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Heteroepitaxial growth of Au@Pd core–shell nanocrystals with intrinsic chiral surfaces for enantiomeric recognition

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Abstract

Noble metal surfaces with intrinsic chirality serve as an ideal candidate for investigating enantioselective chemistry due to their superior chemical durability and high catalytic activity. Recently, significant advance has been made in synthesizing metal nanocrystals with intrinsic chirality. Nonetheless, the majority reports are limited to gold. Herein, through a heteroepitaxial growth strategy, the synthesis of metal nanocrystals with intrinsic chirality to palladium was extended for the first time and their application in enantioselective recognition was demonstrated. The heteroepitaxial growth strategy allows for transferring the chirality of homochiral Au nanocrystals to Au@Pd core–shell nanocrystals. By employing the chiral Au@Pd nanocrystals as enantiomeric recognizing elements, a series of electrochemical sensors for chiral discrimination were developed. Under optimal conditions, the peak potential between D-dihydroxyphenylalanine (D-DOPA) and L-dihydroxyphenylalanine (L-DOPA) is about 80 mV, and the peak current of D-DOPA is 2 times as much as that of L-DOPA, which enables the determination of the enantiomeric excess (EE, %) of L-DOPA. Overall, this report not only introduces a heteroepitaxial growth strategy to synthesize metal nanocrystals with intrinsic chirality, but also demonstrates the superior capability of integrating intrinsic chirality and catalytic properties into metal nanocrystals for chiral recognition.

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摘要

本征手性贵金属表面具有优异的化学稳定性和高催化活性，因而成为研究对映选择性化学的理想对象。最近，本征手性金属纳米晶的合成领域取得了一系列重大进展。然而，大多数报道仅限于金元素。在本文中，通过异质外延生长策略，我们首次将本征手性金属纳米晶的合成扩展到钯元素，并应用于对映选择性识别。异质外延生长策略成功地将Au纳米晶的手性转移至Au@Pd核壳纳米晶。通过将手性Au@Pd纳米晶作为对映体识别探针，开发了一系列用于手性识别的电化学传感器。在最佳条件下，D-多巴和L-多巴之间的氧化峰值电位差约为80 mV，D-多巴的氧化峰值电流是L-多巴的2倍。这种性质可以在外消旋体溶液中测定L-多巴的对映体过量百分比。这项工作为合成具有本征手性的金属纳米晶提供了一种异质外延生长策略，并展示了具有本征手性和高催化活性金属纳米晶对手性识别应用的优越潜力。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 22072144, 22102171 and 21974131) and the Department of Science and Technology of Jilin Province (No. 20200201080JC).

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Authors and Affiliations

  1. State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China

    Feng-Xia Wu, Feng-Hua Li, Xia-Li Lv, Qi-Xian Zhang, Guo-Bao Xu & Wen-Xin Niu

  2. University of Chinese Academy of Sciences, Beijing, 100039, China

    Guo-Bao Xu & Wen-Xin Niu

  3. University of Science and Technology of China, Hefei, 230026, China

    Xia-Li Lv, Guo-Bao Xu & Wen-Xin Niu

  4. School of Materials Science and Engineering, Shanghai University, Shanghai, 200436, China

    Qi-Xian Zhang

  5. Zhejiang Institute of Advanced Materials, Shanghai University, Jiashan, 314113, China

    Qi-Xian Zhang

  6. Shaoxing Institute of Technology, Shanghai University, Shaoxing, 312000, China

    Feng-Hua Li & Qi-Xian Zhang

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  1. Feng-Xia Wu
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Wu, FX., Li, FH., Lv, XL. et al. Heteroepitaxial growth of Au@Pd core–shell nanocrystals with intrinsic chiral surfaces for enantiomeric recognition. Rare Met. 43, 225–235 (2024). https://doi.org/10.1007/s12598-023-02402-0

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