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Chiral metal nanostructures: synthesis, properties and applications

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Abstract

Chirality, the property that an object cannot coincide with its mirror image arising from lack of mirror symmetry, is ubiquitous in nature at various length scales. The physical and chemical properties are strongly related to the nature of chiral complexes, playing a significant role in various fields such as photonics, biochemistry, medicine and catalysis. In particular, the recent flexible design of chiral metal nanostructures offers one platform for deeply understanding the origin of chirality and one roadmap for the precise construction of chiral nanomaterials directed by the applications. Herein, we summarize the different geometries and classical synthetic approaches to chiral noble metal nanomaterials. Moreover, chiroptical properties and potential applications of chiral metal nanostructures are discussed as well. Finally, the opportunities and challenges toward the synthesis and application of chiral metal nanostructures are proposed.

Graphical abstract

摘要

手性是物体由于缺乏镜像对称性而不能与其镜像重合的特性，其普遍存在于在自然界不同尺度的事物上。手性 配合物的物理化学性质与其手性性质密切相关，在光子学、生物化学、医学、催化等领域有着重要的应用，特别 是手性金属纳米结构的灵活设计为深入理解手性的起源提供了一个平台，并为由应用指导的手性纳米材料的精确 构建提供了一个路线图。本文综述了手性贵金属纳米材料的不同几何结构和经典的合成方法，此外还讨论了手性 金属纳米结构的手性光学性质和潜在的应用前景，最后对手性金属纳米结构的合成和应用提出了机遇和挑战。

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Fig. 1
Fig. 2

Reproduced with permission from Ref. [38]. Copyright 2013, Springer Nature

Fig. 3

Reproduced with permission from Ref. [61]. Copyright 2016, American Chemical Society. b Structure of tetracationic [Au20(PP3)4]4+ cluster. Reproduced with permission from Ref. [57]. Copyright 2014, John Wiley and Sons. c Schematic illustration of AuCu alloy nanoclusters with (inset) perfect mirror image CD spectra. d, e TEM images of D-Pen-protected AuCu nanoclusters. f–h Chiroptical properties of AuCu, Au and Cu nanoclusters, and i g-factors as a function of molar ratio of two metal precursors. j, k CD spectra of AuCu nanoclusters with different thiolated chiral molecules. Reproduced with permission from Ref. [62]. Copyright 2018 American Chemical Society

Fig. 4

Reproduced with permission from Ref. [65]. Copyright 2009, American Association for the Advancement of Science. e Schematic diagram and TEM image of left- and right-handed nanohelices formed by Au NPs attached on surface of DNA origami 24-helix bundles. f CD spectra of left-handed (red line) and right-handed (blue line) helices of 10 nm Au NPs. g CD spectra of assemblies of 16 nm Au NPs, showing a 400-fold enhancement, compared with f. h CD spectra of left-handed Au@Ag nanohelices (blue line) and left-handed Au@AgAu helices (green line), showing blueshift compared with pure Au one (red line). i Excessive metal deposition leading to large Au NPs and enhancement of CD signal for left-handed (orange line) and right-handed (purple line) Au@Ag helices. Reproduced with permission from Ref. [24]. Copyright 2012, Springer Nature

Fig. 5

Reproduced with permission from Ref. [85]. Copyright 2014, American Chemical Society. b Plasmonic circular dichroism being observed in chiral 3D gold nanorod assemblies made by self-assembling nanoantennas onto a twisted fiber template. c TEM image of left-handedness nanocomposite showing twisted fibers with adsorbed nanorods. Reproduced with permission from Ref. [86]. Copyright 2011, John Wiley and Sons. d TEM image of Au NRs with NR concentrations in presence of α-synuclein fibrils 0.5 nmol·L−1. e Image of a cryo-TEM tomography reconstruction of a composite fiber displaying 3D chiral arrangement of Au NRs. Right image shows an enlarged view of the top marked area of assembly. Reproduced with permission from Ref. [27]. Copyright 2018, National Academy of Sciences. f Tilt angle TEM images of a representative assembled structure on the top; 3D model structures on the bottom. Label's numbers correspond to angle of title. Reproduced with permission from Ref. [87]. Copyright 2019, American Chemical Society

