Sorokin V A, Usenko E L, Valeev V A, Berezniak Ekaterina G, Andrushchenko V V
†B. I. Verkin Institute for Low Temperature Physics and Engineering, National Academy of Sciences of Ukraine, 47 Lenin Avenue, Kharkov, 61103, Ukraine.
‡O. Ya. Usikov Institute for Radiophysics and Electronics, National Academy of Sciences of Ukraine, 12 Proskura Street, Kharkov, 61085, Ukraine.
J Phys Chem B. 2015 Mar 26;119(12):4409-16. doi: 10.1021/acs.jpcb.5b00558. Epub 2015 Mar 12.
Effect of Zn(2+) ions on the conformation of single-stranded polynucleotides polyU and polyC in a wide temperature range at pH 7 was studied by differential UV spectroscopy and by thermal denaturation. The atoms coordinating Zn(2+) ions were determined (O4 and N3 in polyU and N3 in polyC). A three-dimensional phase diagram and its two-dimensional components were constructed for a polyC-Zn(2+) system. The phase diagram revealed a region in which ordered single-stranded structures, stabilized by Zn(2+)-mediated cross-links involving N3 atom of cytosine, are formed. The phase diagram also demonstrated that the behavior of the polyC-Zn(2+) system is similar to the effect of retrograde condensation observed in some binary solutions of simple liquids. A dependence of Zn(2+)-polyC binding constant on the metal ion concentration was obtained. The reason why zinc-induced transition of the sequences with adenine-uracil (AU) base pairs from A-form geometry to a metallized m-form requires higher pH compared to the sequences comprised of guanine-cytosine (GC) base pairs is explained. This information can be useful for the development of possible technological applications based on m-DNA.
通过差示紫外光谱法和热变性研究了锌离子(Zn(2+))在pH 7的宽温度范围内对单链多核苷酸聚尿苷酸(polyU)和聚胞苷酸(polyC)构象的影响。确定了与锌离子配位的原子(polyU中的O4和N3以及polyC中的N3)。构建了聚胞苷酸-锌离子(polyC-Zn(2+))体系的三维相图及其二维分量。相图显示出一个区域,在该区域中形成了由涉及胞嘧啶N3原子的锌介导交联稳定的有序单链结构。相图还表明,polyC-Zn(2+)体系的行为类似于在一些简单液体的二元溶液中观察到的逆行凝聚效应。获得了锌离子与聚胞苷酸(Zn(2+)-polyC)结合常数对金属离子浓度的依赖性。解释了为什么与由鸟嘌呤-胞嘧啶(GC)碱基对组成的序列相比,锌诱导的含有腺嘌呤-尿嘧啶(AU)碱基对的序列从A形几何结构转变为金属化的m形需要更高的pH值。这些信息对于基于m-DNA的可能技术应用的开发可能是有用的。