Light-enabled reversible self-assembly and tunable optical properties of stable hairy nanoparticles
Light-enabled reversible self-assembly and tunable optical properties of stable hairy nanoparticles
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DOI：
10.1073/pnas.1714748115
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发表时间：
2018-02-13
影响因子：
11.1
通讯作者：
Lin, Zhiqun
中科院分区：
文献类型：
--
作者：
Chen, Yihuang;Wang, Zewei;Lin, Zhiqun
通过使用环境触发器（温度、pH值、光或溶剂极性）来动态组织功能纳米粒子（NPs）的能力为快速方便地构建具有新结构和功能的各种复杂组件和材料开辟了重要的前景。在这里，我们报告了一种非常规的策略来制作稳定的毛状NPs，具有光激活可逆和可靠的自组装和可调谐的光学特性。我们的核心策略是明智地设计两亲星形双嵌段共聚物，包括内部亲水嵌段和外部疏水光响应嵌段作为纳米反应器，以指导单分散等离子体NPs的合成，并永久地覆盖光响应聚合物。通过调节星形二嵌段共聚物内部亲水嵌段的长度，可以精确地调整毛状NPs的大小和形状。光响应性聚合物在NP表面的永久锚定使得NP具有在不同波长的光下随需自组装和自拆卸的吸引人的特征，这一点通过可调谐的NP表面等离子体共振吸收和NP在分散和聚集状态之间的可逆转换得到了揭示。染料包封/释放研究表明，这种光响应性NPs可以作为智能客体分子纳米载体。通过扩展，星形嵌段共聚物策略可以制作一系列稳定的刺激响应NPs（例如，温度或ph敏感的聚合物覆盖磁性，铁电，上转换或半导体NPs）及其组件，用于NPs的自组装和结晶动力学的基础研究，以及光学，光电子，磁性技术，传感材料和设备，催化，纳米技术和生物技术的潜在应用。
The ability to dynamically organize functional nanoparticles (NPs) via the use of environmental triggers (temperature, pH, light, or solvent polarity) opens up important perspectives for rapid and convenient construction of a rich variety of complex assemblies and materials with new structures and functionalities. Here, we report an unconventional strategy for crafting stable hairy NPs with light-enabled reversible and reliable self-assembly and tunable optical properties. Central to our strategy is to judiciously design amphiphilic star-like diblock copolymers comprising inner hydrophilic blocks and outer hydrophobic photoresponsive blocks as nanoreactors to direct the synthesis of monodisperse plasmonic NPs intimately and permanently capped with photoresponsive polymers. The size and shape of hairy NPs can be precisely tailored by modulating the length of inner hydrophilic block of star-like diblock copolymers. The perpetual anchoring of photoresponsive polymers on the NP surface renders the attractive feature of self-assembly and disassembly of NPs on demand using light of different wavelengths, as revealed by tunable surface plasmon resonance absorption of NPs and the reversible transformation of NPs between their dispersed and aggregated states. The dye encapsulation/release studies manifested that such photoresponsive NPs may be exploited as smart guest molecule nanocarriers. By extension, the star-like block copolymer strategy enables the crafting of a family of stable stimuli-responsive NPs (e.g., temperature- or pH-sensitive polymer-capped magnetic, ferroelectric, upconversion, or semiconducting NPs) and their assemblies for fundamental research in self-assembly and crystallization kinetics of NPs as well as potential applications in optics, optoelectronics, magnetic technologies, sensory materials and devices, catalysis, nanotechnology, and biotechnology.