Abstract
Insight into the nature of metal-sulfur bond, a meaningful one in life science, interface chemistry and organometallic chemistry, is interesting but challenging. By utilizing the localized surface plasmon resonance properties of silver nanoparticles, herein we visually identified the photosensitivity of silver-dithiocarbamate (Ag-DTC) bond by using dark field microscopic imaging (iDFM) technique at single nanoparticle level. It was found that the breakage of Ag-DTC bond could be accelerated effectively by light irradiation, followed by a pH-dependent horizontal or vertical degradation of the DTC molecules, in which an indispensable preoxidation process of the silver was at first disclosed. These findings suggest a visualization strategy at single plasmonic nanoparticle level which can be excellently applied to explore new stimulus-triggered reactions, and might also open a new way to understand traditional organic reaction mechanisms.
Highlights
Thiol always play important roles in the modification of thiophilic noble metal nanomaterials, such as the gold and silver nanoparticles, for preparing surfaces with tunable physicochemical properties or biological recognition sites[1,2,3]
To investigate the Ag-DTC bond breakage comprehensively, we observed the localized surface plasmon resonance (LSPR) scattering features of silver nanoprobes functionalized with three different monosubstituted DTCs (Fig. 1d), including DTC-DA prepared with dopamine (DA) and CS2 24, DTC-TA prepared with tyramine (TA) and CS2, and DTC-PLA prepared with propargylamine (PLA) and CS2 25
It’s based on the iDFM technology and single plasmonic nanoprobes that the light-driven breakage of Ag-DTC bond is investigated and several main influence factors, such as light irradiation, pH, solvents polarity and reducing agents, are studied comprehensively. This identification of the photosensitive nature of Ag-DTC may promote the wide application of Ag-DTC bond and the formed Ag@Ag2S, a conductor@semiconductor nanocomposites, may be used as a complex thermal conductivity model due to the unique negative correlation between the conductivity and temperature of Ag2S
Summary
Thiol always play important roles in the modification of thiophilic noble metal nanomaterials, such as the gold and silver nanoparticles, for preparing surfaces with tunable physicochemical properties or biological recognition sites[1,2,3]. When single plasmonic nanoparticles used as probes, Dark field microscopic imaging (iDFM) technique[12,13,14], as an important complement scattering analysis technology to the surface plasmon spectroscopy technology[15,16], has several unique advantages owing to the localized surface plasmon resonance (LSPR) scattering features, such as accurate localized information and high continuity and time resolution. In such case, iDFM technique at single nanoparticle level has found exciting applications in various fields, including real-time tracking of bioorganisms[17], real-time monitoring of alloying[14], identifying an critical intermediate in galvanic exchange reactions[13], and monitoring the click reaction[12]. Chemical bond with iDFM technique, and the results showed that the non-scanning iDFM technique could be expected to achieve some new discovery of previously unknown reactions and the mechanism of some traditional reactions
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