Photoactive Yellow Protein Chromophore Photoisomerizes around a Single Bond if the Double Bond Is Locked
Mustalahti, S., Morozov, D., Luk, H. L., Pallerla, R. R., Myllyperkiö, P., Pettersson, M., Pihko, P. M., & Groenhof, G. (2020). Photoactive Yellow Protein Chromophore Photoisomerizes around a Single Bond if the Double Bond Is Locked. Journal of Physical Chemistry Letters, 11(6), 2177-2181. https://doi.org/10.1021/acs.jpclett.0c00060
Published inJournal of Physical Chemistry Letters
© 2020 American Chemical Society
Photoactivation in the Photoactive Yellow Protein, a bacterial blue light photoreceptor, proceeds via photo-isomerization of the double C=C bond in the covalently attached chromophore. Quantum chemistry calculations, however, have suggested that in addition to double bond photo-isomerization, the isolated chromophore and many of its analogues, can isomerize around a single C-C bond as well. Whereas double bond photo-isomerization has been observed with x-ray crystallography, experimental evidence for single bond photo-isomerization is currently lacking. Therefore, we have synthesized a chromophore analogue, in which the formal double bond is covalently locked in a cyclopentenone ring and carried out transient absorption spectroscopy experiments in combination with non-adiabatic molecular dynamics simulations to reveal that the locked chromophore isomerizes around the single bond upon photo-activation. Our work thus provides experimental evidence for single bond photo-isomerization in a photoactive yellow protein chromophore analogue and suggests that photo-isomerization is not restricted to the double bonds in conjugated systems. This insight may be useful for designing light-driven molecular switches or motors. ...
PublisherAmerican Chemical Society
Publication in research information system
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Related funder(s)European Commission; Academy of Finland
Funding program(s)Others, AoF; Academy Project, AoF
The content of the publication reflects only the author’s view. The funder is not responsible for any use that may be made of the information it contains.
Additional information about fundingThis work has been done as part of the BioExcel CoE (www.bioexcel.eu), a project funded by the European Union contracts H2020-INFRAEDI-02-2018-823830, H2020-EINFRA-2015-1-675728. In addition, we received funding from the Academy of Finland (Grants 297874, 290677 and 304455).
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