Zhigang Cui,Hui Cao,Yi Ding,Pan Gao,Xinhua Lu,Yuanli Cai
Herein, we present supramolecular compartmentalization of an ABC triblock copolymer single-chain nanoparticle (SCNP) using coordination-driven orthogonal intramolecular self-assembly in aqueous solution. A well-defined ABC-type triblock copolymer was synthesized via visible-light-mediated RAFT aqueous sequential block copolymerization. It possesses protonated imidazolium-motifs in the A-, NH3+-motifs in C-, and hydroxyl-motifs in B-block. Coordination-driven orthogonal self-assembly locally occurring upon deprotonation (A-block within pH 3.3–4.4 and C-block within pH 5.3–6.4) has been evidenced by UV-vis spectroscopy, 1H NMR, dynamic light scattering (DLS), NMR diffusion-ordered spectroscopy (DOSY), and atomic force microscopy (AFM). A blank regime of pH 4.4–5.3 guarantees locally orthogonal intramolecular self-assembly without mutual interference. Dialysis and pH-cycling results illustrate that the inherent different subdomains are discrete and can individually respond to an external stimulus, with potential biomimetic functions in terms of sub-10 nm ultrafine internal heterogeneity.
Jing Yan,Huiya Huang,Zhiliang Miao,Qiuyu Zhang,Yi Yan
To enrich the building blocks and functions of supramolecular polymer, functioned inorganic polyoxometalate clusters were introduced through a novel and efficient orthogonal self-assembly strategy. The design principle is based on the organic modification of polyoxometalates (POMs) with coordination groups and electrostatic interaction of POMs with surfactants capped by photo-cross-linkable groups. Because of the relatively independent nature of these two interactions, it is possible to prepare POMs-based supramolecular cross-linked network through coordination–photo-cross-linking and vice versa, leading to the formation of main-chain-type POMs-based supramolecular polymer networks and gels. The responsiveness of these two interactions also endows the resulted supramolecular polymer with different responsiveness to light and coordination. Therefore, orthogonal self-assembly supramolecular polymerization of POMs provides a facile strategy to improve the processability of inorganic clusters, paving a new avenue toward cluster-based materials and electronic devices.
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