Photochemical formation of quinone methides from peptides containing modified tyrosine
| Autor: | Nikola Basarić, Benjamin P. Noichl, Margareta Sohora, Nediljko Budisa, Đani Škalamera, Tatjana Šumanovac Ramljak, Antonija Husak |
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| Rok vydání: | 2016 |
| Předmět: |
Stereochemistry
peptide tyrosine quinone methide photodeamination Peptide 010402 general chemistry 01 natural sciences Biochemistry chemistry.chemical_compound Nucleophile Peptide synthesis Reactivity (chemistry) Physical and Theoretical Chemistry Indolequinones Mannich reaction chemistry.chemical_classification Photolysis 010405 organic chemistry Lasers Organic Chemistry food and beverages Quinone methide 0104 chemical sciences Quinone chemistry ddc:540 Tyrosine Organic synthesis Peptides |
| Zdroj: | Organic and Biomolecular Chemistry |
| ISSN: | 1477-0539 |
| Popis: | We 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. |
| Databáze: | OpenAIRE |
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