Compartmentalization of Single Polymer Chains by Stepwise Intramolecular Cross-Linking of Sequence-Controlled Macromolecules

被引:80
作者
Roy, Raj Kumar [1 ]
Lutz, Jean-Francois [1 ]
机构
[1] Inst Charles Sadron, Precis Macromol Chem Grp, CNRS, UPR 22, F-67034 Strasbourg 2, France
基金
欧洲研究理事会;
关键词
SYNTHETIC-POLYMERS; BLOCK-COPOLYMERS; CLICK CHEMISTRY; NANOPARTICLES; COVALENT; COLLAPSE;
D O I
10.1021/ja507889x
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report the intramolecular double compaction of sequence-controlled linear macromolecules into "structured" random coils. These compartmentalized single-chain objects were prepared by performing successive cross-linking reactions in an orthogonal fashion. The foldable precursors were synthesized by sequence-controlled copolymerization of styrene with N-substituted maleimides (MIs), namely pentafluorophenyl 4-maleimidobenzoate (1) and TIPS-protected N-propargyl maleimide (2). These two functional MIs allow intramolecular cross-linking. The activated ester pentafluorophenyl moieties of 1 were reacted with ethylenediamine, whereas the deprotected alkyne functions of 2 were self-reacted by Eglinton coupling. The compaction of model copolymers containing only one cross-linkable zone (i.e., either 1 or 2) was first studied. H-1 NMR and SEC analysis indicated that these structures could be efficiently compacted into single-chain objects. Thus, more complex copolymers containing two individually addressable cross-linking zones were prepared and sequentially compacted. Detailed characterization of the folding process indicated that double-compaction occurred and that the formed single-chain particles contain distinct cross-linked subdomains.
引用
收藏
页码:12888 / 12891
页数:4
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