Chiral Phase Transfer and Enantioenrichment of Thiolate-Protected Au<sub>102</sub> Clusters

Knoppe, Stefan; Wong, O. Andrea; Malola, Sami; Häkkinen, Hannu; Bürgi, Thomas; Verbiest, Thierry; Ackerson, Christopher J.

doi:10.1021/ja500809p

Cited by 133 publications

(112 citation statements)

References 35 publications

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“…Intrinsically chiral gold clusters include the Au 28 (SR) 20 , Au 38 (SR) 24 , Au 40 (SR) 24 , and Au 102 (SR) 44 systems . The CD spectra of their enantiomers are perfect mirror images.…”

Section: Chiral Thiolate‐stabilized Gold Npsmentioning

confidence: 99%

“…Intrinsically chiral gold clusters include the Au 28 (SR) 20 , Au 38 (SR) 24 , Au 40 (SR) 24 , and Au 102 (SR) 44 systems. [39][40][41][42][43][44][45][46][47][48][49][50][51][52] The CD spectra of their enantiomers are perfect mirror images. The chirality of these nanoclusters arises from the chiral arrangement of the thiolates on their surface, forming staple motifs.…”

Section: Chiral Thiolate-stabilized Gold Npsmentioning

confidence: 99%

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Chiral Noble Metal Nanoparticles and Nanostructures

Karimova

Aikens

2019

Part & Part Syst Charact

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The origins of chirality and chiroptical properties in ligand‐protected gold and silver nanoparticles (NPs) are considered herein. Current conceptual models including the chiral core model, dissymmetric field model, and chiral footprint model are described as mechanisms that contribute to the understanding of chirality in these systems. Then, recent studies on thiolate‐stabilized gold NPs, phosphine‐stabilized gold NPs, multi‐ligand‐stabilized silver NPs, and DNA‐stabilized silver NPs are discussed. Insights into the origin of chiroptical properties including reasons for large Cotton effects in circular dichroism spectra are considered using both experimental and theoretical data available. Theoretical calculations using density functional theory (DFT) and time‐dependent DFT methods are found to be extremely useful for providing insights into the origin of chirality. The origin of chirality in ligand‐protected gold and silver NPs can be considered to be a complex phenomenon, arising from a combination of the three conceptual models.

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“…Intrinsically chiral gold clusters include the Au 28 (SR) 20 , Au 38 (SR) 24 , Au 40 (SR) 24 , and Au 102 (SR) 44 systems . The CD spectra of their enantiomers are perfect mirror images.…”

Section: Chiral Thiolate‐stabilized Gold Npsmentioning

confidence: 99%

Section: Chiral Thiolate-stabilized Gold Npsmentioning

confidence: 99%

Chiral Noble Metal Nanoparticles and Nanostructures

Karimova

Aikens

2019

Part & Part Syst Charact

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“…[16] Therefore, we believe MBA plays an important role in protecting the metal core of NCs and can also be chosen to prepare copper clusters, especially water-soluble and stable copper clusters. 1) The use of MBAa st he cap-ping ligand.M BA is as pecial aromatic organic and can be dissolved in most of solvents such as water,a lcohol, and acetone, owing to the co-existence of hydrophilic and hydrophobic groups in the molecule.…”

Section: Synthesis and Characterization Of Cu Ncsmentioning

confidence: 99%

Copper Nanoclusters on Carbon Supports for the Electrochemical Oxidation and Detection of Hydrazine

