A sol-gel method is presented to synthesize molecularly imprinted polymers (MIPs) composed with a copper-based metal-organic framework (referred to as MIP/HKUST-1) on a paper support to selectively recognize tetrabromobisphenol A (TBBPA). The imprinting factor is 7.6 and the maximum adsorption capacity is 187.3 mg g-1. This is much better than data for other MIPs. The degradation of TBBPA is introduced in the procedure. Due to the selective recognition by the MIP, the enzyme-mimicking properties of HKUST-1 under the MIP layer became weak due to the decrease of residue imprinted cavities. And adsorbed TBBPA can be degraded under consumption of hydrogen peroxide (H2O2). The combined effect of H2O2 and HKUST-1 cause the coloration caused by catalytic oxidation of 3,3',5,5'-tetramethylbenzidine to become less distinct. This amplification strategy is used for the ultrasensitive and highly selective colorimetric determination of TBBPA. The gray intensity is proportional to the logarithm concentration of TBBPA in the range of 0.01-10 ng g-1. The limit of detection is as low as 3 pg g-1, and the blank intensities caused by TBBPA analogues are <1% of that caused by TBBPA at the same concentration, this implying excellent selectivity. The spiked recoveries ranged from 94.4 to 106.6% with relative standard deviation values that were no more than 8.6%. Other features include low costs, rapid response, easy operation and on-site testing. Graphical abstractSchematic representation of colorimetric determination of tetrabromobisphenol A (TBBPA) by paper-based metal-organic framework-based molecularly imprinted polymers (MIP/HKUST-1 composites) using 3,3',5,5'-tetramethylbenzidine (TMB) as a substrate.
Keywords: MIP/HKUST-1 composites; On-site monitoring; Paper-based analytical devices; Peroxidase-like activity; Signal amplification strategy.