配体链包覆纳米粒子的表面相分离及自组装的模拟研究

doi:10.7503/cjcu20160086

摘要/Abstract

摘要：

通过耗散粒子动力学方法, 模拟了二元配体链包覆的纳米粒子表面的相分离行为, 并与现有的模拟和实验体系进行对比. 研究结果印证了相分离驱动力是配体链错位所导致的构象熵的结论. 进一步以相分离得到的Janus和三嵌段Janus结构纳米粒子作为构筑单元, 研究了其在选择性溶剂中的自组装行为. 结果表明, Janus粒子易自组装成为双层囊泡结构, 而三嵌段Janus粒子则更易形成单层囊泡结构. 对于从配体链包覆的纳米粒子出发, 设计具有特殊功能的囊泡提供了理论支持.

关键词: 纳米粒子, 相分离, 自组装, 耗散粒子动力学, 囊泡

Abstract:

A simulation study was focused on the phase separation of binary ligands coated on the nanoparticle via the dissipative particle dynamics. After comparing with available simulation and experimental works in literatures, the results support the viewpoint that the driving force comes from the conformational entropy arisen due to a mismatch of ligand chains. A further investigation is conducted on the self-assembly of Janus or triblock Janus nanoparticles in selective solvents. The simulations show that the Janus particles tend to assemble into double-layered vesicle structure, while the triblock Janus particles can form single-layered vesicle structure. This study supplies the theoretical guideline for the design of functional vesicle material via the polymer coated nanoparticles.

Key words: Nanoparticles, Phase separation, Self-assembly, Dissipative particle dynamics, Vesicle

中图分类号:

O641
O631

TrendMD:

徐凡华, 衡晓, 任建学, 周恒为. 配体链包覆纳米粒子的表面相分离及自组装的模拟研究. 高等学校化学学报, 2016, 37(6): 1115.

XU Fanhua, HENG Xiao, REN Jianxue, ZHOU Hengwei. Simulation Study of the Phase Separation and Self-assembly of Nanoparticles Coated with Ligands^†. Chem. J. Chinese Universities, 2016, 37(6): 1115.

图/表 8

Fig.1 Initial configuration of the nanoparticle grafted with binary ligands

Table 1 DPD interaction parameters between different types of beads during the ligand phase separation on the nanoparticles

Species	α_ij
Species	A	B	S	N
A	18.75	33.75	18.75	18.75
B		18.75	18.75	18.75
S			18.75	18.75
N				18.75

Fig.2 Phase separation on the nanoparticle grafted by binary ligands(A1), (A2): NA∶NB=4∶4 ; (B1), (B2): NA∶NB=4∶6 ; (C1), (C2): NA∶NB=4∶10 ; (D1), (D2): NA∶NB=4∶13. (A1—D1) Show only the arrangements of head groups of ligands, in which the pink and purple beads represent head groups of A and B ligands, respectively; (A2—D2) show the corresponding arrangements of the whole ligands, in which the pink and blue beads represent A and B ligands, respectively.

Table 2 DPD interaction parameters between different types of beads during the self-assembly of nanoparticles

Species	α_ij
Species	A	B	S	N
A	25	35	25	50
B		25	60	50
S			25	50
N				25

Fig.3 Double-layered vesicle structures self-assembled by Janus nanoparticles as the building blocks(A) Scheme of Janus particle. (B1) and (B2) mA∶mB=18∶24; (C1) and (C2) mA∶mB=24∶18. (B1) and (C1) show the structure of only the nanoparticle framework, in which pink and blue represent the surface parts of nanoparticles grafted with hydrophilic and hydrophobic ligands, respectively; (B2) and(C2) show the overall structure involving ligands, in which the dark blue represents the nanoparticle, while the pink and blue represent the hydrophilic and hydrophobic ligands.

Fig.4 Morphology evolution during the formation of double-layered vesicleFrom (A) to (I), it indicates the time evolution. The representations are the same as those in the bottom row of Fig.3.

Fig.5 Single-layered vesicle structures self-assembled by triblock Janus nanoparticles as the building blocks (A) Scheme of triblock Janus particle. (B1) and (B2) mA∶mB=8∶34; (C1) and (C2) mA∶mB=13∶29; (D1) and (D2) mA∶mB=18∶24. The representations of the (B1—D1) and (B2—D2) are the same as those in Fig.3.

Fig.6 Morphology evolution during the formation of single-layered vesicleFrom (A) to (I), it indicates the time evolution. The representations are the same as those in the bottom row of Fig.3.

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