SYNTHESIS AND PROPERTIES OF MIRROR-IMAGE DNA
SYNTHESIS AND PROPERTIES OF MIRROR-IMAGE DNA
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DOI：
10.1093/nar/20.13.3325
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发表时间：
1992-07-11
影响因子：
14.9
通讯作者：
AKAGI, M
中科院分区：
文献类型：
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作者：
URATA, H;OGURA, E;AKAGI, M
本文研究了天然D-脱氧核糖的镜像分子L-脱氧核糖所组成的六脱氧核苷酸L-d（CGCGCG）的构象。本文报道了四种L-脱氧核苷的合成以及L-寡核苷酸与溴化乙锭的相互作用。以L-阿拉伯糖为原料，经巴顿-麦康比反应合成了L-脱氧核糖合成子9，总收率为28.5%。通过用1 -氯糖9将适当的核碱基衍生物糖基化获得L-脱氧核苷。衍生化后的核苷亚磷酰胺，L-脱氧胞苷和L-脱氧鸟苷被纳入六脱氧核苷酸，L-d（CGCGCG）通过固相β-氰乙基亚磷酰胺法。该六核苷酸对核酸酶P1的消化具有抗性。在低盐和高盐条件下，L-d（CGCGCG）-溴化乙锭络合物的构象与D-d（CGCGCG）-溴化乙锭络合物的构象也是相同的。这些结果表明，溴化乙锭喜欢的不是右手螺旋的意义，但基地基地堆叠的几何形状的B-形式，而不是Z-形式。因此，L-DNA将是研究DNA-药物相互作用的有用工具。
We have investigated the conformations of the hexadeoxyribonucleotide, L-d(CGCGCG) composed of L-deoxyribose, the mirror image molecule of natural D-deoxyribose. In this paper, we report the synthesis of four L-deoxynucleosides and the L-oligonucleotide-ethidium bromide interactions. The L-deoxyribose synthon 9 was synthesized from L-arabinose with an over all yield of 28.5% via the Barton - McCombie reaction. The L-deoxynucleosides were obtained by a glycosylation of appropriate nucleobase derivatives with the 1 -chloro sugar 9. After derivatization to nucleoside phosphoramidites, L-deoxycytidine and L-deoxyguanosine were incorporated into a hexadeoxynucleotide, L-d(CGCGCG) by a solid-phase beta-cyanoethylphosphoramidite method. This hexanucleotide was resistant to digestion with nuclease P1. The conformations of L-d(CGCGCG) were an exact mirror image of that of the corresponding natural one as described previously, and the conformations of the L-d(CGCGCG)-ethidium bromide complex were also the mirror images of those of the D-d(CGCGCG)-ethidium bromide complex under both low and high salt conditions. These results suggest that ethidium bromide prefers not a right-handed helical sense, but the base-base stacking geometry of the B-form rather than that of the Z-form. Thus, L-DNA would be a useful tool for studying DNA-drug interactions.