Article Reversible Solubility Switching of a Polymer Triggered by Visible‐Light Responsive Azobenzene Photochromism with Negligible Thermal Relaxation

Takeshi Ueki SAMURAI ORCID ; Yuna Osaka ; Kenta Homma ORCID ; Shota Yamamoto SAMURAI ORCID ; Aya Saruwatari SAMURAI ORCID ; Hongxin Wang SAMURAI ORCID ; Masao Kamimura ORCID ; Jun Nakanishi SAMURAI ORCID

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Takeshi Ueki, Yuna Osaka, Kenta Homma, Shota Yamamoto, Aya Saruwatari, Hongxin Wang, Masao Kamimura, Jun Nakanishi. Reversible Solubility Switching of a Polymer Triggered by Visible‐Light Responsive Azobenzene Photochromism with Negligible Thermal Relaxation. Macromolecular Rapid Communications. 2024, 45 (22), 2400419. https://doi.org/10.1002/marc.202400419
SAMURAI

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(abstract)

This study reports the reversible solubility switching of a polymer triggered by non-phototoxic visible light. A photochromic polymerizable azobenzene monomer with four methoxy groups at the ortho-position (mAzoA) was synthesized, exhibiting reversible photoisomerization between transand cis-states using green (546 nm) and blue light (436 nm). Free radical copolymerization of hydrophilic dimethylacrylamide (DMAAm) with mAzoA produced a light-responsive random copolymer (P(mAzoA-r-DMAAm)) that shows a reversible photochromic reaction to visible light. Optimizing mAzoA content resulted in P(mAzoA10.7-r-DMAAm)3.0 kDa exhibiting LCST-type phase separation in PBS (pH 7.4) with transand cis-states at 39.2 °C and 32.9 °C, respectively. The bistable temperature range of 6.3 °C covers 37 °C, suitable for mammalian cell culture. Reversible solubility changes were demonstrated under alternating green and blue light at 37 °C. 1H NMR indicated significant retardation of thermal relaxation from cisto trans-states, preventing undesired thermal mechanical degradation. Madin Darby Canine Kidney (MDCK) cells adhered to the P(mAzoA-r-DMAAm) hydrogel, confirming its non-cytotoxicity and potential for biocompatible interfaces. This principle is useful for developing hydrogels that can reversibly stimulate cells mechanically or chemically in response to visible light.

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Keyword: azobenzene, gels. LCST, mechanobiology, phase transition

Date published: 2024-08-08

Publisher: Wiley

Journal:

  • Macromolecular Rapid Communications (ISSN: 10221336) vol. 45 issue. 22 2400419

Funding:

  • Japan Society for the Promotion of Science 20H02804
  • Japan Society for the Promotion of Science 20K21229
  • Japan Society for the Promotion of Science 23H02030
  • Japan Society for the Promotion of Science 22K14705
  • Japan Society for the Promotion of Science 22H00596
  • Japan Society for the Promotion of Science 23K17481

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.5075

First published URL: https://doi.org/10.1002/marc.202400419

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Updated at: 2024-12-04 14:52:28 +0900

Published on MDR: 2024-12-04 14:52:29 +0900

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