Metallo-Helicoid with Double Rims: Polymerization Followed by Folding by Intramolecular Coordination

Guang-Qiang Yin; Sneha Kandapal; Chung-Hao Liu; Heng Wang; Jianxiang Huang; Shu-Ting Jiang; Tan Ji; Yu Yan; Sandra Khalife; Ruhong Zhou; Libin Ye; Bingqian Xu; Hai-Bo Yang; Mu-Ping Nieh; Xiaopeng Li

doi:10.1002/anie.202010696

Metallo-Helicoid with Double Rims: Polymerization Followed by Folding by Intramolecular Coordination

Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1281-1289. doi: 10.1002/anie.202010696. Epub 2020 Nov 18.

Authors

Guang-Qiang Yin¹, Sneha Kandapal², Chung-Hao Liu³, Heng Wang¹, Jianxiang Huang⁴, Shu-Ting Jiang⁵, Tan Ji⁵, Yu Yan⁶, Sandra Khalife⁶, Ruhong Zhou⁴, Libin Ye⁷, Bingqian Xu², Hai-Bo Yang⁵, Mu-Ping Nieh^{3

8}, Xiaopeng Li¹

Affiliations

¹ College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong, 518055, China.
² Single Molecule Study Laboratory, College of Engineering and Nanoscale Science and Engineering Center, University of Georgia, Athens, GA, 30602, USA.
³ Department of Chemical and Biomolecular Engineering, University of Connecticut, Storrs, CT, 06269, USA.
⁴ Institute of Quantitative Biology, Zhejiang University, Hangzhou, Zhejiang, 310027, China.
⁵ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai, 200062, China.
⁶ Department of Chemistry, University of South Florida, Tampa, FL, 33620, USA.
⁷ Department of Cell Biology, Microbiology and Molecular Biology, University of South Florida, Tampa, FL, 33620, USA.
⁸ Polymer Program, Institute of Material Science, University of Connecticut, Storrs, CT, 06269, USA.

PMID: 33009693
DOI: 10.1002/anie.202010696

Abstract

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.

Keywords: coordination-driven self-assembly; helicoid; metallo-polymers; terpyridine; tetraphenylethylene.

Publication types

Research Support, Non-U.S. Gov't