Evolution of the Ligand Shell Morphology during Ligand Exchange Reactions on Gold Nanoparticles

Luo, Zhi; Hou, Jing; Menin, Laure; Ong, Quy K.; Stellacci, Francesco

doi:10.1002/anie.201708190

Cited by 39 publications

(50 citation statements)

References 29 publications

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“…29 The kinetics and evolution of the ligand shell morphology in thiol-for-thiol exchange reactions were recently studied in great detail. 30 An alternative is the synthesis of AuNPs with a more labile intermediate capping agent to facilitate the exchange. The use of AuNP protectants such as citrate, 31 phosphine, 32,33 4-(N,N-dimethylamino)pyridine (DMAP), 34,35 dioctylamine (DOA), 36 and tetraoctylammonium bromide (TOAB) 37 allows us to separate the synthesis of the AuNP core and the formation of a tailored ligand shell via a thiol-for-agent ligand-exchange procedure.…”

Section: ■ Introductionmentioning

confidence: 99%

A Versatile AuNP Synthetic Platform for Decoupled Control of Size and Surface Composition

Yang¹,

Serrano²,

Guldin³

2018

Preprint

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While a plethora of protocols exist for the synthesis of sub-10-nm gold nanoparticles (AuNPs), independent control over the size and surface composition remains restricted. This poses a particular challenge for systematic studies of AuNP structure− function relationships and the optimization of crucial design parameters. To this end, we report on a modular two-step approach based on the synthesis of AuNPs in oleylamine (OAm) followed by subsequent functionalization with thiol ligands and mixtures thereof. The synthesis of OAm-capped AuNPs enables fine-tuning of the core size in the range of 2−7 nm by varying the reaction temperature. The subsequent thiol-for-OAm ligand exchange allows a reliable generation of thiol-capped AuNPs with target surface functionality. The compatibility of this approach with a vast library of thiol ligands provides detailed control of the mixed ligand composition and solubility in a wide range of solvents ranging from water to hexane. This decoupled control over the AuNP core and ligand shell provides a powerful toolbox for the methodical screening of optimal design parameters and facile preparation of AuNPs with target properties.

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Section: ■ Introductionmentioning

confidence: 99%

A Versatile AuNP Synthetic Platform for Decoupled Control of Size and Surface Composition

Yang¹,

Serrano²,

Guldin³

2018

Preprint

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“…dPET-DDT nanoparticles were synthesized using a different approach, i.e., ligand exchange reaction. It has been demonstrated that ligand exchange reactions at room temperature often leads to nanoparticle morphologies that are not at the equilibrium 26 , 27 . After the ligand exchange reaction and thorough purification, the nanoparticles were annealed in pure toluene for 24 h at 50 °C to allow for the morphology to equilibrate.…”

Section: Resultsmentioning

confidence: 99%

Quantitative 3D determination of self-assembled structures on nanoparticles using small angle neutron scattering

et al. 2018

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The ligand shell (LS) determines a number of nanoparticles’ properties. Nanoparticles’ cores can be accurately characterized; yet the structure of the LS, when composed of mixture of molecules, can be described only qualitatively (e.g., patchy, Janus, and random). Here we show that quantitative description of the LS’ morphology of monodisperse nanoparticles can be obtained using small-angle neutron scattering (SANS), measured at multiple contrasts, achieved by either ligand or solvent deuteration. Three-dimensional models of the nanoparticles’ core and LS are generated using an ab initio reconstruction method. Characteristic length scales extracted from the models are compared with simulations. We also characterize the evolution of the LS upon thermal annealing, and investigate the LS morphology of mixed-ligand copper and silver nanoparticles as well as gold nanoparticles coated with ternary mixtures. Our results suggest that SANS combined with multiphase modeling is a versatile approach for the characterization of nanoparticles’ LS.

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“…Nanoparticle synthesis and purification. Mixed ligand gold NPs were synthesized using the Stucky protocol 56 followed by ligand exchange reaction as reported previously 57 . First, homo-alkanethiol protected NPs were synthesized as following: 123 mg triphenylphosphinegold (I) chloride and 0.25 mmol alkanethiol ligand (e.g.…”

Section: Methodsmentioning

confidence: 99%

“…As the size of a NP is always the primary question in its characterization, we first focus on demonstrating the sensitivity of SANS to the dimension of both the metal core and organic shell. Two series of gold NPs were synthesized according to previous literature 37,56,57 . First, three MNPs with different core sizes but the same ligand shell coating were produced using a ligand exchange protocol 56,57 .…”

Section: Dimensional Informationmentioning

confidence: 99%

Multidimensional Characterization of Mixed Ligand Nanoparticles Using Small Angle Neutron Scattering

et al. 2019

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The properties of ligand protected gold nanoparticles are determined by the synergistic interplay of their structural components, including the metal core, the ligand shell, and its solvation. However, the simultaneous characterization of all these components remains a major challenge given their distinctly different chemical nature. In the case of mixed ligand nanoparticles, this task becomes daunting due to the presence of intercorrelated additional parameters such as the ligand ratio, ligand spatial distribution, and the solvation of the heterogeneous ligand shell. Here we show that small angle neutron scattering (SANS) is a tool capable of simultaneously characterizing the core and the ligand shell of monodisperse mixed ligand gold nanoparticles. We systematicall y examine how each parameter (e.g. the core size, the thickness and composition of the ligand shell, and the mixed ligand spatial heterogeneity) affects nanoparticles' scattering profile. Quantitative information on these parameters is retrieved using ana lytical fitting as well as 3D modelling. Importantly, we show that SANS can evaluate the solvation degree of mixed ligand protected gold nanoparticles, a challenging task for any other characterization methods.

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Evolution of the Ligand Shell Morphology during Ligand Exchange Reactions on Gold Nanoparticles

Cited by 39 publications

References 29 publications

A Versatile AuNP Synthetic Platform for Decoupled Control of Size and Surface Composition

A Versatile AuNP Synthetic Platform for Decoupled Control of Size and Surface Composition

Quantitative 3D determination of self-assembled structures on nanoparticles using small angle neutron scattering

Multidimensional Characterization of Mixed Ligand Nanoparticles Using Small Angle Neutron Scattering

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