Site-Specific Chemistry on Gold Nanorods: Curvature-Guided Surface Dewetting and Supracolloidal Polymerization
Site-Specific Chemistry on Gold Nanorods: Curvature-Guided Surface Dewetting and Supracolloidal Polymerization
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DOI：
10.1021/acsnano.3c03929
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发表时间：
2023-06-21
期刊：
影响因子：
17.1
通讯作者：
He, Jie
中科院分区：
文献类型：
--
作者：
Duan, Hanyi;Jia, Zhenyang;He, Jie
控制颗粒间相互作用的方向和强度高度依赖于在纳米颗粒（NP）构建块上接枝各向异性配体的使用。我们报告了一种配体缺陷交换策略，以实现特定位点的聚合物接枝的金纳米棒（AuNRs）。通过调节配体浓度（C（PS））和溶剂条件（C（水）在二甲基甲酰胺中的溶液），用疏水聚苯乙烯配体和两亲性表面活性剂进行配体交换，可以得到具有可控表面覆盖率的片状AuNR。在< 0.08链/nm（2）的低接枝密度下，通过表面去湿可合成出两端均为聚合物结构域的哑铃状金核受体，纯度> 94%。这些位点特异性修饰的AuNRs在水溶液中表现出很好的胶体稳定性。哑铃状的AuNR在热退火后可以进一步发生超胶体聚合，形成一维等离子体激元链。动力学研究表明，这种超胶体聚合遵循温度-溶剂叠加原理。利用两个不同长宽比的AuNR的共聚，我们通过改变纳米棒构建块的反应性来展示链结构的设计。我们的研究结果提供了见解的各向异性纳米粒子，有可能作为聚合物guidedsupracolloidal自组装的单位的合成后设计。
Control of interparticle interactions in terms of theirdirectionand strength highly relies on the use of anisotropic ligand graftingon nanoparticle (NP) building blocks. We report a ligand deficiencyexchange strategy to achieve site-specific polymer grafting of goldnanorods (AuNRs). Patchy AuNRs with controllable surface coveragecan be obtained during ligand exchange with a hydrophobic polystyreneligand and an amphiphilic surfactant while adjusting the ligand concentration(C (PS)) and solvent condition (C (water) in dimethylformamide). At a low grafting densityof & LE;0.08 chains/nm(2), dumbbell-like AuNRs with twopolymer domains capped at the two ends can be synthesized throughsurface dewetting with a high purity of >94%. These site-specifically-modifiedAuNRs exhibit great colloidal stability in aqueous solution. Dumbbell-likeAuNRs can further undergo supracolloidal polymerization upon thermalannealing to form one-dimensional plasmon chains of AuNRs. Such supracolloidalpolymerization follows the temperature-solvent superpositionprinciple as revealed by kinetic studies. Using the copolymerizationof two AuNRs with different aspect ratios, we demonstrate the designof chain architectures by varying the reactivity of nanorod buildingblocks. Our results provide insights into the postsynthetic designof anisotropic NPs that potentially serve as units for polymer-guidedsupracolloidal self-assembly.