title: Absorption spectra of photoactive yellow protein chromophores in vacuum.
abstract: The absorption spectra of two photoactive yellow protein model chromophores have been measured in vacuum using an electrostatic ion storage ring. The absorption spectrum of the isolated chromophore is an important reference for deducing the influence of the protein environment on the electronic energy levels of the chromophore and separating the intrinsic properties of the chromophore from properties induced by the protein environment. In vacuum the deprotonated trans-thiophenyl-p-coumarate model chromophore has an absorption maximum at 460 nm, whereas the photoactive yellow protein absorbs maximally at 446 nm. The protein environment thus only slightly blue-shifts the absorption. In contrast, the absorption of the model chromophore in aqueous solution is significantly blue-shifted (lambda(max) = 395 nm). A deprotonated trans-p-coumaric acid has also been studied to elucidate the effect of thioester formation and phenol deprotonation. The sum of these two changes on the chromophore induces a red shift both in vacuum and in aqueous solution.
authors.affiliation: Department of Physics and Astronomy, University of Aarhus, Aarhus, Denmark.
authors.forename: I B
authors.initials: IB
authors.lastname: Nielsen
authors.forename: S
authors.initials: S
authors.lastname: Boyé-Péronne
authors.forename: M O A
authors.initials: MO
authors.lastname: El Ghazaly
authors.forename: M B
authors.initials: MB
authors.lastname: Kristensen
authors.forename: S
authors.initials: S
authors.lastname: Brøndsted Nielsen
authors.forename: L H
authors.initials: LH
authors.lastname: Andersen
mesh_terms: D001426:Bacterial Proteins / Q000737:chemistry* / Q000528:radiation effects*; D003198:Computer Simulation; D008027:Light; D008956:Models, Chemical; D020283:Photoreceptors, Microbial / Q000737:chemistry* / Q000528:radiation effects*; D011829:Radiation Dosage; D011874:Radiometry; D013057:Spectrum Analysis / Q000379:methods*; D014618:Vacuum
chemical_list: D001426:Bacterial Proteins; D020283:Photoreceptors, Microbial; C050162:photoactive yellow protein, Bacteria