Dioubankova Natalia N, Malakhov Andrei D, Stetsenko Dmitry A, Gait Michael J, Volynsky Pavel E, Efremov Roman G, Korshun Vladimir A
Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences, Miklukho-Maklaya 16/10, 117997 Moscow, Russia.
Chembiochem. 2003 Sep 5;4(9):841-7. doi: 10.1002/cbic.200300678.
The synthesis of new nucleoside derivatives, ara-uridine-2'-carbamates, and their incorporation into synthetic DNA oligomers is described. The modification directs ligands into the major groove of duplex DNA and somewhat destabilizes the duplexes of modified oligonucleotides with complementary DNA or RNA. In the case of pyrenemethyl carbamate modification in DNA-DNA duplexes, the destabilization is considerably reduced. The pyrenemethyl derivative also shows remarkable spectral properties: a "reversed" absorbance change for pyrene at 350 nm in the course of denaturation of the DNA duplex, as compared to the change seen in the nucleotide absorbance at 260 nm. This derivatization also causes pronounced sequence-dependent excimer formation in the major groove.
描述了新的核苷衍生物——阿糖腺苷-2'-氨基甲酸酯的合成及其掺入合成DNA寡聚物的过程。这种修饰将配体导向双链DNA的大沟，并在一定程度上使修饰的寡核苷酸与互补DNA或RNA形成的双链不稳定。在DNA-DNA双链中进行芘甲基氨基甲酸酯修饰的情况下，这种不稳定作用会显著降低。芘甲基衍生物还表现出显著的光谱特性：与DNA双链变性过程中260nm处核苷酸吸光度的变化相比，350nm处芘的吸光度变化呈现“反向”。这种衍生化还会在大沟中导致明显的序列依赖性准分子形成。
