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The electrophoretic deposition (EPD) of citrate-stabilized Au nanoparticles (cit-Au NPs) occurs on indium tin oxide (ITO)-coated glass electrodes upon electrochemical oxidation of hydroquinone (HQ) due to the release of hydronium ions. Anodic stripping voltammetry (ASV) for Au oxidation allows the determination of the amount of Au NP deposition under a specific EPD potential and time. The binding of Cr 3+ to the cit-Au NPs inhibits the EPD by inducing aggregation and/or reducing the negative charge, which could lower the effective NP concentration of the cit-Au NPs and/or lower the electrophoretic mobility. This lowers the Au oxidation charge in the ASV, which acts as an indirect signal for Cr 3+ . The binding of melamine to cit-Au NPs similarly leads to aggregation and/or lowers the negative charge, also resulting in reduction of the ASV Au oxidation peak. The decrease in Au oxidation charge measured by ASV increases linearly with increasing Cr 3+ and melamine concentration. The limit of detection (LOD) for Cr 3+ is 21.1 ppb and 16.0 ppb for 15.1 and 4.1 nm diameter cit-Au NPs, respectively. Improving the sensing conditions allows for as low as 1 ppb detection of Cr 3+ . The LOD for melamine is 45.7 ppb for 4.1 nm Au NPs.more » « less
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Abstract Aminooxy (–ONH2) groups are well known for their chemoselective reactions with carbonyl compounds, specifically aldehydes and ketones. The versatility of aminooxy chemistry has proven to be an attractive feature that continues to stimulate new applications. This work describes application of aminooxy click chemistry on the surface of gold nanoparticles. A trifunctional amine‐containing aminooxy alkane thiol ligand for use in the functionalization of gold monolayer‐protected clusters (Au MPCs) is presented. Diethanolamine is readily transformed into an organic‐soluble aminooxy thiol (
AOT ) ligand using a short synthetic path. The synthesizedAOT ligand is coated on ≤2‐nm‐diameter hexanethiolate‐(C6S)‐capped Au MPCs using a ligand‐exchange protocol to afford organic‐solubleAOT /C6S (1:1 ratio) Au mixed monolayer‐protected clusters (MMPCs). The synthesis of these Au(C6S)(AOT ) MMPCs and representative oximation reactions with various types of aldehyde‐containing molecules is described, highlighting the ease and versatility of the chemistry and how amine protonation can be used to switch solubility characteristics.