Jump to main content
Jump to site search

Issue 15, 2015
Previous Article Next Article

Efficiency of [2 + 2] photodimerization of various stilbene derivatives within the DNA duplex scaffold

Author affiliations

Abstract

A DNA duplex was used as a scaffold to evaluate the intrinsic reactivity of [2 + 2] photodimerization between stilbene derivatives; the duplex pre-organizes the substrates avoiding the need for an association step. Unmodified stilbenes were first introduced at base-pairing positions on complementary DNA strands. The duplex was then irradiated with 340 nm UV light. HPLC analyses revealed that [2 + 2] photodimerization proceeded rapidly without side reactions. Thus, it was confirmed that the DNA duplex could be used as an ideal scaffold for [2 + 2] photodimerization of stilbenes. Next, we examined homo-photodimerization abilities of various stilbene derivatives. Homo-photodimerization of p-cyanostilbene, p-methylstilbazolium, and p-stilbazole occurred efficiently, whereas homo-photodimerization of p-dimethylaminostilbene and p-nitrostilbene did not proceed at all, probably because the reaction was quenched by dimethylamino and nitro groups. Time-dependent density functional theory calculations revealed that excitation energy was correlated with quantum yield. We further investigated hetero-photodimerization. These reactions were made possible by the use of two complementary oligodeoxyribonucleotides tethering different stilbene derivatives. Reactivities in hetero-photodimerization were highly dependent on the combination of derivatives. A high correlation was observed between the quantum yields and energy gaps of HOMO and LUMO between reactive derivatives. Unexpectedly, nitrostilbene, which was non-reactive in homo-photodimerization, cross-reacted with p-methylstilbazolium and p-stilbazole, both of which had close HOMO or LUMO with nitrostilbene. Evaluation of the intrinsic reactivity of homo- and hetero-photodimerization of stilbene derivatives was made possible by the use of DNA as a scaffold.

Graphical abstract: Efficiency of [2 + 2] photodimerization of various stilbene derivatives within the DNA duplex scaffold

Back to tab navigation

Supplementary files

Publication details

The article was received on 01 Dec 2014, accepted on 05 Feb 2015 and first published on 05 Feb 2015


Article type: Paper
DOI: 10.1039/C4OB02520B
Author version available: Download Author version (PDF)
Citation: Org. Biomol. Chem., 2015,13, 4430-4437
  •   Request permissions

    Efficiency of [2 + 2] photodimerization of various stilbene derivatives within the DNA duplex scaffold

    T. Doi, H. Kashida and H. Asanuma, Org. Biomol. Chem., 2015, 13, 4430
    DOI: 10.1039/C4OB02520B

Search articles by author

Spotlight

Advertisements