Polymerization-like kinetics of the self-assembly of colloidal nanoparticles into supracolloidal polymers. 2018

Xiaodong Ma, and Yaru Zhou, and Liangshun Zhang, and Jiaping Lin, and Xiaohui Tian
Shanghai Key Laboratory of Advanced Polymeric Materials, State Key Laboratory of Bioreactor Engineering, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China. zhangls@ecust.edu.cn jlin@ecust.edu.cn.

The self-assembly of colloidal nanoparticles is conceptually analogous to the polymerization of reactive monomers in molecular systems. However, less is known about the polymerization of colloidal nanoparticles into supracolloidal polymers. Herein, using coarse-grained molecular dynamics and theoretical analysis, we reveal the self-assembly mechanism and kinetics of colloidal nanoparticles constructed from triblock terpolymers. The results show that the formation pathway of supracolloidal polymers involves monomer condensation and oligomer coalescence through the manner of end-to-end collisions. In contrast to the polymerization kinetics of molecular systems, the simulations and theoretical analysis definitely demonstrate that the growth of supracolloidal polymers obeys diffusion-controlled step-growth polymerization kinetics with a variable rate coefficient, where the growth rate is dependent upon the concentration of colloidal nanoparticles and the molecular information of triblock terpolymers. Our findings possess wide implications for understanding the growth of supracolloidal polymers, which is important for the rational and precise design of one-dimensional self-assembled superstructures with new horizons for biomedical applications.

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