Filling Carbon Nanotubes with Prussian Blue Nanoparticles of High Peroxidase-Like Catalytic Activity for Colorimetric Chemo-and Biosensing

摘要

Facile filling of multiwalled carbon nanotubes (MWCNTs) with Prussian blue nanoparticles (PBNPs) of high peroxidase-like catalytic activity was performed to develop novel colorimetric sensing protocols for assaying H_2O_2 and glucose. Fine control of PBNP growth was achieved by modulating the concentration ratio of K_3[Fe(CN)_6] and FeSO_4 precursors in an acidic solution containing ultrasonically dispersed MWCNTs, and thus size-matched PBNPs could be robustly immobilized in the cavities of the MWCNTs (MWCNT-PB_(in)). Unlike other reported methods involving complicated procedures and rigorous preparation/separation conditions, this mild one-pot filling method has advantages of easy isolation of final products by centrifugation, good retention of the pristine outer surface of the MWCNT shell, and satisfactory filling yield of (24±2) %. In particular, encapsulation of PBNPs of poor dispersibility and limited functionality in dispersible and multifunctional MWCNT shells creates new and valuable opportunities for quasihomogeneous-phase applications of PB in liquid solutions. The MWCNT-PB_(in) nanocomposites were exploited as a peroxidase mimic for the colorimetric assay of H_2O_2 in solution by using 3,3',5,5'-tetramethylbenzidine (TMB) as reporter, and they gave a linear absorbance response from 1 mm to 1.5 mm with a limit of detection (LOD) of 100 nm. Moreover, glucose oxidase (GOx) was anchored on the outer surface of MWCNT-PB_(in) to form GOx/MWCNT-PB_(in) bionanocomposites. The cooperation of outer-surface biocatalysis with peroxidase-like catalysis of interior PB resulted in a novel cooperative colorimetric biosensing mode for glucose assay. The use of GOx/MWCNT-PB_(in) for colorimetric biosensing of glucose gave a linear absorbance response from 1 μm to 1.0 mm and an LOD of 200 nm. The presented protocols may be extended to other multifunctional nanocomposite systems for broad applications in catalysis and biotechnology.