Yin Guang-Qiang, Kandapal Sneha, Liu Chung-Hao, Wang Heng, Huang Jianxiang, Jiang Shu-Ting, Ji Tan, Yan Yu, Khalife Sandra, Zhou Ruhong, Ye Libin, Xu Bingqian, Yang Hai-Bo, Nieh Mu-Ping, Li Xiaopeng
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong, 518055, China.
Single Molecule Study Laboratory, College of Engineering and Nanoscale Science and Engineering Center, University of Georgia, Athens, GA, 30602, USA.
Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1281-1289. doi: 10.1002/anie.202010696. Epub 2020 Nov 18.
In this study, we established a feasible strategy to construct a new type of metallo-polymer with helicoidal structure through the combination of covalent polymerization and intramolecular coordination-driven self-assembly. In the design, a tetratopic monomer (M) was prepared with two terminal alkynes in the outer rim for polymerization, and two terpyridines (TPYs) in the inner rim for subsequent folding by selective intramolecular coordination. Then, the linear covalent polymer (P) was synthesized by polymerization of M via Glaser-Hay homocoupling reaction. Finally, intramolecular coordination interactions between TPYs and Zn(II) folded the backbone of P into a right- or left-handed metallo-helicoid (H) with double rims. Owing to multiple positive charges on the inner rim of helicoid, double-stranded DNA molecules (dsDNA) could interact with H through electrostatic interactions. Remarkably, dsDNA allowed exclusive formation of H with right handedness by means of chiral induction.
在本研究中，我们通过共价聚合和分子内配位驱动的自组装相结合，建立了一种可行的策略来构建具有螺旋结构的新型金属聚合物。在设计中，制备了一种四齿单体（M），其在外缘带有两个末端炔烃用于聚合，在内缘带有两个三联吡啶（TPY）用于通过选择性分子内配位进行后续折叠。然后，通过M经由格拉泽-海伊均偶联反应聚合合成线性共价聚合物（P）。最后，TPY与Zn(II)之间的分子内配位相互作用将P的主链折叠成具有双环的右手或左手金属螺旋体（H）。由于螺旋体内缘带有多个正电荷，双链DNA分子（dsDNA）可通过静电相互作用与H相互作用。值得注意的是，dsDNA通过手性诱导允许排他性地形成右手性的H。
