Prompt site-selective DNA hydrolysis by Ce(iv)–EDTA using oligonucleotide multiphosphonate conjugates
作者:Tuomas Lönnberg、Yuta Suzuki、Makoto Komiyama
DOI:10.1039/b807789d
日期:——
conjugates, efficient site-selective hydrolysis of the substrate DNA can be achieved at Ce(IV) concentrations where other single-stranded regions remain intact. At high Ce(IV) concentrations, the cleavage rate becomes independent on [Ce(IV)] and little improvement by the new multiphosphonate conjugates over oligonucleotides with monophosphate termini is observed, suggesting that the origin of the rate acceleration
通过用次氮基三(亚甲基膦酸)(NTP)和乙二胺四(亚甲基膦酸)(EDTP)的2-(4-甲酰基苯氧基)乙基酯对氨基氧基官能化的寡核苷酸进行支持肟化制备了寡脱氧核糖核苷酸多膦酸酯偶联物。这些缀合物以及带有羟基或单磷酸末端的相应寡核苷酸与更长的底物DNA杂交,在两个加成寡核苷酸之间的底物中留有狭窄的单链缺口位点。Ce(IV)-EDTA络合物水解两个多膦酸酯基团侧翼的间隙位点,其水解速度明显快于仅羟基或单磷酸酯末端侧翼的相应间隙位点。使用新的寡核苷酸偶联物,在其他单链区域保持完整的Ce(IV)浓度下,可以实现底物DNA的有效位点选择性水解。在高Ce(IV)浓度下,裂解速率变得与[Ce(IV)]无关,并且观察到新的多膦酸酯偶联物相对于具有单磷酸末端的寡核苷酸几乎没有改善,这表明速率加速的起源是Ce(IV)的较高亲和力。与羟基或单磷酸盐配体相比,Ce(IV)的NTP或EDTP配体。