RESUMO
The use of functionalized nanoparticles (NPs) and their aggregation in the presence of a targeted analyte is a well-established molecular detection strategy predicated on harnessing specific molecular interactions to the NP periphery. Molecules able to specifically interact with the functionalized NPs alter the unique optical and electrochemical properties of the NPs as a function of interparticle spacing. While many intermolecular interactions have been successfully exploited in this manner in conjunction with aqueous NP systems, the use of non-aqueous NPs in the same capacity is significantly less explored. A fundamental interaction that has not been previously investigated in NP schemes is halogen bonding (XB). XB is an orthogonal, electrostatic interaction between a region of positive electrostatic potential (δ+) on a halogen atom (i.e., XB donor) and a negative (δ-) Lewis base (XB acceptor) molecule. To couple XB with NP systems, ligands featuring a molecular structure that promotes XB interactions need to be identified, optimized, and synthesized for subsequent attachment to NPs. Herein, density functional theory (DFT) and NMR techniques are used to identify a strong XB-donor moiety (-C6F4I) and a synthetic scheme for a thiolate ligand featuring that functionality is devised and executed with high purity/yield (78%). Ligand-exchange reactions allow functionalization of non-aqueous alkanethiolate-protected gold NPs or monolayer-protected clusters (MPCs) with the XB-donor ligands. Functionalized MPCs (f-MPCs), within both assembled films and in solution, are shown to engage in XB interactions with target XB-acceptor molecules. Molecular recognition events, including induced aggregation of the f-MPCs, are characterized with UV-vis spectroscopy, cyclic voltammetry, TEM imaging, and diffusion-ordered spectroscopy NMR with limits of detection of 50-100 nM for strong XB acceptors. While fundamental exploration of XB interactions is ongoing, this study represents a step toward utilizing XB within molecular detection schemes, an application with implications for supramolecular chemistry, forensic, and environmental chemical sensing.
RESUMO
Gold and silver salt mixtures are incorporated in ceramic glazes for in situ development of mixtures of gold and silver nanoparticles (NPs) that subsequently allow for a wide spectrum of low metal loading color control within ceramic materials. Prior work has shown that gold NPs can be used to create vibrant, color-rich red pigments in high-temperature ceramic and glass applications, though the achievable diameter of the gold NP ultimately limits the available range of color. The current study significantly expands color control from traditional gold nanoparticle red through silver nanoparticle green via the alteration of gold-to-silver salt ratios incorporated in the glaze formulations prior to sintering. Nanoparticle-based coloring systems are tested in both oxidative and reductive firing atmospheres. While the oxidation environment is found to be prohibitive for silver NP stability, the reductive atmosphere is able to form and sustain mixtures of gold and silver NPs across a wide color spectrum. All glazes are analyzed via reflectance spectrometry for color performance and samples are characterized via TEM and EDS for composition and sizing trends. This study creates new groundwork for a color-controlled NP system based on noble metal ratio blends that are both nontoxic and achieved with radically lower metal pigment loading than traditional glazes.
