Binary Chiral Nanoparticles Exhibit Amplified Optical Activity and Enhanced Refractive Index Sensitivity

Yang, Lin; Nandi, Proloy; Ma, Yuchen; Liu, Junjun; Mirsaidov, Utkur; Huang, Zhifeng

doi:10.1002/smll.201906048

Cited by 15 publications

(22 citation statements)

References 44 publications

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“…We have reported that the chirality can be effectively transferred from the host CNPs to the dopant M using the LbL‐GLAD, due to the diffusion of M into the chiral lattices of the host that is promoted by the GLAD‐induced heating effect. [ 38 ] The thermally diffused M atoms are spatially located in the chiral fashion duplicated from the chiral lattices of the host CNPs, i.e., the chiral alloying effect. The chiral alloying was observed in the binary Cu:Au nanostructures.…”

Section: Resultsmentioning

confidence: 99%

“…LbL-GLAD of Binary Cu:M CNPs (M: Au, Ag, TiO 2 ): Binary CNPs were generated through three-step LbL-GLAD processes. [38] The first and third step was the GLAD-FSR of the host unary Cu CNPs having a nominal P of roughly 10 nm and H of ≈50 nm, and the second step was the GLAD of dopant M without substrate rotation, with a nominal thickness of T M . M included Au (99.999%, Fuzhou Innovation Photoelectric Technology Co., LTD), Ag (99.99%, Kurt J. Lesker), and TiO 2 (99.9%, Kurt J. Lesker).…”

Section: Glad-fsr Of Unary Cnpsmentioning

confidence: 99%

“…In this work, a thin layer of metals with high electrode potential (e.g., Au) was doped into the unary Cu CNPs through layer‐by‐layer GLAD (or LbL‐GLAD) to form the binary Cu:Au CNPs. [ 38 ] The dopant Au, which is resistant to the galvanic oxidation/dissolution in a given electrolyte, serves as structural scaffold to assist the chirality transmission from the CST Cu CNPs mediated with the GRR, leading to the formation of ternary CNPs (such as Cu:Au:Pt, and Cu:Au:Ag). The composition of the ternary CNPs was facilely tuned as a function of GRR duration ( t ).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Zhu

Liu

et al. 2020

Advanced Science

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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.

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Section: Resultsmentioning

confidence: 99%

Section: Glad-fsr Of Unary Cnpsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

Zhu

Liu

et al. 2020

Advanced Science

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“…To extend the compositional space in Cu CNPs, Au with relatively high electrode potential was doped in the host using layer-by-layer GLAD (or LbL-GLAD) to generate the Cu:Au binary CNPs, where the GLAD heating effect caused the Au dopants to diffuse into the host chiral lattices and to duplicate the host's chirality. [54] The chiral Au functions as a structural scaffold to support the GRR-mediated chirality transfer, resulting in the generation of ternary Cu:Au:Pt and Cu:Au:Ag CNPs. [55] The composition and chiroplasmonic OA of polyelemental CNPs can be facilely adjusted as a function of the GRR duration.…”

