用均三甲苯甲酰氯研究单核苷酸和寡核苷酸中磷酸基团的活化
Investigation of activation of phosphate groups in mono- and oligonucleotides with mesitoyl chloride.
作者信息
Drutsa V L, Zarytova V F, Knorre D G, Lebedev A V, Sokolova N I, Shabarova Z A
出版信息
Nucleic Acids Res. 1978 Jan;5(1):185-93. doi: 10.1093/nar/5.1.185.
It has been demonstrated with the use of 31P NMR pulsed spectroscopy that the reaction of mesitoyl chloride (MsCOCl) both with terminal and internucleotide phosphate groups pA, d(MeOTr)TpT and dpTpT (Ac) proceeds in a quantitative fashion within less than 2 min at 0 degrees C with the respective mixed anhydrides being thereby formed. The anhydrides of phosphomonoesters are resistant, unlike those of phosphodiesters which may be readily split by water, alcohol or amine without the internucleotide bonds being broken. Treatment of poly(U) with an excess of MsCOCl leads to rapid cyclization followed by formation of phosphotriesters. A comparatively easy hydrolysis leads to partial cleavage and isomerization of internucleotide bonds. A similar treatment of UpC showed that about 20% of the internucleotide bonds are cleaved, the remaining UpC being a mixture of approximately equal amounts of 3'-5'- and 2'-5'-isomers.
利用³¹P NMR脉冲光谱法已证明，在0℃下，均三甲酰氯（MsCOCl）与末端磷酸基团以及核苷酸间磷酸基团pA、d（MeOTr）TpT和dpTpT（Ac）的反应在不到2分钟内以定量方式进行，从而形成相应的混合酸酐。与磷酸二酯的酸酐不同，磷酸单酯的酸酐具有抗性，磷酸二酯的酸酐可被水、醇或胺轻易裂解，而核苷酸间的键不会断裂。用过量的MsCOCl处理聚（U）会导致快速环化，随后形成磷酸三酯。相对容易的水解会导致核苷酸间键的部分裂解和异构化。对UpC进行类似处理表明，约20%的核苷酸间键被裂解，剩余的UpC是大约等量的3'-5'-和2'-5'-异构体的混合物。
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