Abstract

An efficient polymer dimerization method is developed on a self-accelerating double strain-promoted azide–alkyne cycloaddition (DSPAAC) click reaction. In this approach, varied polymer dimers can be efficiently prepared by coupling azide terminated polymer building blocks by sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DIBOD) small linkers. The distinct advantages of this method can be summarized as follows. First, the azide terminated polymer building blocks can be easily prepared with varied molecular topologies such as linear, star, and dendritic shapes. Second, the self-accelerating property of DSPAAC coupling reaction allows the method to efficiently prepare pure polymer dimers in the presence of excess molar amounts of DIBOD small linkers to azide-terminated polymer building blocks. Third, the click property of DSPAAC coupling reaction facilitates the dimerization reaction with a very mild ambient reaction condition. As a result, this method provides a powerful tool to fabricate topological polymers with a symmetrical molecular structure such as block, star, and dendritic polymers.

Highlights

  • In nature, the dimerization of biomolecules is a phenomenon worthy of researching, such as the ultraviolet induced thymine dimerization in DNA,[1] the dimerization of transmembrane receptors in cellular communication,[2] and the dimerization of HIV-1 protease.[3]

  • Tillman's group achieved the dimerization of poly(methyl methacrylate) (PMMA) chains using radical trap-assisted atom transfer radical coupling reaction, which altered the mechanistic pathway of the traditional radical–radical termination of PMMA.[4]

  • A convenient and efficient method was developed to prepare topological polymers with a symmetric molecular structure by dimerizing azide terminated polymers based on the selfaccelerating double strain-promoted azide–alkyne cycloaddition (DSPAAC) click reaction

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Summary

Introduction

The dimerization of biomolecules is a phenomenon worthy of researching, such as the ultraviolet induced thymine dimerization in DNA,[1] the dimerization of transmembrane receptors in cellular communication,[2] and the dimerization of HIV-1 protease.[3]. The self-accelerating property of DSPAAC coupling reaction allows the method to efficiently prepare pure polymer dimers in the presence of excess molar amounts of DIBOD small linkers to azide-terminated polymer building blocks.

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