ABSTRACT
We present a novel approach to produce gold nanoclusters (Au NCs) in the pores of mesoporous silica nanoparticles (MSNs) by sequential and controlled addition of metal ions and reducing agents. This impregnation technique was followed to confine Au NCs inside the pores of MSNs without adding external ligands or stabilizing agents. TEM images show a uniform distribution of monodisperse NCs with an average size of 1.37 ± 0.4 nm. Since the NCs are grown in situ in MSN pores, additional support and high temperature calcination are not required to use them as catalysts. The use of Au NC/MSNs as a catalyst for the epoxidation of styrene in the presence of tert-butyl hydroperoxide (TBHP) as a terminal oxidant resulted in an 88% conversion of styrene in 12 h with a 74% selectivity towards styrene epoxide. Our observations suggest that this remarkable catalytic performance is due to the small size of Au NCs and the strong interaction between gold and the MSNs. This catalytic conversion is environmentally friendly as it is solvent free. We believe our synthetic approach can be extended to other metal NCs offering a wide range of applications.
ABSTRACT
Controlling the size, number, and shape of nanogaps in plasmonic nanostructures is of significant importance for the development of novel quantum plasmonic devices and quantitative sensing techniques such as surface-enhanced Raman scattering (SERS). Here, we introduce a new synthetic method based on coordination interactions and galvanic replacement to prepare core-shell plasmonic nanorods with tunable enclosed nanogaps. Decorating Au nanorods with Raman reporters that strongly coordinate Ag+ ions (e.g., 4-mercaptopyridine) afforded uniform nucleation sites to form a sacrificial Ag shell. Galvanic replacement of the Ag shell by HAuCl4 resulted in Au-AgAu core-shell structure with a uniform intra-nanoparticle gap. The size (length and width) and morphology of the core-shell plasmonic nanorods as well as the nanogap size depend on the concentration of the coordination complexes formed between Ag+ ions and 4-mercaptopyridine. Moreover, encapsulating Raman reporters within the nanogaps afforded an internal standard for sensitive and quantitative SERS analysis. To test the applicability, core-shell plasmonic nanorods were functionalized with aptamers specific to circulating tumor cells such as MCF-7 (Michigan Cancer Foundation-7, breast cancer cell line). This system could selectively detect as low as 20 MCF-7 cells in a blood mimicking fluid employing SERS. The linking DNA duplex on core-shell plasmonic nanorods can also intercalate hydrophobic drug molecules such as Doxorubicin, thereby increasing the versatility of this sensing platform to include drug delivery. Our synthetic method offers the possibility of developing multifunctional SERS-active materials with a wide range of applications including biosensing, imaging, and therapy.
Subject(s)
Neoplastic Cells, Circulating , Gold , Humans , Metal Nanoparticles , Nanostructures , Nanotubes , SilverABSTRACT
The synthesis of a luminescent quantum cluster (QC) of gold with a quantum yield of approximately 4 % is reported. It was synthesized in gram quantities by the core etching of mercaptosuccinic acid protected gold nanoparticles by bovine serum albumin (BSA), abbreviated as Au(QC)@BSA. The cluster was characterized and a core of Au(38) was assigned tentatively from mass spectrometric analysis. Luminescence of the QC is exploited as a "turn-off" sensor for Cu(2+) ions and a "turn-on" sensor for glutathione detection. Metal-enhanced luminescence (MEL) of this QC in the presence of silver nanoparticles is demonstrated and a ninefold maximum enhancement is seen. This is the first report of the observation of MEL from QCs. Folic acid conjugated Au(QC)@BSA was found to be internalized to a significant extent by oral carcinoma KB cells through folic acid mediated endocytosis. The inherent luminescence of the internalized Au(QC)@BSA was used in cell imaging.
