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Direct SERS tracking of a chemical reaction at a single 13 nm gold nanoparticle.

ABSTRACT: Metal nanoparticles (NPs) with decreased sizes are promising catalysts in energy and medicine. Measuring the local reactions and simultaneously acquiring molecular insights at single small NPs, however, remain an experimental challenge. Here we report on surface-enhanced Raman spectroscopic (SERS) tracking of catalytic reactions of single 13 nm gold NPs (GNPs) in situ. We designed spatially isolated (>1.5 ?m of inter-dimer space) GNP dimers, each of which consisted of two GNPs with sizes of ?200 and ?13 nm, respectively. This design integrates the SERS and catalytic activities into a single entity, while eliminating the crosstalk between adjacent particles, which allows us to trace the redox-derived spectral evolution at single 13 nm GNPs for the first time. We also quantified the reaction kinetics of each individual GNP and analyzed the average behavior of multiple GNPs. There is a large variability among different particles, which underscores the significance of single particle analysis.

SUBMITTER: Zhang K

PROVIDER: S-EPMC6374737 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Direct SERS tracking of a chemical reaction at a single 13 nm gold nanoparticle.

Zhang Kun K Liu Yujie Y Wang Yuning Y Zhao Jingjing J Liu Baohong B

Chemical science 20181204 6

Metal nanoparticles (NPs) with decreased sizes are promising catalysts in energy and medicine. Measuring the local reactions and simultaneously acquiring molecular insights at single small NPs, however, remain an experimental challenge. Here we report on surface-enhanced Raman spectroscopic (SERS) tracking of catalytic reactions of single 13 nm gold NPs (GNPs) <i>in situ</i>. We designed spatially isolated (>1.5 μm of inter-dimer space) GNP dimers, each of which consisted of two GNPs with sizes ...[more]

PMID: 30842839

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Project description:Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization-Diels-Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensors, medical diagnostics, information storage, and catalysis applications. Herein, the control of the synthesis of sub-2-nm gold NPs is achieved by the formation of dense networks, which are assembled in a single step reaction by employing ditopic polymantanethiols. By using 1,1'-bisadamantane-3,3'-dithiol (BAd-SH) and diamantane-4,9-dithiol (DAd-SH), serving both as bulky surface stabilizers and short-sized linkers, we provide a simple method to form uniformly small gold NPs (1.3 ± 0.2 nm to 1.6 ± 0.3 nm) embedded in rigid frameworks. These NP arrays are organized alongside short interparticular distances ranging from 1.9 to 2.7 nm. The analysis of gold NP surfaces and their modification were achieved in joint experimental and theoretical studies, using notably XPS, NMR, and DFT modeling. Our experimental studies and DFT analyses highlighted the necessary oxidative surface reorganization of individual nanoparticles for an effective enyne cycloisomerization. The modifications at bulky stabilizing ligands allow surface steric decongestion for the alkyne moiety activation but also result in network alteration by overoxidation of sulfurs. Thus, sub-2-nm nanoparticles originating from networks building create convenient conditions for generating reactive Au(I) surface single-sites-in the absence of silver additives-useful for heterogeneous gold-catalyzed enyne cyclization. These nanocatalysts, which as such ease organic products separation, also provide a convenient access for building further polycyclic complexity, owing to their high reactivity and selectivity.

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Direct SERS tracking of a chemical reaction at a single 13 nm gold nanoparticle.

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Direct SERS tracking of a chemical reaction at a single 13 nm gold nanoparticle.

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