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聚合物接枝纳米粒子的自组装在功能材料领域的应用越来越广泛. 然而, 目前对于不同自组装形貌结构的动态转变路径的分析仍存在不足, 这将导致在实验和工业生产中无法实现进一步的精确调节和定向设计. 本文通过构建聚合物接枝斑块化三分纳米颗粒的粗粒度模型, 采用耗散粒子动力学模拟方法, 研究了斑块性质、接枝链的长度、比例以及接枝密度等因素对聚合物接枝柔性斑块化纳米粒子自组装行为和结构的影响. 本文系统地探讨了这些因素对柔性斑块化纳米粒子自组装结构转变的影响和调控机制, 得到了枝状结构、柱状结构、双层膜结构等多种结构. 研究中所获得的柔性斑块化纳米粒子的自组装结构(例如双层膜结构)为新型药物载体的设计提供了潜在的应用基础. 通过精确调控体系的特定结构特征, 能够实现药物的高效包载以及靶向递送功能, 从而显著提升药物的生物利用度和治疗效果.The self-assembly of polymer grafted nanoparticles is more and more used in the field of functional materials. However, there is still a lack of analysis on the dynamic transformation paths of different self-assembly morphologies, which makes it impossible to achieve further precise regulation and targeted design in experiments and industrial production. In this work the effects of block property, grafted chain length, ratio and grafting density on the self-assembly behavior and structure of polymer grafted flexible blocky nanoparticles are investigated by dissipative particle dynamics simulation method through the construction of coarse-grained model of polymer grafted ternary nanoparticles. The influence and regulation mechanisms of these factors on the self-assembly structure transformation of flexible blocky nanoparticles are systematically studied, and a variety of structures such as dendritic structure, columnar structure, and bilayer membrane are obtained. The self-assembly structure of flexible blocky nanoparticles obtained in this work (such as bilayer membrane structure) provides a potential application basis for designing drug carriers. By precisely regulating the specific structural characteristics of the system, it is possible to achieve efficient loading of drugs and targeted delivery functions, thus significantly improving the bioavailability and effect of drugs.
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Keywords:
- dissipative particle dynamics /
- self-assembly /
- dynamic pathways /
- flexible blocky nanoparticles
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图 1 聚合物接枝纳米粒子模型. 白色链段和灰色链段分别代表亲水链段和疏水链段. 蓝色斑块和黄色斑块分别对应接枝亲水链段(C)和疏水链段(D)的接枝区域, 红色斑块对应未接枝区域
Fig. 1. Polymer grafted nanoparticle model. The white and grey segments represent hydrophilic and hydrophobic segments, respectively. The blue and yellow patches correspond to the grafting regions of the hydrophil (C) and hydrophobic (D) chains, respectively, and the red patch corresponds to the non-grafting region.
图 2 柔性斑块化纳米粒子自组装过程中典型的结构 (a) 表示离散结构; (b) 表示枝状结构; (c) 表示柱状结构; (d) 表示双层膜结构
Fig. 2. Typical structures during self-assembly processes of flexible blocky nanoparticles: (a) Discrete structure; (b) dendritic structure; (c) columnar structure; (d) bilayer membrane structure.
图 3 柔性斑块化纳米粒子自组装结构随作用力参数$ {\alpha _{{\text{AS}}}} $和链段长度$ L $变化的相图
Fig. 3. Phase diagram of flexible block copolymer self-assembly structures varying with the parameter of the driving force and the segment length L.
图 4 (a) 不同接枝密度聚合物接枝纳米粒子自组装结构的相图, 其中
Fig. 4. (a) Phase diagram of self-assembled structure of grafted nanoparticles with different grafting density polymers.
图 5 疏水链段长度对聚合物形态影响的相位图, 其中
Fig. 5. Phase diagram of the influence of solvent-swollen segment length on polymer morphology.
图 6 双层膜结构平均膜厚度随疏溶剂链长的变化
Fig. 6. Variation of the average membrane thickness of the bilayer structure with the length of the hydrophobic solvent chain.
图 7 中心粒子在体系内的径向分布函数g(r), 其中黑色线代表枝状结构, 红色线代表柱状结构, 蓝色线代表双层膜结构
Fig. 7. Rdial distribution function g(r) of the central particle in the system. Black line represents the dendritic structure; red line represents the columnar structure; blue line represents the bilayer membrane structure.
图 8 枝状结构、柱状结构、双层膜结构自组装过程中的不同构象
Fig. 8. Different conformations of the self-assembly process of branched, columnar, and double-layer membrane structures.
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