Rapid isotopic exchange in nanoparticles

Chakraborty, Papri; Nag, Abhijit; Natarajan, Ganapati; Bandyopadhyay, Nayanika; Paramasivam, Ganesan; Panwar, Manoj Kumar; Chakrabarti, Jaydeb; Pradeep, Thalappil

doi:10.1126/sciadv.aau7555

Cited by 29 publications

(43 citation statements)

References 23 publications

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“…The metastable species transform their geometrical structures into thermodynamically stable ones in solution through inter‐cluster (and intra‐cluster) metal exchange (metal exchange of type 3; Figure A and Figure 15B (a); 2) when [Au 38− x Ag x (SC 4 H 9 ) 24 ] 0 is synthesized by simultaneously reducing Au and Ag salts (co‐reduction [ 145 ] ), thermodynamically stable NCs can be mainly synthesized, and inter‐cluster metal exchange is relatively suppressed for those NCs (Figure 15B (b)). The observed phenomenon occurred under this experimental condition, and even if the same [Au 38 −x Ag x (SC 4 H 9 ) 24 ] 0 was used, the dynamic behavior might differ depending on the temperature [ 261 ] or concentration used. The reaction rate also appears to be different when the functional group structure of the ligand or/and the number of Ag substitutions differ.…”

Section: Recent Developmentmentioning

confidence: 99%

“…Currently, the number of methods for observing the geometrical structure of the reaction intermediates generated in solution is limited. However, if the number of such structural analysis methods [ 249,261 ] increases in the future, it should become possible to obtain a deeper understanding of the reaction processes. In addition, it is expected that methods to stop the reaction on the way and thereby to obtain alloy NCs with heteroatoms of different substitution sites will be established.…”

Section: Recent Developmentmentioning

confidence: 99%

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Thiolate‐Protected Metal Nanoclusters: Recent Development in Synthesis, Understanding of Reaction, and Application in Energy and Environmental Field

Kawawaki

Ebina

Hosokawa

et al. 2021

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Metal nanoclusters (NCs), which are composed of about 250 or fewer metal atoms, possess great potential as novel functional materials. Fundamental research on metal NCs gradually started in the 1960s, and since 2000, thiolate (SR)‐protected metal NCs have been the main metal NCs actively studied. The precise and systematic isolation of SR‐protected metal NCs has been achieved in 2005. Since then, research on SR‐protected metal NCs for both basic science and practical application has rapidly expanded. This review describes this recent progress in the field of SR‐protected metal NCs in three areas: synthesis, understanding, and application. Specifically, the recent study of alloy NCs and connected structures composed of NCs is highlighted in the “synthesis” section, recent knowledge on the reactivity of NCs in solution is highlighted in the “understanding” section, and the applications of NCs in the energy and environmental field are highlighted in the “application” section. This review provides insight on the current state of research on SR‐protected metal NCs and discusses the challenges to be overcome for further development in this field as well as the possibilities that these materials can contribute to solving the problems facing modern society.

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Section: Recent Developmentmentioning

confidence: 99%

Section: Recent Developmentmentioning

confidence: 99%

Thiolate‐Protected Metal Nanoclusters: Recent Development in Synthesis, Understanding of Reaction, and Application in Energy and Environmental Field

Kawawaki

Ebina

Hosokawa

et al. 2021

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“…Isotopic exchange reactions have been widely used to understand dynamics in the structures of proteins and polymers. − Similarly, isotopic exchange in NCs also resolved their structural dynamics. , Two Ag 25 (DMBT) 18 – NCs, prepared with isotopically pure 107 Ag and 109 Ag, respectively, reacted to produce isotopically mixed Ag 25 (DMBT) 18 – . The isotopic exchange was similar to the exchanges observed in H 2 O and D 2 O, which revealed that NCs indeed behave as simple molecules.…”

