Luetzel, Kyra and Laqua, Henryk and Sathian, Manjima B. and Nissl, Benedikt and Szanto, Judit Katalin and Senser, Christina-Anna and Savasci, Goekcen and Allmendinger, Lars and Kicin, Bilal and Ruf, Vincent and Kammerer, Dominik and Lohmueller, Theobald and Karaghiosoff, Konstantin and Ali, Ahmed M. and Storch, Ursula and Mederos y Schnitzler, Michael and Ochsenfeld, Christian and Konrad, David B. (2025) A Platform for the Development of Highly Red-Shifted Azobenzene-Based Optical Tools. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 64 (32). ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
Azobenzenes are versatile photoswitches that can be used to generate elaborate optical tools, including photopharmaceuticals. However, the targeted application-guided design of new photoswitches with specific properties remains challenging. We have developed synthetic protocols for derivatives of the dfdc (di-ortho-fluoro-di-ortho-chloro) azobenzene scaffold with chemical alterations in the para-/ortho-positions and performed an in-depth study into the effects of their structures on their photophysical properties with an emphasis on the n -> pi* absorption band using NMR, UV-vis, and X-ray analysis. The data was used to establish and validate a computational approach that allows to compute realistic UV-vis spectra by combining TD-DFT excited-state calculations from 6000 thermally accessible structures generated through MD simulations while considering the high structural flexibility of ortho-substituted azobenzenes. We added 15 new visible light-operated photoswitches to the toolbox for the development of optical devices with relaxation rates across multiple orders of magnitude and identified several examples with stronger bathochromic shifts than the dfdc azobenzene lead structure. Our combined experimental and computational study forms the foundation for the advanced in silico design and synthesis of new highly red-shifted photoswitches. To showcase the potential of dfdc azobenzenes for the development of chemical tools, we synthesized dfdc-OptoBI-1 and demonstrated its biological activity as a red light-operated activator of TRPC6 channels in HEK293 cells.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | GENERALIZED GRADIENT APPROXIMATION; IN-VIVO; PHOTOSWITCHES; TRANS; PHOTOISOMERIZATION; SULFASALAZINE; EFFICIENT; DYNAMICS; Chemical probe development; In silico design; Photophysical properties; Red-shifted azobenzenes |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institute of Pharmacy |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 26 May 2026 12:02 |
| Last Modified: | 26 May 2026 12:02 |
| URI: | https://pred.uni-regensburg.de/id/eprint/67423 |
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