Self-Assembly of Amphiphilic Plasmonic Micelle-Like Nanoparticles in Selective Solvents
Self-Assembly of Amphiphilic Plasmonic Micelle-Like Nanoparticles in Selective Solvents
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DOI：
10.1021/ja402015s
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发表时间：
2013-05-29
影响因子：
15
通讯作者：
Nie, Zhihong
中科院分区：
文献类型：
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作者：
He, Jie;Huang, Xinglu;Nie, Zhihong
由金纳米颗粒 (AuNP) 和两亲嵌段共聚物 (BCP) 组成的两亲等离子体胶束状纳米粒子 (APMN) 在结构上类似于聚合物胶束，具有明确的结构和化学性质。 APMN 可以被视为模拟更高水平的胶束自组装的原型。对这种二次自组装的理解对于新的分层纳米结构的自下而上的设计特别重要。本文描述了 APMN 组件在选择性溶剂中的自组装、建模和应用。在水/四氢呋喃的混合物中，APMN 组装成各种超结构，包括单分子胶束、APMN 数量受控的簇和囊泡，具体取决于聚合物系链的长度和 AuNP 核的大小。熵和焓对与组装过程相关的整体自由能的微妙相互作用，强烈依赖于 APMN 的球形结构，产生了与线性 BCP 组装不同的组装图。我们的实验和计算研究表明，组件的形态很大程度上取决于有效纳米颗粒（即纳米颗粒与系链作为一个整体）的可变形性。由于金核显着的等离子体耦合，APMNs 的组装在近红外范围内产生强烈的吸收，从而促进其在癌症生物成像和光热治疗中的生物医学应用。
Amphiphilic plasmonic micelle like nanoparticles (APMNs) composed of gold nanoparticles (AuNPs) and amphiphilic block copolymers (BCPs) structurally resemble polymer micelles with well-defined architectures and chemistry. The APMNs can be potentially considered as a prototype for modeling a higher level self assembly of micelles The understanding of such secondary self assembly is of particular importance for the bottom up design of new hierarchical nanostructures. This, article describes the self assembly, modeling, and applications of APMN assemblies in selective solvents. In a mixture of water/tetrahydrofuran, APMNs assembled into various superstructures, including unimolecular micelles, clusters with controlled number of APMNs, and vesicles, depending on the lengths of polymer tethers and the sizes of AuNP cores. The delicate interplay of entropy and enthalpy contributions to the overall free energy associated with the assembly process, which is strongly dependent on the spherical architecture of APMNs, yields an assembly diagram that is different from the assembly of linear BCPs. Our experimental and computational studies suggested that the morphologies of assemblies were largely determined by the deformability of the effective nanoparticles (that is, nanoparticles together with tethered chains as a whole). The assemblies of APMNs resulted in strong absorption in near-infrared range due to the remarkable plasmonic coupling of Au cores, thus facilitating their biomedical applications in bioimaging and photothermal therapy of cancer.