title: Photochemical control of RNA structure by disrupting π-stacking.
abstract: Photolabile nucleotides that disrupt nucleic acid structure are useful mechanistic probes and can be used as tools for regulating biochemical processes. Previous probes can be limited by the need to incorporate multiple modified nucleotides into oligonucleotides and in kinetic studies by the rate-limiting step in the conversion to the native nucleotide. Photolysis of aryl sulfide 1 produces high yields of 5-methyluridine, and product formation is complete in less than a microsecond. Aryl sulfide 1 prevents RNA hairpin formation and complete folding of the preQ(1) class I riboswitch. Proper folding is achieved in each instance upon photolysis at 350 nm. Aryl sulfide 1 is a novel tool for modulating RNA structure, and formation of 5-methyluridine within a radical cage suggests that it will be useful in kinetic studies.
authors: Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States.
authors: Marino J E
authors: MJ
authors: Resendiz
authors: Arne
authors: A
authors: Schön
authors: Ernesto
authors: E
authors: Freire
authors: Marc M
authors: MM
authors: Greenberg
mesh_terms: D001483:Base Sequence; D002942:Circular Dichroism; D008958:Models, Molecular; D009690:Nucleic Acid Conformation / Q000528:radiation effects*; D010782:Photolysis; D012313:RNA / Q000737:chemistry*; D058928:Riboswitch / Q000528:radiation effects; D013440:Sulfides / Q000737:chemistry*; D014529:Uridine / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: D058928:Riboswitch; D013440:Sulfides; C009182:ribothymidine; D012313:RNA; D014529:Uridine