通过电偶置换反应将合金手性纳米粒子的组成空间扩展到三元,Advanced Science

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通过电偶置换反应将合金手性纳米粒子的组成空间扩展到三元
Advanced Science ( IF 15.1 ) Pub Date : 2020-10-27 , DOI: 10.1002/advs.202001321
Ziyue Ni ₁ , Yuanmin Zhu _{2,

3} , Junjun Liu _{1,

4} , Lin Yang _{1,

4} , Peng Sun _{1,

2} , Meng Gu ₂ , Zhifeng Huang _{1,

4,

5}

Affiliation

金属手性纳米粒子（CNP）由原子手性晶格组成，是一种新兴的手性纳米材料，具有独特的不对称性质。通过电取代反应（GRR）介导的宿主 CNP 的手性传递已被进行，以将其组成空间从一元扩展到二元。进一步的组合扩展，例如三元，具有根本意义和实际需求。这里，采用逐层掠射角沉积在主体 Cu CNP 中掺杂电“惰性”掺杂剂 Au，以生成二元 Cu:Au CNP。“惰性”掺杂剂充当结构支架，协助手性从主体传递到 CNP 中阴极沉淀的第三种金属（M：Pt 和 Ag），从而形成其成分定制的多晶三元 Cu:Au:M CNP设计 GRR 持续时间。更多的支架Au原子有利于更快的手性转移，并且Au辅助的手性转移遵循一级动力学，在室温下反应速率系数约为0.3 h ^{-1 。}这项工作提供了对GRR介导的手性转移的进一步理解，并为增强对映体分化、对映体分离、不对称催化、生物成像和生物检测中的应用功能铺平了道路。

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Extension of Compositional Space to the Ternary in Alloy Chiral Nanoparticles through Galvanic Replacement Reactions

Metal chiral nanoparticles (CNPs), composed of atomically chiral lattices, are an emerging chiral nanomaterial showing unique asymmetric properties. Chirality transmission from the host CNPs mediated with galvanic replacement reactions (GRRs) has been carried out to extend their compositional space from the unary to binary. Further compositional extension to, e.g., the ternary is of fundamental interest and in practical demand. Here, layer‐by‐layer glancing angle deposition is used to dope galvanically “inert” dopant Au in the host Cu CNPs to generate binary Cu:Au CNPs. The “inert” dopants serve as structural scaffold to assist the chirality transmission from the host to the third metals (M: Pt and Ag) cathodically precipitating in the CNPs, enabling the formation of polycrystalline ternary Cu:Au:M CNPs whose compositions are tailored with engineering the GRR duration. More scaffold Au atoms are favored for the faster chirality transfer, and the Au‐assisted chirality transfer follows the first‐order kinetics with the reaction rate coefficient of ≈0.3 h⁻¹ at room temperature. This work provides further understanding of the GRR‐mediated chirality transfer and paves the way toward enhancing the application functions in enantiodifferentiation, enantioseperation, asymmetric catalysis, bioimaging, and biodetection.

更新日期：2020-12-03

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