Division of Molecular Imaging and Photonics, Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200 F, B-3001 Leuven, Belgium.
J Am Chem Soc. 2011 Nov 9;133(44):17764-71. doi: 10.1021/ja206437c. Epub 2011 Oct 18.
The formation of DNA nucleoside-assisted π-conjugated nanostructures was studied by means of scanning tunneling microscopy (STM) and force field simulations. Upon adsorption of the achiral oligo(p-phenylenevinylene) (OPV) derivative at the liquid/solid interface, racemic conglomerates with mirror related rosettes are formed. Addition of the DNA nucleosides D- and L-thymidine, which act as "chiral handles", has a major effect on the supramolecular structure and the expression of chirality of the achiral OPV molecules. The influence of these "chiral handles" on the expression of chirality is probed at two levels: monolayer symmetry and monolayer orientation with respect to the substrate. This was further explored by tuning the molar ratio of the building blocks. Molecular modeling simulations give an atomistic insight into the monolayer construction, as well as the energetics governing the assembly. Thymidine is able to direct the chirality and the pattern of OPV molecules on the surface, creating chiral lamellae of π-conjugated dimers.
通过扫描隧道显微镜（STM）和力场模拟研究了 DNA 核苷辅助的π共轭纳米结构的形成。在手性寡聚（对苯撑乙烯）（OPV）衍生物吸附在液/固界面上时，形成具有镜像相关玫瑰花结的外消旋聚集体。添加作为“手性手柄”的 DNA 核苷 D-和 L-胸腺嘧啶对非手性 OPV 分子的超分子结构和手性表达有重大影响。这些“手性手柄”在手性表达方面的影响在两个层次上进行了探测：单层对称性和单层相对于衬底的取向。通过调整构建块的摩尔比进一步探索了这一点。分子建模模拟提供了对单层结构以及组装的能量学的原子级见解。胸腺嘧啶能够在手表面上定向非手性 OPV 分子的手性和图案，形成π共轭二聚体的手性层片。
