Multifunctional Hollow–Shell Microspheres Derived from Cross-Linking of MnO2 Nanoneedles by Zirconium-Based Coordination Polymer: Enzyme Mimicking, Micromotors, and Protein Immobilization

Multifunctional Hollow–Shell Microspheres Derived from Cross-Linking of MnO2 Nanoneedles by Zirconium-Based Coordination Polymer: Enzyme Mimicking, Micromotors, and Protein Immobilization
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DOI:
10.1021/acs.chemmater.7b04945
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发表时间:
2018-02
影响因子:
8.6
通讯作者:
Jian Sun-;Yaqi Fu;Rong Li;W. Feng
Jian Sun-;Yaqi Fu;Rong Li;W. Feng
中科院分区:
材料科学2区
文献类型:
--
作者:
Jian Sun-;Yaqi Fu;Rong Li;W. Feng

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制备了二氧化锰微球,并在其表面垂直生长纳米针。以二氧化锰微球为模板,以Zr(IV)离子与2-甲基咪唑在甲醇中室温配位合成锆基配位聚合物(Zr- cp)/金属-有机-骨架。纳米针被Zr-CP包裹,纳米针的碱基与Zr-CP交联。核心MnO2的蚀刻产生了一个空心壳结构h-MnO2@Zr-CP。壳由松散的外层和致密的内层组成,具有类似氧化酶和过氧化氢酶的活性。h-MnO2@Zr-CP可以用H2O2作为燃料作为微电机。六组氨酸标记的酶可以利用六组氨酸标记与Zr-CP之间的协同相互作用,选择性地强吸附到大容量的空心壳微球上。将d-氨基酸氧化酶(DAAO)固定在空心壳微球上,并测定了其偶联物DAAO/h-。
MnO2 microspheres were prepared with nanoneedles vertically growing on their surfaces. The MnO2 microspheres were used as templates for the growth of zirconium-based coordination polymer (Zr-CP)/metal–organic-framework, which was synthesized by coordination between Zr(IV) ions and 2-methylimidazole in methanol at room temperature. The nanoneedles were enwrapped by Zr-CP, and the bases of the MnO2 nanoneedles were cross-linked with Zr-CP. Etching of the core MnO2 produced a hollow–shell structure h-MnO2@Zr-CP. The shell, consisting of a loose outer layer and a dense inner layer, possesses oxidase- and catalase-like activities. h-MnO2@Zr-CP can work as a micromotor with H2O2 as the fuel. Hexahistidine-tagged enzymes can be selectively and strongly absorbed onto the hollow–shell microspheres with a large capacity by taking advantage of the coordinative interactions between the hexahistidine-tags and Zr-CP. d-Amino acid oxidase (DAAO) was immobilized on the hollow–shell microspheres, and the conjugate DAAO/h-...