Fig. 6

Reproduced with permission from Ref. [35]. Copyright 2020, the American Association for the Advancement of Science. e, f Experimental and simulated HRTEM images of a BCB Au nanowire (Δf =  −35 nm). g Model of a BCB tetrahelix. h Schematic diagram of pseudoperiodicity in BCB tetrahelix. i Schematic illustration of a BCB tetrahelix. j, k Experimental and simulated HRTEM images of a BCB Au nanowire (Δf =  −30 nm), showing two types of helical pitches (τ1 and τ2). Reproduced with permission from Ref. [88]. Copyright 2014, American Chemical Society. l Schematic diagram of formation process of double helix by depositing a metal layer on AuAg alloy nanowire. m, n TEM images of as-prepared AuAg nanowire and AuAg@Pd double helix, respectively. o–q TEM images of AuAg@Pd double helices by using precursors of 80, 270, 540 μmol·L−1 H2PdCl4, respectively. r TEM image of AuAg@Pd quadruple helix. SEM images of AuAg@Pd double helices of s, t right-handed and u left-handed chirality. Reproduced with permission from Ref. [89]. Copyright 2011, American Chemical Society

Fig. 7

Reproduced with permission from Ref. [67]. Copyright 2018, Springer Nature. i SEM image of L-P+ NPs after 0, 5, 10, 20, 30 and 40 min of illumination at 594 nm with 84 mW·cm−2, scale bar 20 nm. j TEM tomography images of L-P+, D-P−, L-P− and L-P0 NPs. k, l CD spectra and g-factor spectra of NPs. Reproduced with permission from Ref. [66]. Copyright 2022, Springer Nature

Fig. 8

Reproduced with permission from Ref. [95]. Copyright 2015, John Wiley and Sons. d Enantioselective photocyclodimerization of 2-anthracenecarboxylic acid (AC) by metallic NH under 365-nm non-polarized light (NPL). Si and Re faces of AC molecules are depicted in purple and green, respectively. Structures on the right show that (+)-3 is formed by Si–Si stacking of AC pairs, and (−)-3 is formed by Re–Re stacking; HRTEM images of e LH-AgNHs and f RH-AgNHs with a helical pitch (P) of 5 nm. Dots represent wavelike chiral lattices. g Optical chirality (C) distribution on helical surface. Reproduced with permission from Ref. [97]. Copyright 2020, Springer Nature

Fig. 9

Reproduced with permission from Ref. [107]. Copyright 2018, Springer Nature. In vivo experiments: f CT and g PA imaging of HeLa tumor-bearing mice taken at different time points after injection with an agent (SS15-d-Cys). Reproduced with permission from Ref. [108]. Copyright 2017, John Wiley and Sons

Fig. 10

Reproduced with permission from Ref. [120]. Copyright 2015, American Chemical Society

Fig. 11
Fig. 12

Reproduced with permission from Ref. [130]. Copyright 2014, Royal Society of Chemistry. g Schematic illustration of self-assembly of chiral fluorescent CQD/CNC nanostructures. h Inkjet printing of chemically designed chiral luminous CNC films; i PL spectra of o-CQD dispersion at various pH solutions. Patterned chiral luminous CNC films with a diameter of 10 cm under j natural light and k UV light at 365 nm. Reproduced with permission from Ref. [131]. Copyright 2019, American Chemical Society

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 22071172, 21902148, 12205165, 50835002 and 51105102).

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  1. Sulaiman Umar Abbas, Jun-Jun Li and Xing Liu have contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, School of Science, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin, 300072, China

    Sulaiman Umar Abbas, Jun-Jun Li, Yong-Xia Shi, Man Hou & Zhi-Cheng Zhang

  2. School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, 450001, China

    Xing Liu & Guang-Chao Zheng

  3. Ministry of Education Key Laboratory of Protein Sciences, Beijing Advanced Innovation Center for Structural Biology, School of Life Sciences, Tsinghua University, Beijing, 100084, China

    Xiao-Ya Cui

  4. Beijing Frontier Research Center for Biological Structures, Tsinghua University, Beijing, 100084, China

    Xiao-Ya Cui

  5. Institute of Chemistry, University of Sargodha, Sargodha, 40100, Pakistan

    Ayesha Siddique & Farhat Nosheen

  6. Department of Electrical and Electronic Engineering, Advanced Technology Institute, University of Surrey, Surrey, GU2 7XH, UK

    Kai Yang

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Abbas, S.U., Li, JJ., Liu, X. et al. Chiral metal nanostructures: synthesis, properties and applications. Rare Met. 42, 2489–2515 (2023). https://doi.org/10.1007/s12598-023-02274-4

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