手性钌(Ⅱ)配合物与DNA作用性质的计算研究

Computational investigation into properties of chiral Ru(Ⅱ) complexes with DNA

理论考察了手性钌(Ⅱ)配合物1和2与DNA作用性质.首先,构建了手性钌(Ⅱ)配合物1、2与DNA对接模型,并对对接模型进行了优化,通过计算得到的手性钌(Ⅱ)配合物1、2与DNA的结合能,解释了手性钌(Ⅱ)配合物1、2与DNA键合力大小次序,即K_(b)(Λ-1)<K_(b)(Δ-1)<K_(b)(Λ-2)<K_(b)(Δ-2).另外,通过计算得到的电子转移活化能及自然电荷解释了手性钌(Ⅱ)配合物1和2裂解DNA的效率次序,即K_(b)(Λ-1)φ(Δ-2)>φ(Λ-1)>φ(Δ-1).最后,通过计算得到的对接模型的分子轨道分析了光裂解DNA的原因.

The interactions of chiral Ru(Ⅱ) polypyridyl complexes 1 and 2 with DNA were explored theoretically. Firstly, the DNA-docking models of chiral complexes 1 and 2 were constructed and optimized. The sequence of DNA binding affinity of chiral Ru(Ⅱ) complexes 1 and 2, i.e. K_(b)(Λ-1) < K_(b)(Δ-1) < K_(b)(Λ-2) < K_(b)(Δ-2), was explained by the calculated DNA-binding energies. Besides, the sequence of DNA-cleavage efficiencies(?) of these complexes, i.e., K_(b)(Λ-1)φ(Δ-2)>φ(Λ-1)>φ(Δ-1). were explained by the calculated electron-transfer activation energies and nature charges. Finally, the cause of DNA photolysis was analyzed by the molecular orbitals of docking structures.