Hierarchically Structured Nanocomposites via Mixed-Graft Block Copolymer Templating: Achieving Controlled Nanostructure and Functionality

Abstract

Integrating inorganic and polymerized organic functionalities to create composite materials presents an efficient strategy for the discovery and fabrication of multifunctional materials. The characteristics of these composites go beyond a simple sum of individual component properties; they are profoundly influenced by the spatial arrangement of these components and the resulting homo-/hetero-interactions. In this work, we develop a facile and highly adaptable approach for crafting nanostructured polymer−inorganic composites, leveraging hierarchically assembling mixed-graft block copolymers (mGBCPs) as templates. These mGBCPs, composed of diverse polymeric side chains that are covalently tethered with a defined sequence to a linear backbone polymer, self-assemble into ordered hierarchical structures with independently tuned nano-and mesoscale lattice features. Through the coassembly of mGBCPs with diversely sized inorganic fillers such as metal ions (ca. 0.1 nm), metal oxide clusters (0.5−2 nm), and metallic nanoparticles (>2 nm), we create three-dimensional filler arrays with controlled interfiller separation and arrangement. Multiple types of inorganic fillers are simultaneously integrated into the mGBCP matrix by introducing orthogonal interactions between distinct fillers and mGBCP side chains. This results in nanocomposites where each type of filler is selectively segregated into specific nanodomains with matrix-defined orientations. The developed coassembly strategy offers a versatile and scalable pathway for hierarchically structured nanocomposites, unlocking new possibilities for advanced materials in the fields of optoelectronics, sensing, and catalysis.

Efficient Strategy to Synthesize Tunable pH-Responsive Hybrid Micelles Based on Iron Oxide and Gold Nanoparticles

“…Inorganic hybrid nanomaterials have been attracting a great interest in the past decade in the medical research field as promising agents for the diagnosis and treatment of multiple diseases. − This class of materials are mainly made by the combination of inorganic nanoparticles (NPs) with organic materials. − Sphere- and cube-shaped iron oxide-based NPs in different sizes are the most studied colloidal magnetic NPs due to their excellent characteristics as magnetic resonance imaging contrast agents and also as heat mediators in magnetic hyperthermia. − AuNPs and gold-based NPs are also intensively studied as bioimaging and biosensing agents . On the other hand, organic materials such as micelles, liposomes, dendrimers, and polymers are combined with inorganic NPs to render hybrid nanomaterials highly soluble under physiological conditions without altering their initial properties .…”

Polymerization-Induced Hierarchical Hybrid Particles from Siloxane Emulsification Endowing Polyurethane Composite Coating with Superhydrophobicity, Thermal Insulation, and Fluorescence

“…To date, a variety of hierarchically structured particles have been prepared, mainly including dumbbell shape, popcorn shape, strawberry shape, , and so on. Owing to the rough surface morphology and large specific surface area, , these particles have been extensively studied and applied in many areas, such as superhydrophobic coating, drug delivery, catalyst carriers, , environmental protection, and nanocomposites . Among them, superhydrophobic coating (water contact angle ≥ 150°) plays an increasing importance in applications, such as antifouling, self-cleaning, and anti-icing. , …”

“…At present, a lot of methods to prepare hierarchically structured particles have been developed through pioneering research, including self-templating, template-assisting synthesis, spray drying, , seed-assisted hydrothermal method, chemical/physical self-assembly method, and secondary nucleation method. Template methods mainly include hard and soft template methods derived from polymers, inorganic particles, emulsion droplets, micelles, and so on.…”