%0 Generic %A Zhao, Ying-hu %A Ren, Fu-de %A Gao, Li %A Tan, Ying-xin %A Wang, Ying-yong %D 2019 %T Theoretical explanation for the DNA cleavage by GO with cation: anti-cooperativity effect among the π⋯π, cation⋯π/σ and H-bonding interactions in cytosine⋯GO⋯Mn+ (Mn+ = Na+, Mg2+, Al3+)* %U https://tandf.figshare.com/articles/dataset/Theoretical_explanation_for_the_DNA_cleavage_by_GO_with_cation_anti-cooperativity_effect_among_the__cation__and_H-bonding_interactions_in_cytosine_GO_M_sup_n_sup_M_sup_n_sup_Na_sup_sup_Mg_sup_2_sup_Al_sup_3_sup_sup_sup_/10746257 %R 10.6084/m9.figshare.10746257.v1 %2 https://tandf.figshare.com/ndownloader/files/19257311 %K Graphene oxide⋯Mn+ %K anti-cooperativity and solvent effect %K DNA cleavage %K π⋯π %K RDG %X

In order to reveal the nature of DNA cleavage by inorganic intercalator GO (graphene oxide) with cation, the cooperativity effects among the π⋯π, cation⋯π/σ and H-bonding interactions were evaluated in the cytosine⋯GO⋯Mn+ (Mn+ = Na+, Mg2+, Al3+) model systems using the M06-2X, MP2 and ω B97X-D methods with the 6-311++G(2d,p) and 6-311++G(3df,3pd) basis sets. The Mn+⋯O (ether) and N–H⋯O interactions induce the formation of the π⋯π stacking between cytosine and GO, and the anti-cooperativity effect are dominant in controling of the aggregation process of cytosine, GO and Mn+, which was confirmed by the AIM (atoms-in-molecules) and RDG (reduced density gradient) analyses. Furthermore, the solvent effects of H2O weaken greatly the anti-cooperativity effects. Thus, a deduction on the DNA cleavage by GO⋯cation with the intercalation mode is put forward: due to the anti-cooperativity effect and solvent effect, the π⋯π stacking is weakened in the complexes with Na+ or broken in those with Mg2+ or Al3+. Then the GO⋯Mg2+ moiety is squeezed out from the intercalating sites, leading to an invalid cleavage of DNA, while Na+ or Al3+ is bound tightly to cytosine, with a notable DNA cleavage. This deduction was used to explain reasonably the previous experimental phenomena.

%I Taylor & Francis