Pore-enlarged mesoporous silica nanoparticles (MSNs) were prepared directly from as-prepared MSNs through a new, simple method using divalent Ca or Mg salts as both efficient silica etching reagents and as ion exchangers in methanolic solution under mild conditions. The resultant MSNs became almost template-free simultaneously during this etching process. The pore-enlarged MSNs, referred to as Ca-MSN or Mg-MSN, maintained their original hexagonal pore symmetry and particle sizes, but several ultra-large mesopores were generated inside and outside the MSNs together with regular mesopores having expanded pore dimension of around 4-5 nm. The average pore diameters for ultra-large pores were 47.5 nm for Ca-MSN and 52.4 nm for Mg-MSN. The generation of ultra-large pores can be regarded as the collapse of several mesopores into an ultra-large pore. Both Ca-MSN and Mg-MSN were good sorbents for positively charged porphyrin molecules. Additionally, these ultra-large pore MSNs exhibited better adsorption ability than calcined MSN for large proteins and antibodies, such as bovine serum albumin (BSA) and immunoglobulin G (IgG).
Imaging, Three-Dimensional Magnetic Resonance Spectroscopy