Light-activated oligonucleotide hairpins for regulating RNase H activity

BIOL 127

XinJing Tang, xinjingt@sas.upenn.edu, Julia L. Richards, and Ivan J. Dmochowski, ivandmo@sas.upenn.edu. Department of Chemistry, University of Pennsylvania, 231 South 34th St., Philadelphia, PA 19104-6323
Regulating gene expression with light-activated compounds has become increasingly important for elucidating gene function and developing oligonucleotide therapeutics. Hybridization of an antisense oligodeoxynucleotide (asODN) to a target mRNA can inhibit translation by sterically blocking the ribosome and/or recruiting endogenous ribonucleases. We set out to photomodulate asDNA/mRNA hybridization using a single photoactive moiety, in order to control gene expression most efficiently. With this goal, we designed and synthesized a series of light-activated DNA hairpins by covalently attaching a 20-mer asODN to a complementary sense strand through a heterobifunctional photocleavable linker, 1-(5-(N-maleimidomethyl)-2-nitrophenyl)ethanol N-hydroxysuccinimide ester. By varying the size of the hairpin loop, and the number of complementary base pairs and mismatches, the photoactive conjugates were stabilized by ~ 1-4 kcal/mole compared to the corresponding asODN/sODN duplexes. These differences in stability made it possible to regulate asODN/RNA duplex formation. In vitro RNase H assays showed 3-10-fold increases in RNA degradation upon photoactivation of the asODN/sODN hairpin. Experiments to photoregulate gene expression inside living cells will be described.