Water‐soluble π‐conjugated polymers are increasingly considered for DNA biosensing. However, the conformational rearrangement, supramolecular organization and dynamics upon interaction with DNA have been overlooked, which prevents the rational design of such detection tools. To elucidate the binding of a cationic polythiophene (CPT) to DNA with atomistic resolution, we performed molecular simulations of their supramolecular assembly. Comparison of replicated simulations show a multiplicity of CPT binding geometries that contribute to the wrapping of CPT around DNA. The different binding geometries are stabilized by both electrostatic interactions between CPT lateral cations and DNA phosphodiesters and van der Waals interactions between the CPT backbone and the DNA grooves. Simulated circular dichroism (CD) spectra show that the induced CD signal stems from a conserved geometrical feature across the replicated simulations, i. e. the presence of segments of syn configurations between thiophene units along the CPT chain. At the macromolecular scale, we inspected the different shapes related to the CPT binding modes around the DNA through symmetry metrics. Altogether, molecular dynamics (MD) simulations, model Hamiltonian calculations of the CD spectra, and symmetry indices provide insights into the origin of induced chirality from the atomic to the macromolecular scale. Our multidisciplinary approach points out the hierarchical aspect of CPT chiral organization induced by DNA.

中文翻译：

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DNA和π共轭聚合物的超分子组装中的结合模式多重性和多尺度手性。

越来越多地考虑将水溶性π共轭聚合物用于DNA生物传感。然而，与DNA相互作用时的构象重排，超分子组织和动力学已被忽略，这妨碍了这种检测工具的合理设计。为了阐明具有原子分辨力的阳离子聚噻吩（CPT）与DNA的结合，我们对其超分子组装进行了分子模拟。复制模拟的比较表明，CPT结合的几何形状多种多样，有助于CPT围绕DNA包裹。CPT侧向阳离子与DNA磷酸二酯之间的静电相互作用以及CPT骨架与DNA凹槽之间的范德华相互作用都可以稳定不同的结合几何形状。一世。e。 沿着CPT链的噻吩单元之间存在syn构型的片段。在大分子尺度上，我们通过对称性指标检查了与DNA周围CPT结合模式有关的不同形状。总而言之，分子动力学（MD）模拟，CD光谱的模型哈密顿量计算和对称性指数提供了从原子尺度到大分子尺度的手性诱导原因的见解。我们的多学科方法指出了由DNA诱导的CPT手性组织的层次结构。