AB共聚物和纳米粒子组装形成有序结构的设计规则
Design Rules of Ordered Structure Formed by AB Diblock Copolymers and Nanoparticles in Dilute Solution
DOI: 10.12677/JAPC.2023.121002, PDF,    国家科技经费支持
作者: 李 洋*, 王科飞, 胡海燕, 王志超：吉林工商学院工学院，吉林 长春；李延春：吉林大学化学学院理论化学研究所，吉林 长春
关键词: AB两嵌段共聚物；纳米粒子；耗散粒子动力学；胶束；囊泡；AB Diblock Copolyme； Nanoparticle； Dissipative Particle Dynamics； Micelle； Vesicle
摘要: 利用耗散粒子动力学方法，我们系统研究了纳米粒子接枝AB两嵌段共聚物在稀溶液中的自组装过程，不仅得到了胶束和囊泡等有序结构，还探究了该类体系的设计规则。我们发现嵌段共聚物的亲疏水比例对有序结构起到决定性的影响，纳米粒子复合体系的浓度对最终的结构也有一定程度的影响。无论是形成胶束还是形成囊泡，都会先形成纳米簇的聚集体，进而聚集甚至弯曲形成更加有序的结构。结合实验现象，我们通过调控初始结构中纳米粒子的排列方式，发现囊泡有两种截然不同的形成机制。最后，我们总结了这类自组装的设计规则，即亲疏水比例大于2:1时，很容易形成胶束，亲疏水比例小于1:2时，则很容易形成囊泡。
Abstract: 利用耗散粒子动力学方法，我们系统研究了纳米粒子接枝AB两嵌段共聚物在稀溶液中的自组装过程，不仅得到了胶束和囊泡等有序结构，还探究了该类体系的设计规则。我们发现嵌段共聚物的亲疏水比例对有序结构起到决定性的影响，纳米粒子复合体系的浓度对最终的结构也有一定程度的影响。无论是形成胶束还是形成囊泡，都会先形成纳米簇的聚集体，进而聚集甚至弯曲形成更加有序的结构。结合实验现象，我们通过调控初始结构中纳米粒子的排列方式，发现囊泡有两种截然不同的形成机制。最后，我们总结了这类自组装的设计规则，即亲疏水比例大于2:1时，很容易形成胶束，亲疏水比例小于1:2时，则很容易形成囊泡。
文章引用：李洋, 王科飞, 胡海燕, 王志超, 李延春. AB共聚物和纳米粒子组装形成有序结构的设计规则[J]. 物理化学进展, 2023, 12(1): 13-20. https://doi.org/10.12677/JAPC.2023.121002

参考文献

[1] Shim, M.K., Yang, S., Sun, I.-C. and Kim, K. (2022) Tumor-Activated Carrier-Free Prodrug Nanoparticles for Targeted Cancer Immunotherapy: Preclinical Evidence for Safe and Effective Drug Delivery. Advanced Drug Delivery Reviews, 183, Article ID: 114177. [Google Scholar] [CrossRef] [PubMed]
[2] Gagliardi, A., Giuliano, E., Venkateswararao, E., Fresta, M., Bulotta, S., Awasthi, V. and Cosco, D. (2021) Biodegradable Polymeric Nanoparticles for Drug Delivery to Solid Tumors. Frontiers in Pharmacology, 12, Article 601626. [Google Scholar] [CrossRef] [PubMed]
[3] Yan, L.-T. and Xie, X.-M. (2013) Computational Modeling and Simulation of Nanoparticle Self-Assembly in Polymeric Systems: Structures, Properties and External Field Effects. Progress in Polymer Science, 38, 369-405. [Google Scholar] [CrossRef] 
[4] Yi, C., Yang, Y., Liu, B., He, J. and Nie, Z. (2020) Polymer-Guided Assembly of Inorganic Nanoparticles. Chemical Society Reviews, 49, 465-508. [Google Scholar] [CrossRef] 
[5] Shifrina, Z.B., Matveeva, V.G. and Bronstein, L.M. (2020) Role of Polymer Structures in Catalysis by Transition Metal and Metal Oxide Nanoparticle Composites. Chemical Reviews, 120, 1350-1396. [Google Scholar] [CrossRef] [PubMed]
[6] Kakkar, A., Traverso, G., Farokhzad, O.C., Weissleder, R. and Langer, R. (2017) Evolution of Macromolecular Complexity in Drug Delivery Systems. Nature Reviews Chemistry, 1, Article No. 0063. [Google Scholar] [CrossRef] [PubMed]
[7] Boles, M.A., Engel, M. and Talapin, D.V. (2016) Self-Assembly of Colloidal Nanocrystals: From Intricate Structures to Functional Materials. Chemical Reviews, 116, 11220-11289. [Google Scholar] [CrossRef] [PubMed]
[8] Mai, Y. and Eisenberg, A. (2010) Controlled Incorporation of Particles into the Central Portion of Vesicle Walls. Journal of the American Chemical Society, 132, 10078-10084. [Google Scholar] [CrossRef] [PubMed]
[9] Guo, Y.Y., Harirchian-Saei, S, Izumi, C.M.S. and Moffitt, M.G. (2011) Block Copolymer Mimetic Self-Assembly of Inorganic Nanoparticles. ACS Nano, 5, 3309-3318. [Google Scholar] [CrossRef] [PubMed]
[10] Song, J.B., Cheng, L., Liu, A.P., Yin, J., Kuang, M. and Duan, H.W. (2011) Plasmonic Vesicles of Amphiphilic Gold Nanocrystals: Self-Assembly and External-Stimuli-Triggered Destruction. Journal of the American Chemical Society, 133, 10760-10763. [Google Scholar] [CrossRef] [PubMed]
[11] Hu, J.M., Wu, T., Zhang, G.Y. and Liu, S.Y. (2012) Efficient Synthesis of Single Gold Nanoparticle Hybrid Amphiphilic Triblock Copolymers and Their Controlled Self-Assembly. Journal of the American Chemical Society, 134, 7624- 7627. [Google Scholar] [CrossRef] [PubMed]
[12] He, J., Liu, Y.J., Babu, T., Wei, Z.J. and Nie, Z.H. (2012) Self-Assembly of Inorganic Nanoparticle Vesicles and Tubules Driven by Tethered Linear Block Copolymers. Journal of the American Chemical Society, 134, 11342-11345. [Google Scholar] [CrossRef] [PubMed]
[13] Yuan, S.L., Cai, Z.T. and Xu, G.Y. (2002) Dynamic Simulation of Aggregation Morphology in Surfactant Solution. Acta Chimica Sinica, 60, 241-245.
