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Thiolate-Protected Gold Nanoparticles Via Physical Approach: Unusual Structural and Photophysical Characteristics.

ABSTRACT: Here we report a novel physical approach for thiolate-protected fluorescent gold nanoparticles with a controlled size of the order of a few nanometers. This approach is based on a sputtering of gold into a liquid matrix containing thiolate ligand as a stabilizer at various concentrations, thus no reductant was used. The size of the gold nanoparticles was successfully controlled to range from 1.6 to 7.4 nm by adjusting the thiol concentrations. Surface plasmon absorption was observed in larger nanoparticles, but it was not observed in smaller ones. Such smaller nanoparticles fluoresced at around 670 nm with a small spectral shift according to their size, however, the diameter (1.6-2.7 nm) was very strange to show such red emission compared with photophysical characteristics of reported gold cluster or nanoparticles synthesized by chemical method. By detailed investigations using TEM, HAADF-STEM, XPS, and TGA, and size fractionation by size exclusion chromatography, we finally arrived at the plausible mechanism for the origin of unusual fluorescence property; the obtained gold nanoparticles are not single-crystal and are composed of aggregates of very small components such as multinuclear gold clusters or complexes.

SUBMITTER: Ishida Y

PROVIDER: S-EPMC4947912 | biostudies-literature |

REPOSITORIES: biostudies-literature

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A Novel Physical Approach for Cationic-Thiolate Protected Fluorescent Gold Nanoparticles.

Project description:Knowledge on the synthesis of cationically charged fluorescent gold nanoparticles (Au NPs) is limited because the electrostatic repulsion between cationic ligands on the surface of NP hinders the formation of small Au NPs (usually less than ca. 2 nm) during nucleation in solvents. We herein propose a novel methodology for a synthesis of water-dispersible, cationic-thiolate protected fluorescent Au NPs by the sputtering of Au into liquid matrix containing thiolate ligands. By controlling mercaptan concentration the size and photophysical characteristics of Au NPs were directly controlled, resulting in near IR fluorescence with a 0.9% of absolute quantum yield. Cationically charged fluorescent metal NPs are promising, especially in biological fields, and this work provides a novel methodology towards the synthesis of a new series of functional metal NPs.

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Project description:Ligand exchange reactions are widely used for imparting new functionality on or integrating nanoparticles into devices. Thiolate-for-thiolate ligand exchange in monolayer protected gold nanoclusters has been used for over a decade; however, a firm structural basis of this reaction has been lacking. Herein, we present the first single-crystal X-ray structure of a partially exchanged Au(102)(p-MBA)(40)(p-BBT)(4) (p-MBA = para-mercaptobenzoic acid, p-BBT = para-bromobenzene thiol) with p-BBT as the incoming ligand. The crystal structure shows that 2 of the 22 symmetry-unique p-MBA ligand sites are partially exchanged to p-BBT under the initial fast kinetics in a 5 min timescale exchange reaction. Each of these ligand-binding sites is bonded to a different solvent-exposed Au atom, suggesting an associative mechanism for the initial ligand exchange. Density functional theory calculations modeling both thiol and thiolate incoming ligands postulate a mechanistic pathway for thiol-based ligand exchange. The discrete modification of a small set of ligand binding sites suggests Au(102)(p-MBA)(44) as a powerful platform for surface chemical engineering.

| S-EPMC4624284 | biostudies-literature

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Biomimetic monolayer-protected gold nanoparticles for immunorecognition.

Project description:Gold nanoparticles (AuNPs) protected by self-assembled monolayers (SAMs) are capable of presenting precisely engineered surfaces at the nanoscale, allowing the mimicry of biomacromolecules on an artificial platform. Here we review the generation, characterization, and applications of monolayer-protected AuNPs that have been designed for immunorecognition by the integration of an oligopeptide epitope into the protecting monolayer. The resulting peptide-AuNP conjugate is an effective platform for biomimesis, as demonstrated by multiple studies. Recent work is presented and future directions for this field of research are discussed.

| S-EPMC3376232 | biostudies-literature

Chiral Inversion of Thiolate-Protected Gold Nanoclusters via Core Reconstruction without Breaking a Au-S Bond.

