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    刘子强, 张国颖. 基于不对称星形聚合物制备Janus杂化金纳米粒子[J]. 功能高分子学报, 2020, 33(4): 342-349. doi: 10.14133/j.cnki.1008-9357.20190819001
    引用本文: 刘子强, 张国颖. 基于不对称星形聚合物制备Janus杂化金纳米粒子[J]. 功能高分子学报, 2020, 33(4): 342-349. doi: 10.14133/j.cnki.1008-9357.20190819001
    LIU Ziqiang, ZHANG Guoying. Preparation of Janus Hybrid Gold Nanoparticles Based on Asymmetric Star Polymers[J]. Journal of Functional Polymers, 2020, 33(4): 342-349. doi: 10.14133/j.cnki.1008-9357.20190819001
    Citation: LIU Ziqiang, ZHANG Guoying. Preparation of Janus Hybrid Gold Nanoparticles Based on Asymmetric Star Polymers[J]. Journal of Functional Polymers, 2020, 33(4): 342-349. doi: 10.14133/j.cnki.1008-9357.20190819001

    基于不对称星形聚合物制备Janus杂化金纳米粒子

    Preparation of Janus Hybrid Gold Nanoparticles Based on Asymmetric Star Polymers

    • 摘要: 利用原子转移自由基聚合(ATRP)和叠氮-炔基点击化学反应,对β-环糊精(β-CD)进行不对称改性,在其宽截面一侧聚合得到14条亲水性聚(N-异丙基丙烯酰胺)(PNIPAM)链,在其窄截面一侧偶联7个硫辛酸(LA)基元,得到不对称星形聚合物(LA)7-CD-(PNIPAM4614,采用配体交换法以此聚合物对金纳米粒子进行表面修饰,得到表面具有不对称化学组成和亲疏水性的Janus杂化金纳米粒子(Au3.1-CD-(PNIPAM4614),该两亲性Janus杂化金纳米粒子可以在选择性溶剂水中组装形成类似于胶束结构的球状组装体。

       

      Abstract: A highly efficient and simple method for preparing small-size Janus gold nanoparticles (AuNPs) capable of self-assembling was developed. Firstly, the asymmetric star polymers ((LA)7-CD-(PNIPAM46)14) were fabricated based on β-cyclodextrin (β-CD) by combining atom transfer radical polymerization (ATRP) and click chemistry. Secondary, the hydroxyl groups on the wide cross-section of the β-CD molecule were modified to be ATRP initiator moieties, which then initiated the polymerization of N-isopropyl acrylamide (NIPAM) to form fourteen PNIPAM chains via ATRP. The primary hydroxyl groups on the narrow cross-section of the β-CD molecule were converted into azide groups and then coupled with 5-(1,2-dithiolan-3-yl)-N-(prop-2-ynyl) pentanamide molecules by click chemistry. The obtained asymmetric star polymers ((LA)7-CD-(PNIPAM46)14) were used to modify AuNPs that were formerly surface-stabilized by n-butylthiol through the ligand exchange process. Due to the steric effect of (LA)7-CD-(PNIPAM46)14 macromolecules, Janus hybrid AuNPs, Au3.1-CD-(PNIPAM46)14, with amphiphilic surface were prepared, which could self-assemble in water into micelle-like aggregates, i.e. supermicelles. The chemical and chain structures of asymmetric (LA)7-CD-(PNIPAM46)14 star polymers and the amphiphilic Janus hybrid Au3.1-CD-(PNIPAM46)14 nanoparticles were characterized by Nuclear Magnetic Resonance (NMR), Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-TOF MS), Gel Permeation Chromatography (GPC) and Thermal Gravimetric (TG) analysis. The morphology and structure of the prepared micelle-like self-assemblies were investigated by Transmission Electron Microscope (TEM).

       

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