纳米粒子引导两亲嵌段共聚物的自组装。
Nanoparticle-directed self-assembly of amphiphilic block copolymers.
机构信息
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
出版信息
Langmuir. 2010 Sep 7;26(17):14345-50. doi: 10.1021/la1025558.
Nanoparticles can form unique cavity-like structures in core-shell type assemblies of block copolymers through the cooperative self-assembly of nanoparticles and block copolymers. We show that the self-assembly behavior is general for common as-synthesized alkyl-terminated nanoparticles for a range of nanoparticle sizes. We examined various self-assembly conditions such as solvent compositions, nanoparticle coordinating ligands, volume fraction of nanoparticles, and nanoparticle sizes in order to elucidate the mechanism of the radial assembly formation. These experiments along with strong segregation theory calculations indicated that both the enthalpic interaction and the polymer stretching energy are important factors in the coassembly formation. The slightly unfavorable interaction between the hydrophobic segment of polymers and alkyl-terminated nanoparticles causes the accumulation of nanoparticles at the interface between the polymer core and the shell, forming the unique cavity-like structure. The coassemblies were stabilized for a limited range of nanoparticle volume fractions within which the inclusion of nanoparticle layers reduces the polymer stretching. The volume fraction range yielding the well-defined radial coassembly structure was mapped out with varying nanoparticle sizes. The experimental and theoretical phase map provides the guideline for the coassembly formation of as-synthesized alkyl-terminated nanoparticles and amphiphilic block copolymers.
纳米粒子可以通过纳米粒子和嵌段共聚物的协同自组装,在嵌段共聚物的核壳型组装中形成独特的腔状结构。我们表明,自组装行为对于一系列纳米粒子尺寸的常见合成的烷基封端纳米粒子是普遍的。我们研究了各种自组装条件,例如溶剂组成、纳米粒子配位配体、纳米粒子的体积分数和纳米粒子尺寸,以阐明径向组装形成的机制。这些实验以及强分离理论计算表明,焓相互作用和聚合物拉伸能都是共组装形成的重要因素。聚合物疏水区段和烷基封端纳米粒子之间的相互作用略有不利,导致纳米粒子在聚合物核和壳之间的界面处聚集,形成独特的腔状结构。共组装在纳米粒子体积分数的有限范围内稳定,其中纳米粒子层的包含会降低聚合物的拉伸。通过改变纳米粒子的尺寸,绘制出产生明确定义的径向共组装结构的体积分数范围。实验和理论相图为合成的烷基封端纳米粒子和两亲嵌段共聚物的共组装形成提供了指导。