Project description:On the basis of density functional theory computations of the well-known chiral Au38(SR)24 nanocluster and its Pd- and Ag-doped derivatives, we propose here a mechanism for chiral inversion that does not require the breaking of a metal-sulfur bond at the metal-ligand interface but features a collective rotation of the gold core. The calculated energy barriers for this mechanism for Au38 and Pd-doped Au38 are in the range of 1-1.5 eV, significantly lower than barriers involving the breakage of Au-S bonds (2.5 eV). For Ag-doped Au38, barriers for both mechanisms are similar (1.3-1.5 eV). Inversion barriers for a larger chiral Au144(SR)60 are much higher (2.5-2.8 eV). Our computed barriers are in good agreement with racemization barriers estimated from existing experiments for bare and doped Au38. These results highlight the sensitivity of chiral inversion to the size, structure, and metal composition of the metal core and sensitivity to the detailed structure of the metal-thiolate interface. Our work also predicts that enantiopure Au144(SR)60 clusters would be promising materials for applications requiring high resistance to chiral inversion.

| S-EPMC6727375 | biostudies-literature

Ligand Migration from Cluster to Support: A Crucial Factor for Catalysis by Thiolate-protected Gold Clusters.

Project description:Thiolate protected metal clusters are valuable precursors for the design of tailored nanosized catalysts. Their performance can be tuned precisely at atomic level, e. g. by the configuration/type of ligands or by partial/complete removal of the ligand shell through controlled pre-treatment steps. However, the interaction between the ligand shell and the oxide support, as well as ligand removal by oxidative pre-treatment, are still poorly understood. Typically, it was assumed that the thiolate ligands are simply converted into SO2, CO2 and H2O. Herein, we report the first detailed observation of sulfur ligand migration from Au to the oxide support upon deposition and oxidative pre-treatment, employing mainly S K-edge XANES. Consequently, thiolate ligand migration not only produces clean Au cluster surfaces but also the surrounding oxide support is modified by sulfur-containing species, with pronounced effects on catalytic properties.

| S-EPMC6348379 | biostudies-literature

Absolute configuration retention of a configurationally labile ligand during dynamic processes of thiolate protected gold clusters.

Project description:Monolayer protected metal clusters are dynamic nanoscale objects. For example, the chiral Au38(2-PET)24 cluster (2-PET: 2-phenylethylthiolate) racemizes at moderate temperature. In addition, ligands and metal atoms can easily exchange between clusters. Such processes are important for applications of monolayer protected metal clusters; however, the mechanistic study of such processes turns out to be challenging. Here we use a configurationally labile, axially chiral ligand, biphenyl-2,2'-dithiol (R/S-BiDi), as a probe to study dynamic cluster processes. It is shown that the ligand exchange of free R/S-BiDi on a chiral Au38(2-PET)24 cluster is diastereospecific. Using chiral chromatography, isolated single diastereomers of the type anticlockwise/clockwise-Au38(2-PET)22(R/S-BiDi)1 could be isolated. Upon heating, the cluster framework racemizes, while the R/S-BiDi ligand does not. These findings demonstrate that during cluster racemization and/or ligand exchange between clusters, the R/S-BiDi ligand is sufficiently confined, thus preventing its racemization, and exclude the possibility that the ligand desorbs from the cluster surface.

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Controlled reduction for size selective synthesis of thiolate-protected gold nanoclusters Aun(n?=?20, 24, 39, 40).

Project description:This work presents a controlled reduction method for the selective synthesis of different sized gold nanoclusters protected by thiolate (SR?=?SC2H4Ph). Starting with Au(III) salt, all the syntheses of Aun(SR)m nanoclusters with (n, m)?=?(20, 16), (24, 20), (39, 29), and (40, 30) necessitate experimental conditions of slow stirring and slow reduction of Au(I) intermediate species. By controlling the reaction kinetics for the reduction of Au(I) into clusters by NaBH4, different sized gold nanoclusters are selectively obtained. Two factors are identified to be important for the selective growth of Au20, Au24, and Au39/40 nanoclusters, including the stirring speed of the Au(I) solution and the NaBH4 addition speed during the step of Au(I) reduction to clusters. When comparing with the synthesis of Au25(SC2H4Ph)18 nanoclusters, we further identified that the reduction degree of Au(I) by NaBH4 also plays an important role in controlling cluster size. Overall, our results demonstrate the feasibility of attaining new sizes of gold nanoclusters via a controlled reduction route.

| S-EPMC3503687 | biostudies-literature

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