Local electric field changes during thephotoconversion of the bathy phytochrome Agp2

dc.contributor.authorKraskov, Anastasia
dc.contributor.authorJohannes von Sass, Johannes von Sass
dc.contributor.authorNguyen, Anh Duc
dc.contributor.authorHoang, Tu Oanh
dc.contributor.authorBuhrke, David
dc.contributor.authorSagie Katz, Sagie Katz
dc.contributor.authorNorbert, Michael
dc.contributor.authorKozuch, Jacek
dc.contributor.authorIngo Zebger, Ingo Zebger
dc.contributor.authorSiebert, Friedrich
dc.contributor.authorScheerer, Patrick
dc.contributor.authorMroginski, Maria Andrea
dc.contributor.authorBudisa, Nediljko
dc.contributor.authorHildebrandt, Peter
dc.date.accessioned2021-11-22T13:05:38Z
dc.date.available2021-11-22T13:05:38Z
dc.date.issued2021-09-27
dc.description.abstractPhytochromes switch between a physiologically inactive and active state via a light-induced reaction cascade, which is initiated by isomerization of the tetrapyrrole chromophore and leads to the functionally relevant secondary structure transition of a protein segment (tongue). Although details of the underlying cause–effect relationships are not known, electrostatic fields are likely to play a crucial role in coupling chromophores and protein structural changes. Here, we studied local electric field changes during the photoconversion of the dark state Pfr to the photoactivated state Pr of the bathy phytochrome Agp2. Substituting Tyr165 and Phe192 in the chromophore pocket by para-cyanophenylalanine (pCNF), we monitored the respective nitrile stretching modes in the various states of photoconversion (vibrational Stark effect). Resonance Raman and IR spectroscopic analyses revealed that both pCNF-substituted variants undergo the same photoinduced structural changes as wild-type Agp2. Based on a structural model for the Pfr state of F192pCNF, a molecular mechanical–quantum mechanical approach was employed to calculate the electric field at the nitrile group and the respective stretching frequency, in excellent agreement with the experiment. These calculations serve as a reference for determining the electric field changes in the photoinduced states of F192pCNF. Unlike F192pCNF, the nitrile group in Y165pCNF is strongly hydrogen bonded such that the theoretical approach is not applicable. However, in both variants, the largest changes of the nitrile stretching modes occur in the last step of the photoconversion, supporting the view that the proton-coupled restructuring of the tongue is accompanied by a change of the electric field.en
dc.description.sponsorshipDFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat"en
dc.description.sponsorshipDFG, 221545957, SFB 1078: Proteinfunktion durch Protonierungsdynamiken
dc.identifier.eissn1520-4995
dc.identifier.issn0006-2960
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/13940
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-12714
dc.language.isoenen
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.ddc572 Biochemiede
dc.subject.otherelectric fieldsen
dc.subject.othernitrogen compoundsen
dc.subject.othercrystal structureen
dc.subject.otherchromophoresen
dc.subject.otherinfrared lighten
dc.titleLocal electric field changes during thephotoconversion of the bathy phytochrome Agp2en
dc.typeArticleen
dc.type.versionacceptedVersionen
dcterms.bibliographicCitation.doi10.1021/acs.biochem.1c00426en
dcterms.bibliographicCitation.issue40en
dcterms.bibliographicCitation.journaltitleBiochemistryen
dcterms.bibliographicCitation.originalpublishernameAmerican Chemical Society (ACS)en
dcterms.bibliographicCitation.originalpublisherplaceColumbus, Ohioen
dcterms.bibliographicCitation.pageend2977en
dcterms.bibliographicCitation.pagestart2967en
dcterms.bibliographicCitation.volume60en
tub.accessrights.dnbdomain*
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Modellierung biomolekularer Systemede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Modellierung biomolekularer Systemede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlinen
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