title: Enantiodifferentiating Z-E photoisomerization of cyclooctene sensitized by DNA and RNA.
abstract: DNA and RNA have been shown for the first time to function as chiral photosensitizers in aqueous solution, to effect the enantiodifferentiating photoisomerization of (Z)-cyclooctene (1Z), giving the chiral (E)-isomer in enantiomeric excesses (ee's) of up to 15%. In order to elucidate the effect of nucleotide sequence, enantiodifferentiating photoisomerization of 1Z was also performed using oligo and homopolynucleotides as chiral sensitizer. The -18.8% ee was observed by using d(T)15.d(A)15 as sensitizer, whereas sensitization by the poly(U).poly(A) duplex gave only racemic (E)-cyclooctene. From these results, oligothymidine sequence is essential for efficient enantioselective photoisomerization of 1Z.
authors.affiliation: Department of Molecular Chemistry, Faculty of Engineering, Osaka University, 2-1, Yamada-oka, Suita 565-0871, Japan.
authors.forename: N
authors.initials: N
authors.lastname: Sugahara
authors.forename: M
authors.initials: M
authors.lastname: Kawano
authors.forename: T
authors.initials: T
authors.lastname: Wada
authors.forename: Y
authors.initials: Y
authors.lastname: Inoue
mesh_terms: D000818:Animals; D002417:Cattle; D034242:Cyclooctanes / Q000737:chemistry* / Q000528:radiation effects*; D004247:DNA / Q000737:chemistry / Q000494:pharmacology*; D066298:In Vitro Techniques; D008297:Male; D008958:Models, Molecular; D009690:Nucleic Acid Conformation; D009838:Oligodeoxyribonucleotides / Q000494:pharmacology; D009841:Oligonucleotides / Q000494:pharmacology; D010777:Photochemistry; D017319:Photosensitizing Agents / Q000737:chemistry / Q000494:pharmacology*; D011063:Poly A-U / Q000494:pharmacology; D011119:Polynucleotides / Q000494:pharmacology; D012313:RNA / Q000737:chemistry / Q000494:pharmacology*; D012996:Solutions; D013237:Stereoisomerism; D014867:Water
chemical_list: D034242:Cyclooctanes; D009838:Oligodeoxyribonucleotides; D009841:Oligonucleotides; D017319:Photosensitizing Agents; D011119:Polynucleotides; D012996:Solutions; D014867:Water; D011063:Poly A-U; C061415:oligo(dT)-oligo(dA); D012313:RNA; D004247:DNA