title: Directional supracolloidal self-assembly via dynamic covalent bonds and metal coordination.
abstract: An emerging strategy towards the sophistication of supramolecular nanomaterials is the use of supracolloidal self-assembly, in which micelles or colloids are used as building blocks. Binding directionality can produce nanostructures with attractive properties. Herein, we present a new directional supracolloidal self-assembly by virtue of dynamic covalent bonds and metal coordination in water. Conjugation of a ligand precursor to a water-soluble block copolymer through dynamic covalent bonds leads to the dehydration and micellization of the functionalized polymer. Reversible reaction facilitates the permeation of metal ions into core-shell interfaces. Conversely, metal-coordination promotes reaction over the interfaces. Cu(ii)-coordination occurs overwhelmingly inside each isolated micelle. However, Zn(ii)-coordination induced a directional self-assembly whose nanostructures evolve stepwise from nanorods, nanowires, necklaces, and finally to supracolloidal networks scaling-up to several tens of micrometres. Post-reactions of simultaneous dynamic covalent bond conversion and Zn(ii)-coordination over the core-shell interfaces endow these supracolloidal networks with a huge specific surface area for hydrophobic dative metal centres accessible to substrates in water. Water-soluble shells play important roles in directional supracolloidal assembly and in the stabilization of nanostructures. Thus the directional self-assembly provides a versatile platform to produce metallo-hybridized nanomaterials that are promising as enzyme-inspired aqueous catalysts.
authors.affiliation: The Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China. ylcai@suda.edu.cn.
authors.forename: Na
authors.initials: N
authors.lastname: Xu
authors.forename: Jie
authors.initials: J
authors.lastname: Han
authors.forename: Zhengguang
authors.initials: Z
authors.lastname: Zhu
authors.forename: Bo
authors.initials: B
authors.lastname: Song
authors.forename: Xinhua
authors.initials: X
authors.lastname: Lu
authors.forename: Yuanli
authors.initials: Y
authors.lastname: Cai