Photoactive Yellow Protein Chromophore Photoisomerizes around a Single Bond if the Double Bond Is Locked
Mustalahti, Satu; Morozov, Dmitry; Luk, Hoi Ling; Pallerla, Rajanish R.; Myllyperkiö, Pasi; Pettersson, Mika; Pihko, Petri M.; Groenhof, Gerrit (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. DOI: 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
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Related funder(s)European Commission; Academy of Finland
Funding program(s)Academy Project, AoF; Others, 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.