Ordered Mesoporous Metal–Phenolic Network Particles

Abstract

Mesoporous metal-organic networks have attracted widespread interest owing to their potential applications in diverse fields including gas storage, separations, catalysis, and drug delivery. Despite recent advances, the synthesis of metal-organic networks with large and ordered mesochannels (>20 nm), which are important for loading, separating, and releasing macromolecules, remains a challenge. Herein, we report a templating strategy using sacrificial double cubic network polymer cubosomes ( 3 ) to synthesize ordered mesoporous metal-phenolic particles (meso-MPN particles) with a large pore (~40 nm) single cubic network ( 3 ). We demonstrate that the large pore network and the phenolic groups in the meso-MPN particles enable high loadings of various proteins (e.g., horseradish peroxidase (HRP), bovine hemoglobin, immunoglobulin G, and glucose oxidase (GOx)), which have different shapes, charges, and sizes (i.e., molecular weights spanning 44-160 kDa). For example, GOx loading in the meso-MPN particles was 362 mg g −1 , which is ~6-fold higher than the amount loaded in commercially available SiO2 particles with an average pore size of 50 nm. Furthermore, we show that HRP, when loaded in the meso-MPN particles (486 mg g −1 ), retained ~82% activity of free HRP in solution and can be recycled at least 5 times with a minimal (~13%) decrease in HRP activity, which exceeds HRP performance in 50-nm pore SiO2 particles (~36% retained activity and ~30% activity loss when recycled 5 times). Considering the wide selection of naturally abundant polyphenols (>8000 species) and metal ions available, the present cubosome-enabled strategy is expected to provide new avenues for designing a range of meso-MPN particles for various applications.

Polyphenol-Mediated Assembly for Particle Engineering

“…5,6 In the last decade, our group has explored a variety of polyphenol-mediated assemblies for materials engineering (Figure 1). [7][8][9][10][11][12][13][14][15][16][17][18][19] In the present Account, the term "polyphenol" is used to refer to catechol-and gallol-containing aromatic building blocks with functionality common to polyphenols, without distinction between natural polyphenols and their synthetic derivatives.…”

Monodisperse Ultrahigh Nitrogen‐Containing Mesoporous Carbon Nanospheres from Melamine‐Formaldehyde Resin

“…Mesoporous materials have been receiving considerable attention due to their unpredictable properties, including high surface areas, large pore volumes, and adjustable morphologies and structures. [ 1–5 ] Mesoporous carbons, owing to high thermal stability, chemical inertness and good electric conductivity, have attracted extensive interests in catalysis, adsorption, gas sensing and energy conversion and storage. [ 6–9 ] Specifically, owing to the unique spherical morphology and short diffusion pathway, mesoporous carbon nanospheres exhibit excellent electrochemical performances.…”

Recent Progress in Polymer Cubosomes and Hexosomes

“…Polymer colloids with ordered internal structures have attracted more and more attention for their potential applications in nanotemplating, [ 12,32e,46 ] drug delivery, [ 13a,16a,c,26,37 ] ultrafiltration, [ 13a ] photonics, [ 12 ] and imaging. [ 13b ] Here, we focus on the examples in nanotemplating and drug delivery.…”

“…Polymer cubosomes can be used as the soft template to produce inorganic or metal‐organic mesoporous particles with ordered internal structures. [ 12,32e,46a,b ] It is interesting to note that the Im m and Pm m polymer cubosomes consist of two interwoven water channels, where one set of channels opens to its surrounding via the perforations presenting on the outer bilayer shell, while the other set hides under the bilayer shell. The open channel could be replicated to yield a skeletal (single) network of SiO 2 or TiO 2 according to La et al.…”