We have developed a rapid and homogeneous method for the highly selective detection of Hg(2+) and Ag(+) using Tween 20-modified gold nanoparticles (AuNPs). Citrate ions were found to still be adsorbed on the Au surface when citrate-capped AuNPs were modified with Tween 20, which stabilizes the citrate-capped AuNPs against conditions of high ionic strength. When citrate ions had reduced Hg(2+) and Ag(+) to form Hg-Au alloys and Ag on the surface of the AuNPs, Tween 20 was removed from the NP surface. As a result, the AuNPs were unstable under a high-ionic-strength solution, resulting in NP aggregation. The formation of Hg-Au alloys or Ag on the surface of the AuNPs was demonstrated by means of inductively coupled plasma mass spectroscopy and energy-dispersive X-ray spectroscopy. Tween 20-AuNPs could selectively detect Hg(2+) and Ag(+) at concentrations as low as 0.1 and 0.1 microM in the presence of NaCl and EDTA, respectively. Moreover, the probe enables the analysis of AgNPs with a minimum detectable concentration that corresponds to 1 pM. This probe was successfully applied to detect Hg(2+) in drinking water and seawater, Ag(+) in drinking water, and AgNPs in drinking water.

This study presents a one-step approach to prepare lysozyme type VI-stabilized gold nanoclusters (Lys VI-AuNCs) for the ultrasensitive detection of Hg(2+) and CH(3)Hg(+) based on fluorescence quenching. The optical properties and size of Lys VI-AuNCs are highly dependent on the concentration of Lys VI, which acts as both a reducing and a stabilizing agent. With an increase in the concentration of Lys VI, we observed a systematic blue shift in the fluorescence maxima, an increase in the quantum yields, and a reduction in the particle size. When using 25 mg/mL Lys VI as a reducing agent, the formed Lys VI-AuNCs (denoted as Au-631) were found to be highly stable in a high-concentration glutathione or NaCl. Additionally, the Au-631 were capable of sensing Hg(2+) and CH(3)Hg(+) through the interaction between Hg(2+)/CH(3)Hg(+) and Au(+) on the Au surface; the limits of detection (LODs) for Hg(2+) and CH(3)Hg(+) were 3 pM and 4 nM, respectively. The selectivity of this probe is more than 500-fold for Hg(2+) over any metal ions. As compared to bovine serum albumin-stabilized AuNCs, Au-631 provided an approximately 330-fold improvement in the detection of Hg(2+). To the best of our knowledge, Au-631 not only provide the first example for detecting CH(3)Hg(+) but also have the lowest LOD value for Hg(2+) when compared to other AuNC-based Hg(2+) sensors. Importantly, this probe was successfully applied to the determination of Hg(2+) and CH(3)Hg(+) in seawater.

This paper presents a one-pot approach for preparing highly fluorescent Au(8) clusters by reacting the Au(3+) precursor solution with lysozyme type VI (Lys VI) at pH 3. The fluorescence band of (Lys VI)-stabilized Au(8) clusters is centered at 455 nm on the excitation at 380 nm. Blue-emitting Au(8) clusters have a high quantum yield (∼56%), two fluorescence lifetimes, and a rare amount of Au(+) on the surface of the Au core. When the pH of a solution of Au(8) clusters increases suddenly to 12, the Au(8) clusters gradually convert to Au(25) clusters over time. This conversion is also observed in the case of (Lys VI)-directed synthesis of Au(25) clusters at pH 12. The pH-induced conversion of Au(8) to Au(25) clusters suggests that the size of (Lys VI)-stabilized gold nanoclusters (AuNCs) relies on the secondary structure of Lys VI, which is susceptible to pH change. Based on these results and previous literature, this paper proposes the possible mechanism for growing (Lys VI)-stabilized Au(8) and Au(25) clusters. Additionally, (Lys VI)-stabilized Au(8) clusters could sense glutathione (GSH) through GSH-induced core-etching of Au(8) clusters; the limit of detection at a signal-to-noise ratio of 3 for GSH is determined to be 20 nm. Except for cysteine, the selectivity of (Lys VI)-stabilized Au(8) clusters for GSH over amino acids is remarkably high. The practicality of using Au(8) clusters to determine the concentration of GSH in a single drop of blood is also validated.