General Synthesis of Ultrafine Monodispersed Hybrid Nanoparticles from Highly Stable Monomicelles

Zaiwang Zhao; Xiao Wang; Xinxin Jing; Yujuan Zhao; Kun Lan; Wei Zhang; Linlin Duan; Dingyi Guo; Changyao Wang; Liang Peng; Xingmiao Zhang; Zesheng An; Wei Li; Zhihong Nie; Chunhai Fan; Dongyuan Zhao

doi:10.1002/adma.202100820

General Synthesis of Ultrafine Monodispersed Hybrid Nanoparticles from Highly Stable Monomicelles

Adv Mater. 2021 Jun;33(23):e2100820. doi: 10.1002/adma.202100820. Epub 2021 Apr 29.

Authors

Zaiwang Zhao¹, Xiao Wang², Xinxin Jing³, Yujuan Zhao⁴, Kun Lan¹, Wei Zhang¹, Linlin Duan¹, Dingyi Guo¹, Changyao Wang¹, Liang Peng¹, Xingmiao Zhang¹, Zesheng An⁵, Wei Li¹, Zhihong Nie¹, Chunhai Fan³, Dongyuan Zhao¹

Affiliations

¹ Department of Chemistry, Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, iChEM and State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai, 200433, P. R. China.
² State Key Laboratory of Coal Resources and Safe Mining, School of Mines, China University of Mining and Technology, Xuzhou, 221116, P. R. China.
³ Institute of Molecular Medicine, Shanghai Key Laboratory for Nucleic Acids Chemistry and Nanomedicine, Renji Hospital, School of Medicine and School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules and National Center for Translational Medicine, Shanghai Jiao Tong University, Shanghai, 200127, P. R. China.
⁴ Centre for High-Resolution Electron Microscopy (CћEM), School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Road, Pudong, Shanghai, 201210, P. R. China.
⁵ State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Key Laboratory for Molecular Enzymology and Engineering of Ministry of Education, School of Life Sciences, Jilin University, Changchun, 130012, P. R. China.

PMID: 33914372
DOI: 10.1002/adma.202100820

Abstract

Ultrafine nanoparticles with organic-inorganic hybridization have essential roles in myriad applications. Over the past three decades, although various efforts on the formation of organic or inorganic ultrasmall nanoparticles have been made, ultrafine organic-inorganic hybrid nanoparticles have scarcely been achieved. Herein, a family of ultrasmall hybrid nanoparticles with a monodisperse, uniform size is synthesized by a facile thermo-kinetics-mediated copolymer monomicelle approach. These thermo-kinetics-mediated monomicelles with amphiphilic ABC triblock copolymers are structurally robust due to their solidified polystyrene core, endowing them with ultrahigh thermodynamic stability, which is difficult to achieve using Pluronic surfactant-based micelles (e.g., F127). This great stability combined with a core-shell-corona structure makes the monodispersed monomicelles a robust template for the precise synthesis of ultrasmall hybrid nanoparticles with a highly uniform size. As a demonstration, the obtained micelles/SiO₂ hybrid nanoparticles display ultrafine sizes, excellent uniformity, monodispersity, and tunable structural parameters (diameters: 24-47 nm and thin shell thickness: 2.0-4.0 nm). Notably, this approach is universal for creating a variety of multifunctional ultrasmall hybrid nanostructures, involving organic/organic micelle/polymers (polydopamine) nanoparticles, organic/inorganic micelle/metal oxides (ZnO, TiO₂ , Fe₂ O₃ ), micelle/hydroxides (Co(OH)₂ ), micelle/noble metals (Ag), and micelle/TiO₂ /SiO₂ hybrid composites. As a proof of concept, the ultrasmall micelle/SiO₂ hybrid nanoparticles demonstrate superior toughness as biomimetic materials.

Keywords: biomimetic materials; monodispersity; monomicelles; organic-inorganic hybrids; superior toughness; ultrafine nanoparticles.

Abstract

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