[14] Zhao, Y., Liu, Y.-T., Lu, Z.-Y. and Sun, C.-C. (2008) Effect of Molecular Architecture on the Morphology Diversity of the Multicompartment Micelles: A Dissipative Particle Dynamics Simulation Study. Polymer, 49, 4899-4909. [Google Scholar] [CrossRef] 
[15] Liu, Y.-T., Zhao, Y., Liu, H., Liu, Y.-H. and Lu, Z.-Y. (2009) Spontaneous Fusion between the Vesicles Formed by A2n(B2)n Type Comb-Like Block Copolymers with a Semiflexible Hydrophobic Backbone. Journal of Physical Chemistry B, 113, 15256-15262. [Google Scholar] [CrossRef] [PubMed]
[16] Zhao, Y., You, L.-Y., Lu, Z.-Y. and Sun, C.-C. (2009) Dissipative Particle Dynamics Study on the Multicompartment Micelles Self-Assembled from the Mixture of Diblock Copolymer Poly(Ethyl Ethylene)-Block-Poly(Ethylene Oxide) and Homopolymer Poly(Propylene Oxide) in Aqueous Solution. Polymer, 50, 5333-5340. [Google Scholar] [CrossRef] 
[17] Zhao, Y., Xie, Y., Lu, Z.-Y. and Sun, C.-C. (2009) Dissipative Particle Dynamics Simulation of Physical Gelation Behavior of P123(PEO20-PPO70-PEO20) Block Copolymer Aqueous Solution. Chemical Journal of Chinese Universities, 30, 2455-2459.
[18] Zhu, P.F., Li, Y., Li, Q.W., Song, X.W., Cao, X.L. and Li, Z.Q. (2011) Mesoscopic Simulation of the Interfacial Behavior of Biosurfactant Rhamnolipids and the Synergistic Systems. Acta Chimica Sinica, 69, 2420-2426.
[19] Li, Y.C., Wang, Y.L., Li, Z.W., Liu, H. and Lu, Z.Y. (2013) Towards Larger Spatiotemporal Scales in Polymer Simulations. Chinese Science Bulletin, 58, 3595-3599. [Google Scholar] [CrossRef] 
[20] Sun, N.N., Li, Y.M., Wang, D.X., Bao, M.T. and Tong, L.J. (2013) Mesoscopic Simulation Studies on the Self-Assembly of Pluronic at Oil/Water Interface. Acta Chimica Sinica, 71, 186-192. [Google Scholar] [CrossRef] 
[21] He, L.L., Zhang, L.X. and Liang, H.J. (2010) Mono- or Bidisperse Nanorods Mixtures in Diblock Copolymers. Polymer, 51, 3303-3314. [Google Scholar] [CrossRef] 
[22] Yue, T.T., Li, S.Y., Zhang, X.R. and Wang, W.C. (2010) The Relationship between Membrane Curvature Generation and Clustering of Anchored Proteins: A Computer Simulation Study. Soft Matter, 6, 6109-6118. [Google Scholar] [CrossRef] 
[23] Ding, H.-M., Tian, W.-D. and Ma, Y.-Q. (2012) Designing Nanoparticle Translocation through Membranes by Computer Simulations. Acs Nano, 6, 1230-1238.. [Google Scholar] [CrossRef] [PubMed]
[24] Huang, M.X., Li, Z.Q. and Guo, H.X. (2012) The Effect of Janus Nanospheres on the Phase Separation of Immiscible Polymer Blends via Dissipative Particle Dynamics Simulations. Soft Matter, 8, 6834-6845. [Google Scholar] [CrossRef] 
[25] Español, P. and Warren, P. (1995) Statistical Mechanics of Dissipative Particle Dynamics. Europhysics Letters, 30, 191-196. [Google Scholar] [CrossRef] 
[26] Groot, R.D. and Warren, P.B. (1997) Dissipative Particle Dynamics: Bridging the Gap between Atomistic and Mesoscopic Simulation. Journal of Chemical Physics, 107, 4423-4435. [Google Scholar] [CrossRef] 
[27] Qian, H.-J., Lu, Z.-Y., Chen, L.-J., Li, Z.-S. and Sun, C.-C. (2005) Computer Simulation of Cyclic Block Copolymer Microphase Separation. Macromolecules, 38, 1395-1401. [Google Scholar] [CrossRef] 
[28] Zhu, Y.-L., Liu, H., Li, Z.-W., Qian, H.-J., Milano, G. and Lu, Z.-Y. (2013) GALAMOST: GPU-Accelerated Large- Scale Molecular Simulation Toolkit. Journal of Computational Chemistry, 34, 2197-2211. [Google Scholar] [CrossRef] [PubMed]