Universal gold nanoparticle modified hybrid monolithic substrate developed for facile in-column post-functionalization

Abstract

Organic-inorganic hybrid monolithic columns, due to the comprehensive advantages, have been applied as promising solid-phase separation matrices for pretreatment of complex samples in biomedical and environmental analyses, however, a tremendous time and efforts are cost to optimize the preparation methods of hybrid monolithic columns with different functional groups for various target analytes. Herein, we proposed a strategy to develop basic hybrid monolithic column materials for flexible and facile post-functionalization. Three kinds of single-functionalized (amine, thiol, and carboxyl) and two kinds of bi-functionalized (amine and thiol, and amine and carboxyl) hybrid monolithic columns were immobilized with gold nanoparticles (GNPs) as intermediary bridge to construct the universal substrates. The GNPs adsorption capacities of the five hybrid monoliths were compared through qualitative characterization and quantitative analysis. Thioglycolic acid (TGA) and an aptamer against human α-thrombin were respectively used for further functionalizing the substrates to select the most suitable hybrid monolith for optional post-functionalization. It was reported for the first time that the coverage density of TGA on functionalized monolithic column modified by GNPs was 168.41 nmol μL^-1. Notably, the coverage density (2205.8 pmol μL^-1) of the aptamer decorated on the hybrid monolithic column was significantly higher than most other similar materials in published works. After that, the aptamer functionalized hybrid monolithic column screened out was applied for the solid-phase microextraction of thrombin, which possessed excellent adsorption selectivity in interference experiment. Consequently, the developed GNPs modified amine- and thiol-bi-functionalized hybrid monolithic column is an attractive universal substrate to realize easy and efficient post-modification of separation materials for other target analytes in complex samples avoiding a lot of time and labor consumption in the optimization of process preparation.

Keywords: Aptamer; Gold nanoparticle; Human α-thrombin; Hybrid monolithic column; Universal substrate.