Section: Nanoparticles With Chiral Atomic Latticesmentioning

confidence: 99%

Recent Advances in Inorganic Chiral Nanomaterials

et al. 2021

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handedness or LH) and d-sugars (only having right handedness or RH) with unknown reason. Such biological homochirality essentially governs asymmetric biochemical reactions with diverse physiological effects, and plays a paramount role in disease therapeutics and pharmaceutical production. [1] When bulk materials are shrunk to the nanometer scale, that is, the formation of nanomaterials or generally called nanoparticles (or NPs) that possess high surface areas and restrictly confine electron movement to remarkably induce a series of compelling chemical, catalytic, optical, plasmonic, (opto)electronic, magnetic, and mechanical properties. [2] Due to these unique properties, inorganic NPs have been developed to function as multifunctional platforms for biomedical applications (or bioapplications) in drug delivery, bioimaging, disease diagnosis, screening, and therapeutic treatments. [3] The homochirality-determined asymmetic biochemical activities and processes intrincially demand the fabrication of inorganic chiral nanomaterials, whose biofunctions fundamentally depend on the asymmetric interactions at nano-bio interfaces. [4] However, most inorganic compounds thermodynamically have achiral crystal structures, and metallic crystals usually have cubic or hexagonal symmetries. [5] Chiral driving forces are indispensably applied to impose chirality onto inorganic NPs, which have been reviewed previously. [6][7][8] Chiral driving forces include chirality transfer from chiral ligands, [9][10][11] chiral templates [12] (such as DNA, [13] proteins, [14] peptides, [15] cellulose nanocrystals, [16] liquid crystals modified with chiral ligands, [17] lipidic nanoribbons, [18] chiral mesoporous silica, [19] nanohelices [20,21] ), circularly polarized light (CPL), [22] spatially chiral arrangement using lithography techniques, [23] helical magnetic fields, [24] orbital angular momentum, [25] macroscopic asymmetric gradients of biaxial strain fields, [26] and macroscopic shear forces. [27,28] A pair of chiral objects are designated as enantiomorphs, and especially a pair of chiral molecules are called enantiomers. It is of fundamental importance to differentiate an enantiomorph from its stereoisomer (i.e., enantiodifferentiation or enantiodiscrimination), mainly through monitoring differential interactions with other chiral objects. The most compelling property of inorganic chiral NPs is optical activity (OA, or the chiroptical effect), denoting the differential interactions with LH and RH CPL (or LCP and RCP conventionally used). Chiral nanomaterials have the linear OA characterized with circular dichroism (CD, denoting the differential absorption) [29] Inorganic nanoparticles offer a multifunctional platform for biomedical applications in drug delivery, biosensing, bioimaging, disease diagnosis, screening, and therapies. Homochirality prevalently exists in biological systems composed of asymmetric biochemical activities and processes, so biomedical applications essentially favor the usage of inorganic chiral nanomaterials...

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“…[37] Chiral topographies at an atomic scale cause an enantiospecific interaction with molecules. [38,39] Furthermore, metal CNPs with chiral lattices have been extended in their compositional space from the unary to binary [40] and ternary, [41] and galvanic replacement reactions have been performed to produce porous binary CNPs. [42] These advanced developments make inorganic CNPs potentially function as asymmetric catalysts.…”

Section: Introductionmentioning

confidence: 99%

Chiral Nanoparticles with Enhanced Thermal Stability of Chiral Structures through Alloying

Lin

Cai

et al. 2022

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Metallic chiral nanoparticles (CNPs) promisingly function as asymmetric catalysts but lack an important study in thermal stability of optical activity that stems from metastable chiral lattices. In this work, annealing is applied to silver (Ag) CNPs, fabricated by glancing angle deposition (GLAD), and causes elimination of optical activity at 200 °C, mainly ascribed to chiral‐to‐achiral lattice transformation. The Ag CNPs are remarkedly enhanced in thermal stability through an alloying with aluminum (Al) via layer‐by‐layer GLAD to generate binary Ag0.5Al0.5 CNPs composed of solid‐state liquids, whose optical activity vanishes at 700 °C. Ease in the diffusion of Al atoms in the host Ag CNPs and thermal insulation from the Al2O3 layers partially covering the binary CNPs effectively prohibit structural relaxation of the metastable chiral lattices, accounting for the significant enhancement in thermal stability of chiral lattices. This is a pioneering work to investigate the fundamental principles determining the thermal stability of metallic CNPs in terms of chiral structures and optical activity. It paves the way toward applying metallic CNPs to asymmetric catalysis at high temperature to accelerate an asymmetric synthesis of enantiomers with designable chirality, which is one of the most important topics in modern chemistry.

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Binary Chiral Nanoparticles Exhibit Amplified Optical Activity and Enhanced Refractive Index Sensitivity

Cited by 15 publications

References 44 publications

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

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

Recent Advances in Inorganic Chiral Nanomaterials

Chiral Nanoparticles with Enhanced Thermal Stability of Chiral Structures through Alloying

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