以Fe3O4磁性纳米粒子为载体、多巴胺（DA）为功能单体、血红蛋白（Hb）为模板分子，用氯铂酸氧化DA生成聚多巴胺（PDA），同时氯铂酸还原为铂纳米粒子（PtNPs），与Hb一起负载于Fe3O4纳米粒子表面，洗脱Hb后合成了表面分子印迹磁性纳米粒子（印迹Fe3O4/PDA-PtNPs）. 将印迹Fe3O4/PDA-PtNPs修饰于磁性玻碳基底表面，制得印迹Fe3O4/PDA-PtNPs修饰电极. 实验结果表明，印迹Fe3O4/PDA-PtNPs具有良好的水溶性，粒径分布均匀，生成的PtNPs具有良好的导电性和刚性. 用印迹Fe3O4/PDA-PtNPs构建的传感器对Hb具有良好的识别性，在0.14 ~ 2.7 μg·mL-1 Hb浓度范围与交流阻抗变化值呈良好的线性关系，检出限（S/N=3）为0.05 μg·mL-1.
Surface molecularly imprinted magnetic nanoparticles (NPs) were prepared by employing dopamine (DA) as a functional monomer, hemoglobin (Hb) as a template, H2PtCl6 as an oxidant triggered DA polymerization on the surface of the Fe3O4 NPs. The Hb and the formed platinum nanoparticles (PtNPs) were embedded into the polydopamine (PDA). After removal of the Hb, the surface molecularly imprinted magnetic nanoparticles (imprinted Fe3O4/PDA-PtNPs) were formed, and then simply immobilized on the magnetic glassy carbon electrode (imprinted Fe3O4/PDA-PtNPs/MGCE) for Hb sensing. The imprinted Fe3O4/PDA-PtNPs were demonstrated magnetic spherical shape with good solubility in water and narrow size distribution. The PtNPs embedded in the imprinted coating could effectively promote the conductivity and the mechanical strength of imprinted cavity. In addition, the imprinted Fe3O4/PDA-PtNPs/MGCE could selectively recognize Hb and was used to detect Hb in the range of 0.14 ~ 2.7 μg?mL-1 with a detection limit of 0.05 μg?mL-1 (S/N=3).
[1] Haupt K, Mosbach K. Plastic antibodies: Developments and applications[J]. Trends in Biotechnology, 1998, 16(11): 468-475.
[2] Li Y, Yang H H, You Q H, et al. Protein recognition via surface molecularly imprinted polymer nanowires[J]. Analytical Chemistry, 2006, 78(1): 317-320.
[3] Riskin M, Tel-Vered R, Willner I. The imprint of electropolymerized polyphenol films on electrodes by donor-acceptor interactions: Selective electrochemical sensing of N,N'-dimethyl-4,4'-bipyridinium(methyl viologen)[J]. Advanced Functional Materials, 2007, 17(18): 3858-3863.
[4] Ge Y, Turner A P F. Too large to fit? Recent developments in macromolecular imprinting[J]. Trends in Biotechnology, 2008, 26(4): 218-224.
[5] Haupt K. Biomaterials: Plastic antibodies[J]. Nature Materials, 2010, 9(8): 612-614.
[6] Tan C J, Tong Y W. Molecularly imprinted beads by surface imprinting[J]. Analytical and Bioanalytical Chemistry, 2007, 389(2): 369-376.
[7] Cai D, Ren L, Zhao H Z, et al. A molecular-imprint nanosensor for ultrasensitive detection of proteins[J]. Nature Nanotechnology, 2010, 5: 597-601.
[8] Zhang W, He X W, Chen Y, et al. Molecularly imprinted polymer anchored on the surface of denatured bovine serum albumin modified CdTe quantum dots as fluorescent artificial receptor for recognition of target protein[J]. Biosensors and Bioelectronics, 2012, 31(1): 84-89.
[9] Yang W H(杨卫海), Wu Y(吴瑶), Zhang Y(张轶), et al. Preparation and application of core-shell magnetic molecularly imprinted polymer microspheres[J]. Progress in Chemistry(化学进展), 2010, 22(9): 1819-1825.
[10] Lu C H, Wang Y, Li Y, et al. Bifunctional superparamagnetic surface molecularly imprinted polymer core-shell nanoparticles[J]. Journal of Materials Chemistry, 2009, 19(8): 1077-1079.
[11] Qu P, Lei J, Zhang L, et al. Molecularly imprinted magnetic nanoparticles as tunable stationary phase located in microfluidic channel for enantioseparation[J]. Journal of Chromatography A, 2010, 1217(39): 6115-6121.
[12] Kan X, Zhao Q, Shao D, et al. Preparation and recognition properties of bovine hemoglobin magnetic molecularly imprinted polymers[J]. Journal of Physical Chemistry B, 2010, 114(11): 3999-4004.
[13] Lee H, Dellatore S M, Miller W M, et al. Mussel-inspired surface chemistry for multifunctional coatings[J]. Science, 2007, 318(5849): 426-430.
[14] Zhou W H, Lu C H, Guo X C, et al. Mussel-inspired molecularly imprinted polymer coating superparamagnetic nanoparticles for protein recognition[J]. Jouranl of Materials Chemistry, 2010, 20(5): 880-883.
[15] Deng H, Li X, Peng Q, et al. Monodisperse magnetic single-crystal ferrite microspheres[J]. Angewandte Chememie International Edition, 2005, 44(18): 2782-2785.
[16] Peng H P, Qiu J D, Liang R P. Facile synthesis of Fe3O4@Al2O3 core-shell nanoparticles and their application to the highly specific capture of heme proteins for direct electrochemistry[J]. Biosensors and Bioelectronics, 2011, 26(6): 3005-3011.
[17] Fu Y, Li P, Xie Q, et al. One-pot preparation of polymer-enzyme-metallic nanoparticle composite films for high-performance biosensing of glucose and galactose[J]. Advanced Functional Materials, 2009, 19(11): 1784-1791.
