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Controlled Self-Assembly of Discrete Amphiphilic Oligourethanes with a Cascade Self-Immolative Motif
Authors:Jie Xu  Changzhu Lv  Dr. Qiangqiang Shi  Jialin Zhang  Ning Wang  Prof. Dr. Guoying Zhang  Prof. Dr. Jinming Hu  Prof. Dr. Shiyong Liu
Affiliation:1. Department of Pharmacy, The First Affiliated Hospital of USTC, Division of Life Sciences and Medicine, Department of Polymer Science and Engineering, University of Science and Technology of China, 96 Jinzhai Road, 230026 Hefei, Anhui Province, China

These authors contributed equally to this work.;2. Department of Pharmacy, The First Affiliated Hospital of USTC, Division of Life Sciences and Medicine, Department of Polymer Science and Engineering, University of Science and Technology of China, 96 Jinzhai Road, 230026 Hefei, Anhui Province, China

Abstract:Discrete polymers offer an excellent platform for comprehending the interplay between precise chain structures, distinctive self-assembly behavior, and functional applications, whereas the development of discrete polymers with self-immolative properties remains scarce. Here, we modularly synthesize a library of discrete self-immolative oligourethanes containing N-naphthylcarbamate or N-(3-fluorophenyl)carbamate repeating units via iterative stepwise growth. These oligourethanes undergo not only cascade 1,6-elimination depolymerizations via photo-mediated removal of o-nitrobenzyl carbamate triggers but also selective cleavage of benzyl-O linkages under MS/MS conditions even without UV light irradiation. In aqueous media, these discrete oligourethanes self-assemble into different morphologies such as flat nanosheets, nanofibers, and nanoribbons, depending on the chain lengths and backbone compositions, and further morphological transitions are observed upon thermal annealing.
Keywords:Discrete Oligourethanes  Morphological Transition  Nanofibers  Self-Assembly  Self-Immolative
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