4.8 Article

Investigations of the Alignment Process of PBPMLG: 2H NMR Analysis reveals a thermoresponsive 90° Flip of the Polymer

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 38, Pages 21040-21046

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202108814

Keywords

alignment medium; isotopic labelling; NMR spectroscopy; thermoresponsive polymers

Funding

  1. Projekt DEAL

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The application of anisotropic parameters in NMR-spectroscopy enables the acquisition of spatial and angular information complementary to conventional isotropic NMR-measurements. PBPMLG, a recently discovered polyglutamate-based alignment medium, exhibits thermoresponsive behavior in the lyotropic liquid crystalline phase, offering potential for deeper understanding of the alignment process. Investigating the thermoresponsive behavior by synthesizing deuterated PBPMLG-isotopologues and their subsequent analyses using H-2 NMR-spectroscopy have revealed new insights in the alignment process.
The application of anisotropic parameters in NMR-spectroscopy enables the acquisition of spatial and angular information, complementary to those from conventional isotropic NMR-measurements. The use of alignment media is a well-established method for inducing anisotropy. PBPMLG is a recently discovered polyglutamate-based alignment medium, exhibiting thermoresponsive behavior in the lyotropic liquid crystalline (LLC) phase, thus offering potential for deeper understanding of the alignment process. We present one approach for investigating the thermoresponsive behavior by synthesizing specifically deuterated PBPMLG-isotopologues and their subsequent analyses using H-2 NMR-spectroscopy. It was possible to relate the observed thermoresponsive behavior to a flip of the polymer with respect to the external magnetic field-an effect never observed before in glutamate-based polymeric alignment media. Furthermore, a solvent-induced temperature dependent gelation was verified in THF, which might provide yet another opportunity to manipulate the properties of this alignment medium in the future.

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