Nearly monodisperse unimolecular micelles via chloro-based atom transfer radical polymerization
Zepeng Li,
Kannan Senthil,
Yawei Sun,
Yi Wang,
Haohui Huo,
Yanyun Hao,
Yutong Liu,
Hongfei Chen,
Hui Li,
Zhiyue Zhang,
Goran Ungar,
Qilu Zhang,
Feng Liu
Affiliations
Zepeng Li
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi'an Jiaotong University, Xi'an 710049, PR China
Kannan Senthil
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi'an Jiaotong University, Xi'an 710049, PR China
Yawei Sun
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi'an Jiaotong University, Xi'an 710049, PR China
Yi Wang
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi'an Jiaotong University, Xi'an 710049, PR China
Haohui Huo
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi'an Jiaotong University, Xi'an 710049, PR China
Yanyun Hao
Department of Pharmaceutics, Key Laboratory of Chemical Biology (Ministry of Education), School of Pharmaceutical Sciences, Shandong University, Jinan 250012, PR China
Yutong Liu
Department of Pharmaceutics, Key Laboratory of Chemical Biology (Ministry of Education), School of Pharmaceutical Sciences, Shandong University, Jinan 250012, PR China
Hongfei Chen
Department of Pharmaceutics, Key Laboratory of Chemical Biology (Ministry of Education), School of Pharmaceutical Sciences, Shandong University, Jinan 250012, PR China
Hui Li
Department of Pharmaceutics, Key Laboratory of Chemical Biology (Ministry of Education), School of Pharmaceutical Sciences, Shandong University, Jinan 250012, PR China
Zhiyue Zhang
Department of Pharmaceutics, Key Laboratory of Chemical Biology (Ministry of Education), School of Pharmaceutical Sciences, Shandong University, Jinan 250012, PR China
Goran Ungar
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi'an Jiaotong University, Xi'an 710049, PR China
Qilu Zhang
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi'an Jiaotong University, Xi'an 710049, PR China; Corresponding author.
Feng Liu
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi'an Jiaotong University, Xi'an 710049, PR China; Corresponding author.
Fabrication of unimolecular micelles with uniform sizes and well-controlled structure is currently a big challenge. Herein, we report an easy-to-handle protocol for the preparation of nearly monodisperse unimolecular micelles via atom transfer radical polymerization (ATRP) mediated by chloroacetylated initiator and chloride catalyst (Cl-ATRP). In contrast to Br-ATRP employing bromoacetylated initiator and CuBr as catalyst, Cl-ATRP can significantly suppress chain coupling during the synthesis of unimolecular micelles and result in well-defined polymers with low molar mass dispersity (Ð < 1.10) even at high monomer conversions (e.g. ~80%) and extended reaction times. In addition, effort was made to inhibit the formation of linear polymer side products (typical for ATRP of unimolecular micelles). With the optimized protocol, no linear polymer could be detected by size exclusion chromatography (SEC). The obtained nearly monodisperse unimolecular micelles may find application in, e.g. cargo delivery and bio-imaging as also demonstrated in this report. Considering its superior control in ATRP, the easily utilized Cl-ATRP protocol could be extended to the ATRP of, e.g. brush polymers and comb-like polymers where high local radical concentration needs to be avoided.
