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Photochemical formation of quinone methides from peptides containing modified tyrosine

Husak, Antonija; Noichl, Benjamin; Šumanovac Ramljak, Tatjana; Sohora, Margareta; Škalamera, Đani; Budiša, Nedeljko; Basarić, Nikola (2016) Photochemical formation of quinone methides from peptides containing modified tyrosine. Organic and Biomolecular Chemistry, 14 (46). pp. 10894-10905. ISSN 1477-0520

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Abstract

We have demonstrated that quinone methide (QM) precursors can be introduced in the peptide structure and used as photoswithcable units for the peptide modifications. QM precursor 1 was prepared from protected tyrosine in a Mannich reaction, and further used as a building block in the peptide synthesis. Moreover, peptides containing tyrosine can be transformed to photoactivable QM precursor by a 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 irradiations in CH3OH where photodeamination and photomethanolysis occur. QM precursors incorporated in peptides undergo photomethanolysis with quantum efficiency ΦR = 0.1-0.2, wherein the peptide backbone does not affect their photochemical reactivity. QMs formed from dipeptides were detected by laser flash photolysis (λmax ≈ 400 nm, τ = 100 μs- 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 ability to photochemically trigger peptide modifications and interactions with other molecules can have numerous applications in organic synthesis, material science, biology and medicine.

Item Type: Article
Uncontrolled Keywords: dipeptide; tyrosine; quinone methide; photodeamination
Subjects: NATURAL SCIENCES > Chemistry > Organic Chemistry
Divisions: Division of Organic Chemistry and Biochemistry
Projects:
Project titleProject leaderProject codeProject type
Supramolecular control of photoeliminationsBasarićIP-2014-09-6312Croatian Science Fondation
JAČANJE KAPACITETA U MEDICINSKOJ KEMIJI I ISTRAŽIVANJU BIOAKTIVNIH SUSTAVAVlahovićek KahlinaHR.3.2.01-0254European Social Fund
Depositing User: Nikola Basarić
Date Deposited: 06 Apr 2017 11:59
Last Modified: 06 Apr 2017 11:59
URI: http://fulir.irb.hr/id/eprint/3444
DOI: 10.1039/c6ob02191c

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