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RESEARCH PRODUCT
Photoactive Yellow Protein Chromophore Photoisomerizes around a Single Bond if the Double Bond Is Locked
Petri M. PihkoRajanish R PallerlaHoi Ling LukMika PetterssonPasi MyllyperkiöSatu MustalahtiGerrit GroenhofDmitry Morozovsubject
double bond0301 basic medicinephotoactive yellow proteinLetterDouble bondPhotoisomerizationisomeriaPhotochemistryConjugated systemsingle bond010402 general chemistryRing (chemistry)Photochemistry01 natural scienceskemialliset sidokset03 medical and health sciencesSingle bondHumansGeneral Materials ScienceBisphenol A-Glycidyl MethacrylatePhysical and Theoretical Chemistrychemistry.chemical_classificationMolecular switchProteinsChromophore0104 chemical sciences030104 developmental biologychemistryphotoactivationCovalent bondvalokemiaproteiinitphoto-isomerizationdescription
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. peerReviewed
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2020-01-01 | The Journal of Physical Chemistry Letters |