Shi Haizhu, Wen Mengzhao, Lin Xuhui, Zhou Lingqiang, Shan Lianhai, Zhang Chungu, Feng Shun
Sichuan Engineering Research Center for Biomiometic Synthesis of Natural Drugs, School of Life Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China.
Sichuan Engineering Research Center for Biomiometic Synthesis of Natural Drugs, School of Life Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China.
J Pharm Biomed Anal. 2022 Oct 25;220:115023. doi: 10.1016/j.jpba.2022.115023. Epub 2022 Aug 30.
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-M-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 FeO 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 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 and 0.024 mg kg, 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.
近年来，金属介导的分子印迹聚合物（MMIPs）因其特殊的吸附/解吸机制而受到广泛关注。金属离子在MMIPs的制备和分子识别中都起着关键作用。但选择一种合适的金属离子仍然是一个大问题。为了克服上述问题，提出了一种计算方法，即在PBE0水平上用GAMESS软件计算三元配合物（单体-M-模板）的相互作用能（ΔE）。最后从四种不同半径的二价金属离子中筛选出了Cu(II)。然后以FeO为核，通过表面印迹技术在水体系中制备了Cu介导的MIP。随后，详细研究了固定化Cu(II)的MMIP的吸附行为。结果表明，微球对四环素（TC）具有优异的特异性和选择性，以及长期稳定性和良好的重现性。表观最大结合容量和印迹因子分别高达163.5 mg g和19。结合HPLC-PDA，微球成功地用作分散固相萃取材料，用于提取鸡肝中的痕量TC。在三个加标水平下，平均回收率在89.3%至97.1%之间，相对标准偏差小于4.0%（n = 3）。检测限和定量限分别为0.0073 mg kg和0.024 mg kg，能够满足欧盟规定的严格要求。此外，初步研究表明，金属离子的半径和配合物的ΔE均影响MMIP的吸附容量、特异性和传质速率。
