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Expanding Cyclic Topology‐Based Biomedical Polymer Panel: Universal Synthesis of Hetero‐“8”‐Shaped Copolymers and Topological Modulation of Polymer Degradation
Author(s) -
Kang GuiYing,
Ma Wei,
Liu MingZhu,
Luo HaiXi,
Yu CuiYun,
Wei Hua
Publication year - 2021
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.202100298
Subject(s) - methacrylate , copolymer , ethylene glycol , polymer , moiety , topology (electrical circuits) , materials science , micelle , monomer , polymer chemistry , click chemistry , hydroxybenzoate , chemistry , stereochemistry , organic chemistry , composite material , aqueous solution , mathematics , combinatorics
Abstract 8‐Shaped copolymers with two macrocycles connected together represent an interesting cyclic topology‐derived polymer species due to the simultaneous incorporation of two cyclic moieties and the reported unique physical and chemical properties. To provide a proof‐of‐concept for a broad readership on biomedical polymers, a well‐defined hetero‐8‐shaped amphiphilic copolymer, cyclic‐poly(oligo(ethylene glycol)monomethyl ether methacrylate)‐ b ‐cyclic PCL ( c POEGMA‐ b ‐ c PCL) is synthesized by an elegant integration of intrachain click cyclization and interchain click coupling. The potential of the self‐assembled micelles of c POEGMA‐ b ‐ c PCL for controlled drug release is evaluated by in vitro drug loading and drug release, cellular uptake, cytotoxicity, and degradation studies. Most importantly, the micelles based on c POEGMA‐ b ‐ c PCL show much slower degradation profiles than the previously reported linear counterpart, POEGMA‐ b ‐PCL and tadpole‐shaped analog, PEG‐ b ‐ c PCL because of the presence of cyclic hydrophilic POEGMA segment. Therefore, this study not only develops a robust strategy for a universal precise synthesis of well‐defined hetero‐8‐shaped copolymers based on diverse vinyl and ring‐structured monomers, but also reveals the first modulation of polymer degradation property by topological control of the nondegradable moiety in the polymer construct through advanced macromolecular engineering.