Reversible Photoswitching of RNA Hybridization at Room Temperature with an Azobenzene C‐Nucleoside |
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| Authors: | Thomas Goldau Keiji Murayama Dr Clara Brieke Sabrina Steinwand Dr Padmabati Mondal Dr Mithun Biswas Prof?Dr Irene Burghardt Prof?Dr Josef Wachtveitl Prof?Dr Hiroyuki Asanuma Prof?Dr Alexander Heckel |
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| Institution: | 1. Institute for Organic Chemistry and Chemical Biology, Goethe University Frankfurt am Main, Max‐von‐Laue‐Str. 9, 60438 Frankfurt/Main (Germany), Fax: (+49)?69‐798‐763‐42505;2. Graduate School of Engineering, Nagoya University, Furo‐cho, Chikusa‐ku, Nagoya 464‐8603 (Japan), Fax: (+81)?52‐789‐2528;3. Department for Biomolecular Mechanisms, Max‐Planck‐Institute for Medical Research, Jahnstrasse 29, 69120 Heidelberg (Germany);4. Institute for Physical and Theoretical Chemistry, Goethe University Frankfurt am Main, Max‐von‐Laue‐Str. 7, 60438 Frankfurt/Main (Germany), Fax: (+49)?69‐798‐763‐29709;5. Institute for Physical and Theoretical Chemistry, Goethe University Frankfurt am Main, Max‐von‐Laue‐Str.7, 60438 Frankfurt/Main (Germany), Fax: (+49)?69‐798‐29709 |
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| Abstract: | Photoregulation of RNA remains a challenging task as the introduction of a photoswitch entails changes in the shape and the stability of the duplex that strongly depend on the chosen linker strategy. Herein, the influence of a novel nucleosidic linker moiety on the photoregulation efficiency of azobenzene is investigated. To this purpose, two azobenzene C‐nucleosides were stereoselectively synthesized, characterized, and incorporated into RNA oligonucleotides. Spectroscopic characterization revealed a reversible and fast switching process, even at 20 °C, and a high thermal stability of the respective cis isomers. The photoregulation efficiency of RNA duplexes upon trans‐to‐cis isomerization was investigated by using melting point studies and compared with the known D ‐threoninol‐based azobenzene system, revealing a photoswitching amplitude of the new residues exceeding 90 % even at room temperature. Structural changes in the duplexes upon photoisomerization were investigated by using MM/MD calculations. The excellent photoswitching performance at room temperature and the high thermal stability make these new azobenzene residues promising candidates for in‐vivo and nanoarchitecture photoregulation applications of RNA. |
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| Keywords: | azobenzenes nucleic acids photoisomerization photoswitches RNA |
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