Functionalized Nanoporous Gyroid SiO₂ with Double-Stimuli-Responsive Properties as Environment-Selective Delivery Systems

Abstract

Herein, we aim to fabricate nanoporous gyroid SiO 2 from templated sol−gel reaction using degradable block copolymer with gyroid-forming nanostructure as a template and then to functionalize the nanoporous materials using "smart" polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), brushes via the "grafting from" method to give double-stimuli-responsive properties. By taking advantage of the responses to environmental stimuli, both thermal and pH, the pore features can be well-defined by the stretching and recoiling of PDMAEMA brushes because of their adjustable chain conformations with reversible character. The responsive properties with respect to environmental stimuli can be successfully traced by temperature-resolved small-angle X-ray scattering (SAXS) in aqueous environment. Owing to the high specific surface area and porosity, 3D pore network, biocompatibility, and environmental responses, the functionalized nanoporous gyroid SiO 2 is further demonstrated as a stimuli-responsive controlled release system.

Engineering Gyroid‐Structured Functional Materials via Templates Discovered in Nature and in the Lab

“…What's more, the surface chemistry and permeability were reported to be versatile, controlled by importing functional groups through chemical methods, or by simply altering the interface energy in the process of membrane fabrication, resulting in flexibly tuned diffusion (Figure c,d) . The opened and closed conditions of the nanopores can also be selectively tuned by controlling their physical and chemical environments, such as pH and solvent . Hence they can also be utilized for drug delivery, and selectively loading and releasing small molecules …”

Preparation of 2‐(dimethylamino) ethyl methacrylate copolymer micelles for shape memory materials

“…It is well known that poly(2‐(dimethylamino)ethyl methacrylate) (pDMAEMA) is widely used as a biomaterials double hydrophilic copolymer and environmentally sensitive coating due to its unique chemical structure containing–N(CH 3 ) 2 functional groups , which can be further quaternized or betainized . The literature reveals that the functional monomer 2‐(dimethylamino)ethyl methacrylate (DMAEMA) has been widely used to design stimuli‐responsive hydrogels, micelles, brushes, and other functional membranes grafted onto various substrates . In addition to their responsiveness to pH and temperature, DMAEMA‐based copolymers can also respond to external stimuli such as ion strength, selected ions and other factors in solution .…”

Strategies for Inorganic Incorporation using Neat Block Copolymer Thin Films for Etch Mask Function and Nanotechnological Application

“…[ 104 ] Owing to the degradable PLA component, porous templates can be formed through simple wet etching. Ming-Ho and co-workers have produced excellent 3D inorganic replicas (e.g., silica, [105][106][107] titania [ 108 ] ) with PS-b -PLA gyroid templating structures via sol-gel reactions for environmental use, drug delivery application, and anti-refl ection purposes. The work has been reviewed extensively.…”