State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science , Fudan University , Shanghai , 200438 , People's Republic of China.
Department of Chemistry and Biochemistry , University of Maryland , College Park , Maryland 20742 , United States.
J Am Chem Soc. 2019 May 15;141(19):7917-7925. doi: 10.1021/jacs.9b02316. Epub 2019 May 2.
Nanoparticle self-assembly has emerged as an indispensable tool in designing structured materials with a wide range of applications, but quantitatively predicting the assembly process and structures still remains challenging. Drawing inspiration from the toolbox of molecular reactions and behaviors is of utmost importance in further advancement of principles and theories for assembling nanoparticles at a length scale orders of magnitude larger. Here we represent a general paradigm for the predictive self-assembly of binary inorganic nanoparticles into linear nanostructures in periodic sequence by expanding the horizon of alternating copolymerization at the molecular level to nanoscale colloidal systems. Nanoparticles grafted with reactive block copolymers are viewed as nanoscale monomers ("nanomers"), and the rapid dimerization of co-nanomers into molecular dipole-like dimers, resembling the preferential formation of dimeric intermediates or charge-transfer complexes from co-monomers in molecular copolymerization, is crucial to the organization of co-nanomers in alternating sequence. We also demonstrate that the classic kinetics and statistics of polycondensation of molecular alternating copolymers (e.g., Nylon-66) can be utilized to quantitatively predict the copolymerization process of nanomers.
纳米粒子自组装已成为设计具有广泛应用的结构化材料不可或缺的工具，但定量预测组装过程和结构仍然具有挑战性。从分子反应和行为的工具箱中汲取灵感，对于进一步推进组装纳米粒子的原理和理论具有重要意义，因为这些原理和理论可以将组装尺度扩大到数量级。在这里，我们通过将分子水平上的交替共聚扩展到纳米级胶体体系，提出了一种将二元无机纳米粒子预测性地自组装成线性纳米结构的通用范例。接枝有反应性嵌段共聚物的纳米粒子被视为纳米级单体（“纳米单体”），而共纳米单体的快速二聚化形成类似于分子偶极二聚体的分子偶极二聚体，类似于从分子共聚的共单体中优先形成二聚体中间体或电荷转移配合物，这对于共纳米单体在交替序列中的组织至关重要。我们还证明，可以利用经典的缩聚动力学和统计学来定量预测纳米单体的共聚过程，例如聚酰胺-66。
