Photoreactivities of 5-Bromouracil-containing RNAs

5-Bromouracil (BrU) was incorporated into three types of synthetic RNA and the products of the photoirradiated BrU-containing RNAs were investigated using HPLC and MS analysis. The photoirradiation of r(GCABrUGC)2 and r(CGAABrUUGC)/r(GCAAUUCG) in A-form RNA produced the corresponding 2′-keto adenosine (ketoA) product at the 5′-neighboring nucleotide, such as r(GCketoAUGC) and r(CGAketoAUUGC), respectively. The photoirradiation of r(CGCGBrUGCG)/r(CmGCACmGCG) in Z-form RNA produced the 2′-keto guanosine (ketoG) product r(CGCketoGUGCG), whereas almost no products were observed from the photoirradiation of r(CGCGBrUGCG)/r(CmGCACmGCG) in A-form RNA. The present results indicate clearly that hydrogen (H) abstraction by the photochemically generated uracil-5-yl radical selectively occurs at the C2′ position to provide a 2′-keto RNA product.