The synthesis of atomically precise thiolate-stabilized silver (Ag) nanoclusters is the subject of intense research interest, yet the formation mechanism of such nanoclusters remains obscure. Here, electrospray ionization mass spectrometry is successfully applied to monitor the reaction intermediates formed during the sodium-borohydride-reduction of silver 4-tert-butylbenzenethiolate (AgSPh-tBu). We demonstrate a unique evolution route to thiolate-stabilized Ag nanoclusters mediated by Ag-thiolate clusters. The Ag-thiolate clusters form in the initial stage of reduction contain tens of Ag atoms and similar number of ligands, and they are transformed into Ag17(SPh-tBu)123− and Ag44(SPh-tBu)304− nanoclusters in the later reduction process. The number of Ag atoms in the Ag-thiolate clusters determines the reaction path to each final nanocluster product. A similar mechanism is found when silver 2,4-dimethylbenzenethiolate (AgSPhMe2) is used as precursor. This mechanism differs markedly from the long-established bottom-up evolution process, providing valuable new insights into the synthesis of metal nanoclusters.
The electrospray ionization (ESI) is a complex process and there has been a long debate regarding the gas-phase effect on ion generation in the process. In this paper we investigated the effect of liquid chromatographic mobile phase additives (formic acid, aqueous ammonia and their combination) on the ESI signal intensities for a wide variety of compounds. The addition of a trace amount of aqueous ammonia to the common formic acid-methanol mobile phase significantly enhances the ESI signals of protonated molecules and suppresses the formation of sodium adduct ions. This effect is well observed for the compounds containing the -N-C=O group but not for those without N or O atoms. The ESI signal intensity of deprotonated molecules increases with increase in pH of the mobile phase for neutral compounds, such as substituted urea, whereas this trend is not observed for acidic compounds such as phenoxy acids. The mechanistic analysis regarding liquid- and gas-phase protonation and deprotonation is discussed.
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