Self-assembled monolayers of sulfur-terminated oligonucleotide duplexes were formed on flat gold surfaces, either by exposure of a self-assembled monolayer bearing one oligonucleotide strand to the complementary strand or by preformation of a oligonucleotide duplex that was then deposited on a fresh gold surface. Virtually identical spectral behavior was observed whether the duplex was produced before deposition or by in situ complementary association. With a duplex bearing an appropriate pyrene end-label, the resulting thin film was photoresponsive. Surface emission measurements show no evidence for pyrene aggregation on the modified surfaces. The polarity of the photocurrent, reflecting photoinduced electron transfer initiated by photoexcitation of pyrene, is opposite that expected from the oligonucleotide-mediated reduction of the appended pyrene excited state.Key words: oligonucleotide, self-assembled monolayer, duplex formation, photoelectrochemistry, surface emission.
Synthesis of 2′-O-monohaloethoxymethyl-modified RNAs and their duplex formation ability
