Abstract

Recently, metal mediated molecularly imprinted polymers (MMIPs) raise extensive attention due to their special adsorption/desorption mechanism. And the metal ion plays a key role both for MMIPs preparation and molecular recognition. But it is still a big question to select one suitable metal ion. To overcome above problem, one computational approach was proposed by calculating interaction energy (ΔE) of ternary complexes (monomer-M2+-template) with GAMESS software at the PBE0 level. Finally Cu(II) was screened from four doubly charged metal ions with different radii. Then Cu mediated MIP was prepared via surface imprinting technique with Fe3O4 as the core in a water system. Subsequently, the adsorption behavior of the MMIP immobilized Cu(II) was investigated in detail. The results indicated the microspheres own excellent specificity and selectivity towards tetracycline (TC), as well as long-term stability and good reproducibility. The apparent maximum binding capacity and the imprinting factor were as high as 163.5 mg g− 1 and 19, respectively. Coupled with HPLC-PDA, the microspheres was successfully used as a dispersed solid phase extraction material to extract trace TC in chicken liver. At three spiking levels, mean recoveries ranged from 89.3% to 97.1% with relative standard deviations less than 4.0% (n = 3). Limits of detection and quantitation were 0.0073 mg kg− 1 and 0.024 mg kg− 1, respectively, which can meet the strict requirement of the regulations stipulated by EU. Moreover, preliminary studies showed the radius of the metal ion and ΔE of the complexes all affect the adsorption capacity, specificity and mass transfer rate of the MMIP.

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