基于RAFT聚合反应的核壳型磁性分子印迹纳米材料的制备及分析应用
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摘要
分子印迹聚合物(MIPs)以其构效预定性、比拟抗体的亲和性、特异识别性以及超越抗体的广泛适用性、稳定性、廉价性,成功应用在化学生物传感、模拟酶催化、临床药物分析等诸多领域。然而,在MIPs研究中仍存在一些亟待克服的问题,例如印迹位点深埋聚合物内部,导致传质速率慢,吸附容量低;水相识别能力弱等。本工作以超顺磁性纳米颗粒Fe_3O_4为载体,利用表面引发可逆加成链转移(si-RAFT)这种活性可控聚合技术,以广谱抗菌药氧氟沙星为模板,成功制备了印迹壳层清晰、厚度均一的核壳型MIPs。实验结果表明,MIPs具有识别选择性好、识别速率快、吸附容量高等优点,实现了人尿液中五种氟喹诺酮类药物的同时选择性富集分离与检测。进一步,鉴于MIPs在水相识别过程中易受样品中大分子物质的掩蔽而影响吸附性能的问题,通过在聚合反应中加入亲水性大分子链转移剂(macro-CTA),成功构建水相识别性能高的亲水性核壳型MIPs,成功实现了未处理血清样品中β-受体阻滞剂-普萘洛尔的高选择性富集检测。
Molecularly imprinted polymers(MIPs),mimicking nature macromolecular recognition systems,are potential artificial alternatives to antibodies,enzymes and biological receptors.In this study,the superparamagnetic core-shell MIP nanoparticles were prepared via surface initiated reversible addition fragmentation chain transfer(si-RAFT) polymerization using ofloxacin as template.The living/controlled nature of si-RAFT polymerization reaction and optimum polymerization conditions allowed the construction of distinct core-shell structure with a 50 nm MIP layer,which favors fast mass transfer and rapid binding kinetics.The target binding assays demonstrate the fast adsorption kinetics and high imprinting efficiency of Fe_3O_4@MIPs.In real sample application,five kinds of fluoroquinolones were enriched simultaneously from human urine using MIPs.Further,in complex biological samples,imprinting sites of MIPs could be covered by large molecules such as proteins in the matrix.To overcome this problem,hydrophilic macro-chain transfer agents(macro-CTA) was added in the RAFT polymerization to construct MIPs with high recognition ability.
引文
[1]Mahon,C.;Fulton,D.Nat.Chem.2014,6:665.
    [2]He,Y.;Huang,Y.;Jin,Y.;Liu,X.;Liu,G.;Zhao,R.ACS Appl.Mater.Interfaces 2014,6:9634.
    [3]Liu,Y.;He,Y.;Jin,Y.;Huang,Y.;Liu,G.;Zhao,R.J.Chromatogr.A 2014,1323:11.
    [4]Liu,Y.;Huang,Y.;Liu,J.;Wang,W.;Liu,G.;Zhao,R.J.Chromatogr.A 2012,1246:15.
    [5]Liu,J.;Wang,W.;Xie,Y.;Huang,Y.;Liu,Y.;Liu,X.;Zhao,R.;Liu,G.;Chen,Y.J.Mater.Chem.2011,21:9232.

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