Section: Introductionmentioning

confidence: 78%

“…Isotopically pure 107 Ag 25 (DMBT) 18 – and 109 Ag 25 (DMBT) 18 – NCs were synthesized using isotopically pure 107 AgNO 3 and 109 AgNO 3 salts and following the previously established synthetic protocols. , Details of synthesis are mentioned in the Supporting Information, and ESI MS of the NCs is presented in Figure S1.…”

Section: Experimental Methodsmentioning

confidence: 99%

Isotopic Exchange of Atomically Precise Nanoclusters with Materials of Varying Dimensions: From Nanoscale to Bulk

et al. 2021

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We present isotopic exchange reactions of atomically precise silver nanoclusters (NCs) with materials of different dimensions, namely, NCs, plasmonic nanoparticles (NPs), and bulk metals, all made of silver. Isotopically pure 109Ag25(DMBT)18 – and 107Ag25(DMBT)18 – (DMBT is 2,4-dimethyl benzene thiol) were reacted with Ag NPs of different sizes in the range of ∼2–11 nm, protected with the same ligand. The exchange of 107Ag/109Ag atoms in the NC was monitored using electrospray ionization mass spectrometry. The reaction kinetics was analyzed by fitting the temporal evolution of the reactant concentration to a kinetic model. The reaction timescales of NC–NP reactions were significantly longer compared to those of the NC–NC exchange process under similar conditions. Differences between NC–NC exchange and NC–NP exchange highlighted the importance of the structure in controlling the reaction. Moreover, isotopic exchanges of the NC were also studied with the bulk metal to obtain a complete understanding of how the kinetics of atom transfer varies upon changing the size of the reacting partner from nanoscale to bulk.

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“…Salassa et al used MALDI MS and NMR spectroscopy to show that monolayers of clusters are dynamic in nature, and inter-cluster ligand exchanges can occur during collision between the NCs 111 . Using isotopically pure silver clusters made of 107 Ag and 109 Ag, Chakraborty et al studied rapid isotopic exchange in silver clusters by HR ESI MS and found that the solution-state exchange dynamics of the clusters is similar to that occurring in water (H 2 O + D 2 O = 2HDO) 112 .…”

Section: Reactions Between Nanoparticlesmentioning

confidence: 99%

The emerging interface of mass spectrometry with materials

Chakraborty

Pradeep

2019

NPG Asia Mater

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Mass spectrometry (MS), a hundred-year-old subject, has been a technique of profound importance to molecular science. Its impact in solid-state materials science has not been evident, although many materials of modern science, such as fullerenes, have their origins in MS. Of late, mass spectrometric interface with materials is increasingly strengthened with advances in atomically precise clusters of noble metals. Advances in instrumentation along with recent developments in synthetic approaches have expanded the chemistry of clusters, and new insights into matter at the nanoscale are emerging. High-resolution MS coupled with soft ionization techniques enable efficient characterization of atomically precise clusters. Apart from that, techniques such as ion mobility, tandem MS, etc. reveal structural details of these systems. Growth, nucleation, and reactivity of clusters are also probed by MS. Some of the recent advancements in this field include the development of new hyphenated techniques. Finer structural details may be obtained by coupling MS with spectroscopic tools, such as photoelectron spectroscopy, vacuum ultraviolet spectroscopy, etc. With such advancements in instrumentation, MS can evolve into a universal tool for the characterization of materials. The present review captures highlights of this area.

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Rapid isotopic exchange in nanoparticles

Abstract: Rapid isotopic exchange reveals the solution-state dynamics existing in nanoparticles, very similar to that in H2O and D2O.

Cited by 29 publications

References 23 publications

Thiolate‐Protected Metal Nanoclusters: Recent Development in Synthesis, Understanding of Reaction, and Application in Energy and Environmental Field

Thiolate‐Protected Metal Nanoclusters: Recent Development in Synthesis, Understanding of Reaction, and Application in Energy and Environmental Field

Isotopic Exchange of Atomically Precise Nanoclusters with Materials of Varying Dimensions: From Nanoscale to Bulk

The emerging interface of mass spectrometry with materials

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