Shao et al. 10.1073/pnas.0408128101.
Fig. 5. Photooxidation of N4-cyclopropylcytidine (rCPC) by Rh(phi)2(bpy′)3+ (Rh). Thirty-microliter aliquots of 250 m M rCPC, 25 m M Rh in 50 mM NaCl, and 10 mM sodium phosphate (pH 7.0) were irradiated at 365 nm for 40 min. Shown are the HPLC traces before (blue) and after (red) irradiation; rCPC decomposed to produce two major products, rC and rHPC. The products were confirmed by MS: M.W. (rC) = 243; M.W. (rHPC) = 315. Similar results were obtained with anthraquinone (AQ).
Fig. 6. DNA-mediated photooxidation of N4-cyclopropylcytosine (CPC) by Rh is an intraduplex reaction. Duplexes containing Rh without CPC (Rh-I-1/C-1) and containing CPC without Rh (I-1/Cp-1) were mixed after annealing separately (30-m l aliquots of 5 m M each duplex in 50 mM NaCl and 10 mM sodium phosphate, pH 7.0). Shown are the HPLC traces of the enzymatically digested duplexes before (a) and after (b) 40 min of irradiation at 365 nm. No decomposition of CPC is detected when Rh and CPC are not within the same duplex. The analogous interduplex control was also conducted by using AQ-tethered assemblies where, again, no interduplex reaction was detected.