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Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides
Published on: July 14, 2015
Magnetic hierarchically mesoporous UIO-66(Ce/Ti) core-shell nanocomposites for efficient enrichment of
Jieling Zhang1, Nan Li2, Hui Lv1
1Key Laboratory of Analytical Chemistry for Life Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, 620 West Chang'an Street, Xi'an, 710119, China.
Abstract:
Hierarchically mesoporous metal-organic frameworks (HMUIO-66(Ce/Ti)) was designed and fabricated firstly by using a relatively rigid hydroxypropyl methylcellulose (HPMC) coupled with poly(ethylene oxide-b-propylene oxide-b-ethylene oxide, P123) as a soft template. By introducing the synergistic effect of Hofmeister ions and the soft template of HPMC coupled with P123 into the water-rich micelle system, the obtained HMUIO-66(Ce/Ti) possessed irregularly mesoporous architecture with a wide pore size distribution of 8.4 ~ 26.8 nm. Furthermore, the robust lysozyme coating layer self-organized on Fe3O4@SiO2 nanoparticles readily mediated the heterogeneous nucleation and growth of MOF nanocrystals to form the magnetic hierarchically mesoporous UIO-66(Ce/Ti) core-shell nanocomposites (MHMUIO-66(Ce/Ti) CSNCs). The MHMUIO-66(Ce/Ti) CSNCs exhibited high BET surface area of 471.6 m2·g-1 with large pore volume of 0.39 cm3·g-1, a central pore size of 13.7 nm with a wide pore size distribution of 7.8 ~ 24.5 nm, good chemical stability, and superparamagnetic properties. Consequently, the hierarchically mesoporous architecture of MHMUIO-66(Ce/Ti) CSNCs provided the high accessibility of bimetallic Ce/Ti inside binding sites and thus the enhanced phosphopeptides enrichment performance with low detection limit (0.5 fmol) and high selectivity (mass ratio of β-casein/BSA, 1:1000). Furthermore, the successful identification of 24 phosphopeptides enriched by MHMUIO-66(Ce/Ti) CSNCs from an actual sample of skim milk suggested that this method could be a good candidate for identifying phosphopeptide biomarkers in more complex biological samples.

