Photochemical formation of quinone methides from peptides containing modified tyrosine

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dc.contributor.authorHusak, Antonija
dc.contributor.authorNoichl, Benjamin P.
dc.contributor.authorRamljak, Tatjana Šumanovac
dc.contributor.authorSohora, Margareta
dc.contributor.authorŠkalamera, Đani
dc.contributor.authorBudiša, Nediljko
dc.contributor.authorBasarić, Nikola
dc.date.accessioned2017-10-24T06:17:28Z
dc.date.available2017-10-24T06:17:28Z
dc.date.issued2016
dc.description.abstractWe have demonstrated that quinone methide (QM) precursors can be introduced in the peptide structure and used as photoswitchable units for peptide modifications. QM precursor 1 was prepared from protected tyrosine in the Mannich reaction, and further used as a building block in peptide synthesis. Moreover, peptides containing tyrosine can be transformed into a photoactivable QM precursor by the Mannich reaction which can afford monosubstituted derivatives 2 or bis-substituted derivatives 3. Photochemical reactivity of modified tyrosine 1 and dipeptides 2 and 3 was studied by preparative irradiation in CH3OH where photodeamination and photomethanolysis occur. QM precursors incorporated in peptides undergo photomethanolysis with quantum efficiency phi(R) = 0.1-0.2, wherein the peptide backbone does not affect their photochemical reactivity. QMs formed from dipeptides were detected by laser flash photolysis (lambda(max) approximate to 400 nm, iota = 100 mu s- 20 ms) and their reactivity with nucleophiles was studied. Consequently, QM precursors derived from tyrosine can be a part of the peptide backbone which can be transformed into QMs upon electronic excitation, leading to the reactions of peptides with different reagents. This proof of principle showing the ability to photochemically trigger peptide modifications and interactions with other molecules can have numerous applications in organic synthesis, materials science, biology and medicine.en
dc.identifier.eissn1477-0539
dc.identifier.issn1477-0520
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/6887
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-6226
dc.language.isoen
dc.rights.urihttps://creativecommons.org/licenses/by-nc/3.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titlePhotochemical formation of quinone methides from peptides containing modified tyrosineen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c6ob02191c
dcterms.bibliographicCitation.issue46
dcterms.bibliographicCitation.journaltitleOrganic & biomolecular chemistry : OBCen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend10905
dcterms.bibliographicCitation.pagestart10894
dcterms.bibliographicCitation.volume14
tub.accessrights.dnbfree
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Biokatalysede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Biokatalysede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin

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