Triggering DNAzymes with light: a photoactive C8 thioether-linked adenosine.
Herein we report evidence for a light-inducible DNAzyme. In so doing, we also disclose the synthesis and photochemical properties of a novel nucleoside: 8-(2-(4-imidazolyl)ethyl-1-thio)-2'-deoxyriboadenosine (d1). The light sensitivity of (d1) was evaluated via an examination of the photoinduced reactivation of DNAzyme 8-17E from an inactive form that contained a single nucleotide (d1) modification. Restoration of DNAzyme activity results from a photoinduced reversion of (d1) to unmodified deoxyadenosine. Deuterium studies indicate that water is the source of hydrogen in the C8-H product and not the alkylthio group, suggesting that reversion of (1) to adenosine is not a consequence of simple homolysis of the C8-S bond but of an unprecedented photochemical conversion. This adenosine, which affords significant control of catalytic reactivation of a DNAzyme, may find general use in photodecaging other biological systems.
Ting
Richard
R
Department of Chemistry, The University of British Columbia, Vancouver, BC, V6T-1Z1, Canada.
Lermer
Leonard
L
Perrin
David M
DM
D000241:Adenosine / Q000737:chemistry*; D001483:Base Sequence; D021881:DNA, Catalytic / Q000737:chemistry* / Q000378:metabolism; D008027:Light; D009690:Nucleic Acid Conformation; D010777:Photochemistry; D012313:RNA / Q000737:chemistry / Q000378:metabolism; D013056:Spectrophotometry, Ultraviolet; D013440:Sulfides / Q000737:chemistry* / Q000378:metabolism
D021881:DNA, Catalytic; D013440:Sulfides; D012313:RNA; D000241:Adenosine