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    许升, 徐振宇, 王乾坤, 王满, 张雨珩, 陈彦儒, 刘晓亚. “项链状”聚合物/碳纳米管杂化组装体构建多巴胺传感器[J]. 功能高分子学报, 2019, 32(3): 307-315. doi: 10.14133/j.cnki.1008-9357.20180712001
    引用本文: 许升, 徐振宇, 王乾坤, 王满, 张雨珩, 陈彦儒, 刘晓亚. “项链状”聚合物/碳纳米管杂化组装体构建多巴胺传感器[J]. 功能高分子学报, 2019, 32(3): 307-315. doi: 10.14133/j.cnki.1008-9357.20180712001
    XU Sheng, XU Zhenyu, WANG Qiankun, WANG Man, ZHANG Yuheng, CHEN Yanru, LIU Xiaoya. Fabrication of Dopamine Sensor Based on Hybrid Assembly of Necklace-Like Polymer/Carbon Nanotubes[J]. Journal of Functional Polymers, 2019, 32(3): 307-315. doi: 10.14133/j.cnki.1008-9357.20180712001
    Citation: XU Sheng, XU Zhenyu, WANG Qiankun, WANG Man, ZHANG Yuheng, CHEN Yanru, LIU Xiaoya. Fabrication of Dopamine Sensor Based on Hybrid Assembly of Necklace-Like Polymer/Carbon Nanotubes[J]. Journal of Functional Polymers, 2019, 32(3): 307-315. doi: 10.14133/j.cnki.1008-9357.20180712001

    “项链状”聚合物/碳纳米管杂化组装体构建多巴胺传感器

    Fabrication of Dopamine Sensor Based on Hybrid Assembly of Necklace-Like Polymer/Carbon Nanotubes

    • 摘要: 首先以7-(4-乙烯基苄氧基)-4-甲基香豆素、丙烯酸异辛酯及丙烯酸为功能单体合成了一种双亲性无规共聚物聚丙烯酸-7-(4-乙烯基苄氧基)-4-甲基香豆素-丙烯酸异辛酯(PAVE);随后将PAVE与碳纳米管(CNTs)在选择性溶剂NN-二甲基甲酰胺(DMF)/H2O中共组装,得到聚合物/碳纳米管杂化组装体PAVE/CNTs,利用透射电子显微镜对PAVE/CNTs的形貌进行表征;最后将PAVE/CNTs修饰在玻碳电极表面,紫外光交联固化后制备得到复合传感涂层,并用于检测多巴胺,利用扫描电子显微镜与电化学工作站分别对传感器涂层形貌与传感性能进行表征与测试。结果表明:PAVE与CNTs共组装形成了以PAVE纳米粒子为"珠",以CNTs为"线"的"项链状"杂化组装体;传感涂层为交错互穿的"网络状"复合结构;所构建的传感器对多巴胺具有较宽的检测范围(4~90 μmol/L)与较低的检测下限(0.24 μmol/L),并具有优异的选择性与稳定性。

       

      Abstract: A novel kind of nanohybrids with a "necklace-like" morphology was prepared via one-step co-assembly of amphiphilic random copolymer and multi-walled carbon nanotubes (CNTs), which is successfully employed as the effective electrode material to construct an electrochemical sensor for highly sensitive detection of dopamine. A photo-crosslinkable amphiphilic copolymer poly(acrylic acid-co-(7-(4-vinylbenzyloxy)-4-methyl coumarin)-co-ethylhexyl acrylate) (PAVE) was synthesized firstly via one-step free radical polymerization. The chemical structure of the resultant PAVE copolymer was confirmed by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (1H-NMR). Then PAVE copolymer was co-assembled with CNTs in aqueous solution, generating hybrid assembly of PAVE/CNTs. As characterized by transmission electron microscopy (TEM), the obtained PAVE/CNTs hybrids showed "necklace-like" morphology with PAVE nanoparticles as the beads and CNTs as the long axis. Thanks to the enhanced binding interactions between PAVE copolymers and CNTs sidewalls upon photo-crosslinking as well as the steric exclusion among PAVE/CNTs nanohybrids, the obtained nanohybrids showed good dispersion stability in aqueous solution and preserved the intrinsic structural properties of CNTs. For application as a sensor, PAVE/CNTs were used as the electrode material to modify the surface of glassy carbon electrode (GCE). A robust composite film with cross-conjugated network was formed on the electrode surface, resulting in an electrochemical sensor. Due to the large surface area of the resulting sensor film and the superior electrical conductivity of such long conducting nanohybrids, the as-prepared dopamine sensor showed a significantly wide linear detection range (4-90 μmol/L) and low detection limitation (0.24 μmol/L) for dopamine. The sensor also showed excellent anti-interference property, which is successfully applied to detect dopamine in real urine samples, demonstrating a promising feature for practical application in biomedical diagnosis. This rationally integrated hierarchical nano-micro architecture, which can be served as a versatile platform for immobilizing functional factors, gives rise to a series of advantages compared with the traditional cloddy polymer/CNTs nanocomposites, such as increased mechanical stability, higher specific surface area, larger loading capacity of functional factors, and better electrical conductivity, thereby showing great application potential in a wide range of fields, like biosensors and other microelectronic devices.

       

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