7-Deazapurine and 8-Aza-7-deazapurine Nucleoside and Oligonucleotide Pyrene ``Click'' Conjugates: Synthesis, Nucleobase Controlled Fluorescence Quenching, and Duplex Stability

Autor(en): Ingale, Sachin A.
Pujari, Suresh S.
Sirivolu, Venkata Ramana
Ding, Ping
Xiong, Hai
Mei, Hui
Seela, Frank
Stichwörter: AZIDE; BASE; BRANCHED SIDE-CHAINS; CHARGE-TRANSFER; Chemistry; Chemistry, Organic; DNA OLIGOMERS; ELECTRON-TRANSFER; EXCIMER FLUORESCENCE; HYBRIDIZATION; INTERCALATING NUCLEIC-ACIDS; TERMINAL TRIPLE BONDS
Erscheinungsdatum: 2012
Herausgeber: AMER CHEMICAL SOC
Journal: JOURNAL OF ORGANIC CHEMISTRY
Volumen: 77
Ausgabe: 1
Startseite: 188
Seitenende: 199
Zusammenfassung: 
7-Deazapurine and 8-aza-7-deazapurine nucleosides related to dA and dG bearing 7-octadiynyl or 7-tripropargylamine side chains as well as corresponding oligonucleotides were synthesized. ``Click'' conjugation with 1-azidomethyl pyrene (10) resulted in fluorescent derivatives. Octadiynyl conjugates show only monomer fluorescence, while the proximal alignment of pyrene residues in the tripropargylamine derivatives causes excimer emission. 8-Aza-7-deazapurine pyrene `click'' conjugates exhibit fluorescence emission much higher than that of 7-deazapurine derivatives. They are quenched by intramolecular charge transfer between the nucleobase and the dye. Oligonucleotide single strands decorated with two ``double clicked'' pyrenes show weak or no excimer fluorescence. However, when duplexes carry proximal pyrenes in complementary strands, strong excimer fluorescence is observed. A single replacement of a canonical nucleoside by a pyrene conjugate stabilizes the duplex substantially, most likely by stacking interactions: 6-12 degrees C for duplexes with a modified ``adenine'' base and 2-6 degrees C for a modified ``guanine'' base. The favorable photophysical properties of 8-aza-7-deazapurine pyrene conjugates improve the utility of pyrene fluorescence reporters in oligonucleotide sensing as these nucleoside conjugates are not affected by nucleobase induced quenching.
ISSN: 00223263
DOI: 10.1021/jo202103q

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