Gao

Zhang

et al. 2016

ChemElectroChem

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Owing to the definite composition and unique properties, metal nanoclusters have attracted much attention in recent years. In this work, we design a simple one‐pot chemical method to synthesize a new type of copper clusters. The structures and composition of the clusters are characterized by using various techniques. Electrospray ionization mass spectrometry characterizations clearly show that the product is mainly composed of a seven‐copper‐atom core and three thiolate ligands with the formula of Cu7(C7H5O2S)3−, together with four‐ and six‐copper‐atom clusters. On the other hand, direct hydrazine fuel cells have attracted extensive research interests and more and more efforts have been devoted into the development of novel catalysts for the electrochemical oxidation and detection of hydrazine. Here, we investigate the electrocatalytic performance of the copper clusters towards the oxidation and detection of hydrazine. Electrochemical studies display that the synthesized cluster compounds supported on activated carbon show an onset potential of −0.42 V and a current density of 20 mA cm−2 at the potential of 0.36 V for the oxidation of hydrazine. Meanwhile, the copper clusters show a limit of detection of 1.04 μm and a sensitivity of 0.408 mA cm−2 mm−1 in the detection of hydrazine. These studies clearly demonstrate that the as‐synthesized copper clusters exhibit excellent electrocatalytic performance for the oxidation and detection of hydrazine. Notably, the catalytic performance is superior to the previously reported Cu‐based or Ni‐based, and even noble‐metal‐based, catalysts.

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“…10 In addition, it still represents the largest cluster whose structure has been determined from single crystal x-ray diffraction. For Au 102 (p-MBA) 44, 19 Au 38 (2-PET) 24 (2-PET: 2-phenylethanethiolate, -SCH 2 CH 2 Ph), 20 Au 40 (2-PET) 24 , 21 and Au 28 (TBBT) 20 (4-tert-butylbenzenethiolate), 15 intrinsic chirality is observed. This is due to the chiral arrangement of the protecting (SR-Au) x -SR (x = 1, 2, 3) units on the surface of an otherwise achiral core (small perturbations in the core are still observed).…”

Section: Introductionmentioning

confidence: 99%

Nonlinear Optical Properties of Thiolate-Protected Gold Clusters

et al. 2015

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Thiolate-protected gold clusters are promising candidates for imaging applications due to their interesting, size-dependent properties. Their high stability and the ability to functionalize the clusters with biocompatible ligands render the clusters for various imaging techniques such as fluorescence microscopy or Second-Harmonic Generation microscopy. The latter nonlinear optical effect has not yet been observed on this type of ultra-small nanoparticles.We hereby present Second-and Third-Harmonic Generation and multi-photon luminescence of two thiolate-protected gold clusters, Au 25 (SCH 2 CH 2 Ph) 18 and Au 38 (SCH 2 CH 2 Ph) 24 . At a fundamental wavelength of 800 nm, the Au 38 (SCH 2 CH 2 Ph) 24 cluster is active. In contrast, Au 25 (SCH 2 CH 2 Ph) 18 does not yield significant SHG signal. We ascribe this to the center of inversion in the Au 25 cluster. Measurements on chiral Au 25 (capt) 18 (capt: captopril) gave an SHG response, supporting this interpretation. We also observed Third-Harmonic Generation at a fundamental wavelength of 1200 nm. At 800 and 1,100 nm, the clusters decompose after short illumination time, but are stable at illumination at 1,200 nm. This may be exploited in combined deep tissue imaging and photothermal heating for theranostics applications.

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Chiral Phase Transfer and Enantioenrichment of Thiolate-Protected Au₁₀₂ Clusters

Cited by 133 publications

References 35 publications

Chiral Noble Metal Nanoparticles and Nanostructures

Chiral Noble Metal Nanoparticles and Nanostructures

Copper Nanoclusters on Carbon Supports for the Electrochemical Oxidation and Detection of Hydrazine

Nonlinear Optical Properties of Thiolate-Protected Gold Clusters

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Chiral Phase Transfer and Enantioenrichment of Thiolate-Protected Au102 Clusters

Cited by 133 publications

References 35 publications

Chiral Noble Metal Nanoparticles and Nanostructures

Chiral Noble Metal Nanoparticles and Nanostructures

Copper Nanoclusters on Carbon Supports for the Electrochemical Oxidation and Detection of Hydrazine

Nonlinear Optical Properties of Thiolate-Protected Gold Clusters

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Chiral Phase Transfer and Enantioenrichment of Thiolate-Protected Au₁₀₂ Clusters