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一锅法对PMMA及聚酯类材料的表面改性及抗生物垢性能评价

赵  莹1,2,董继程1,2,方  元1,2,张立军3,4,靳  琳3,4,刘  波1,2,程  昉1,2   

  1. 1. 大连理工大学化工学院制药工程系

    2.精细化工国家重点实验室

    3. 医学部 4. 大连市第三人民医院

  • 收稿日期:2024-12-27 修回日期:2025-03-19 网络首发:2025-04-01 发布日期:2025-04-01
  • 通讯作者: 程昉 E-mail:ffcheng@dlut.edu.cn
  • 基金资助:
    国家自然科学基金(批准号:82171032, 21773022),辽宁省应用基础研究项目(批准号:2022JH2/101300036)和大连市第三人民医院科研项目(批准号:2022ky001, 2022ky002)资助

Evaluation of Surface Modification and Anti-biofouling Performance of PMMA and Polyester Materials by One-pot Method

ZHAO Ying1,2, DONG Jicheng1,2, FANG Yuan1,2, ZHANG Lijun3,4, JIN Lin3,4, LIU Bo1,2, CHENG Fang1,2   

  1. 1. Department of Pharmaceutical Engineering, School of Chemical Engineering

    2. State Key Laboratory of Fine Chemicals

    3. Faculty of Medicine, Dalian University of Technology 4. Dalian Third People’s Hospital

  • Received:2024-12-27 Revised:2025-03-19 Online First:2025-04-01 Published:2025-04-01
  • Contact: CHENG Fang E-mail:ffcheng@dlut.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China(Nos.82171032, 21773022), the Liaoning Province Applied Research Program for Basic Research, China(No.2022JH2/101300036) and the Dalian Third People’s Hospital Research Program, China(Nos.2022ky001, 2022ky002)

摘要: 报道了一种针对PMMA及聚酯类材料表面改性的通用方法,制备了广谱性和可后续反应活性的具有抗蛋白抗细菌性能的涂层,同时该方法也避免了引入特定反应基团的限制. 以有机玻璃(PMMA)为例,采用一锅法和两步法在PMMA上聚合两性离子单体甲基丙烯酸磺基甜菜碱(SBMA),通过元素分析优选一锅法深入研究. 同时该优化的改性方法在其他聚酯类材料包括聚对苯二甲酸丁二醇酯有机玻片(PBT)、聚碳酸酯有机玻片(PC)、聚对苯二甲酸-1, 4-环己烷二甲醇酯有机玻片(PCT)和聚对苯二甲酸乙二醇酯有机玻片(PET)的表面上验证了广谱性. Ellman’s assay定量涂层中的残余乙烯基砜基团密度,确定了该涂层具有可后续反应活性. 对改性后的PMMA 抗生物垢实验研究表明:采用石英电子微天平(QCM)评价涂层抗牛血清白蛋白(BSA)的吸附能力,一锅法涂层显著减少了72.3%的蛋白质非特异性吸附;考察了静态涂层抗细菌黏附能力,对于蜡样芽孢杆菌、大肠杆菌和金黄色葡萄球菌,静态下涂层细菌附着面积减少80%以上;采用设计的流动池和流场计算,在两种剪切力(0.16 dynes/cm2和1.6 dynes/cm2)的流动条件下均可以抵抗细菌附着能力.

关键词: 一锅法, 两性离子, 抗细菌黏附, 流动条件, 剪切力

Abstract: A generalized method for surface modification of poly(methyl methacrylate)(PMMA) and polyester materials has been reported to prepare broad-spectrum and subsequently reactive coatings, which have anti-protein and anti-bacterial properties, while avoiding the restriction of introducing specific reaction groups. Taking plexiglass(PMMA) as an example, amphoteric monomer(Sulfobetaine methacrylate, SBMA) was polymerized on PMMA by one-pot and two-step methods, and the one-pot method was optimized for in-depth study by elemental analysis. At the same time, the optimized modification method was verified to be broad-spectrum on the surface of other polyester materials including PBT, PC, PCT and PET. Ellman's assay quantified the density of residual vinyl sulfone groups in the coating to determine the subsequent reactivity of the coating. The anti-biofouling experimental study of the modified PMMA showed that: (1) the anti-BSA adsorption ability of the modified PMMA was evaluated by quartz electronic microbalance(QCM), and the one-pot coating significantly reduced the non-specific adsorption of the protein by 72.3%; (2) the anti-bacterial adhesion ability of the static coating was investigated, and the bacterial adhesion area of the coating was reduced by more than 80% in the case of Bacillus cereus, Escherichia coli and Staphylococcus aureus under the static condition; (3) using the designed flow cell and flow field calculations, the bacterial adhesion resistance was achieved under two flow conditions of shear forces(0.16 dynes/cm2 and 1.6 dynes/cm2).

Key words: One-pot method, Zwitterion; Anti-bacterial adhesion, Flow condition, Shear force

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