane functionalized poly(2-oxazoline)s with broadly tunable LCST-behavior by molecular recognition,” POLYMERS, vol. 13, no. 3, 2021.
@article{8711187,
  abstract     = {{Smart or adaptive materials often utilize stimuli-responsive polymers, which undergo a phase transition in response to a given stimulus. So far, various stimuli have been used to enable the modulation of drug release profiles, cell-interactive behavior, and optical and mechanical properties. In this respect, molecular recognition is a powerful tool to fine-tune the stimuli-responsive behavior due to its high specificity. Within this contribution, a poly(2-oxazoline) copolymer bearing adamantane side chains was synthesized via triazabicyclodecene-catalyzed amidation of the ester side chains of a poly(2-ethyl-2-oxazoline-stat-2-methoxycarbonylpropyl-2-oxazoline) statistical copolymer. Subsequent complexation of the pendant adamantane groups with sub-stoichiometric amounts (0-1 equivalents) of hydroxypropyl beta-cyclodextrin or beta-cyclodextrin enabled accurate tuning of its lower critical solution temperature (LCST) over an exceptionally wide temperature range, spanning from 30 degrees C to 56 degrees C. Furthermore, the sharp thermal transitions display minimal hysteresis, suggesting a reversible phase transition of the complexed polymer chains (i.e., the beta-cyclodextrin host collapses together with the polymers) and a minimal influence by the temperature on the supramolecular association. Analysis of the association constant of the polymer with hydroxypropyl beta-cyclodextrin via H-1 NMR spectroscopy suggests that the selection of the macrocyclic host and rational polymer design can have a profound influence on the observed thermal transitions.}},
  articleno    = {{374}},
  author       = {{Van Guyse, Joachim and Bera, Debaditya and Hoogenboom, Richard}},
  issn         = {{2073-4360}},
  journal      = {{POLYMERS}},
  keywords     = {{CRITICAL SOLUTION TEMPERATURE,CYCLODEXTRIN INCLUSION COMPLEXES,RESPONSIVE POLYMERS SYNTHESIS,HOST-GUEST COMPLEXATION,THERMORESPONSIVE,POLYMERS,SUPRAMOLECULAR CONTROL,BETA-CYCLODEXTRIN,AQUEOUS-SOLUTIONS,COPOLYMERS,AMIDATION,stimuli-responsive polymer,post-polymerization modification,supramolecular association,poly(2-oxazoline)s,cyclodextrin}},
  language     = {{eng}},
  number       = {{3}},
  pages        = {{16}},
  title        = {{Adamantane functionalized poly(2-oxazoline)s with broadly tunable LCST-behavior by molecular recognition}},
  url          = {{http://dx.doi.org/10.3390/polym13030374}},
  volume       = {{13}},
  year         = {{2021}},
}

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