Template Directed Synthesis and Characterization of Organic Mesoporous Polymers and their Adsorption Performance for Lysozyme

摘要

Three homologous series of MCFs with diverse pore topologies have been synthesized by symbiotic interplay of TMB/P123 (R1) and TEOS/P123 (R2) weight ratios in the initial microemulsion. It was found that the MCFs synthesized at R2 greater than the conventional value suffered significant lag in the mesopore volumes and areas at low concentrations of TMB. However, when R1 is increased beyond 1.0, the difference in the pore volumes and areas became negligible. Many key findings were reported through this study. TEM images revealed that the MCFs synthesized at higher values of R2 prematurely attained larger average pore sizes accompanied with portions displaying constricted worm-like mesostructures. Such bimodal mesophases are accounted by the swelling action of excess amounts of ethanol discharged due to the hydrolysis of increased amounts of TEOS present in the microemulsion along with partial TEOS dissolution in the hydrophobic PPO cores of the TMB/P123 micelles.;MCFs synthesized at highest R2 value of 4.4 exhibits unique interconnected rod-like morphologies which are usually not observed for conventional MCFs. MCF produced using R1 = 2.5 and R2 = 3.0 exhibit bimodal mesophases consisting of polyhedral nanofoam-like textures along with regular spherical pores. USAXS results indicate wall thickness as large as 11 nm for MCFs produced at R2 =4.4. These MCFs of interesting mesostructures were employed as nanoscopic templates to produce Mesocellular Phenol Formaldehyde Foams (MPFFs) using vacuum-assisted incipient wetness impregnation technique. The nanocasted MPFFs show large pore volumes up to 1.4 cm3/g, BET surface areas more than 900 m2/g and large pore diameters in the range 27--99 nm depending on the MCF scaffold used. All the MPFFs showed faithful replication of the cavity sizes of their corresponding MCF parent templates. Stunningly, trimodal MPFFs resulted from the nanocasting of MCFs with R1 > 2.2. The resulting pore sizes were attributed to the original bimodal mesophases and the tertiary pore size resulting from the dissolution of silica pore walls.;The organic, biocompatible MPFFs were employed as sorbents for Lysozyme immobilization at ambient temperature and under isoelectric condition. MPFFs exhibiting loading capacities of more than 230 mg/g serve to be highly encouraging in pursuing our interests further to achieve even higher uptake through post-synthesis functionalization.