ABSTRACT
Recent advancements in metal-enhanced fluorescence (MEF) suggest that it can be a promising tool for detecting molecules at very low concentrations when a fluorophore is fixed near the surface of metal nanoparticles. We report a simple method for aggregating multiple gold nanoparticles (GNPs) on Rhodamine B (RhB)-doped silica nanoparticles (SiNPs) utilizing dithiocarbamate (DTC) chemistry to produce MEF in solution. Dye was covalently incorporated into the growing silica framework via co-condensation of a 3-aminopropyltriethoxysilane (APTES) coupled RhB precursor using the Stöber method. Electron microscopy imaging revealed that these mainly non-spherical particles were relatively large (80 nm on average) and not well defined. Spherical core-shell particles were prepared by physisorbing a layer of RhB around a small spherical silica particle (13 nm) before condensing an outer layer of silica onto the surface. The core-shell method produced nanospheres (~30 nm) that were well defined and monodispersed. Both dye-doped SiNPs were functionalized with pendant amines that readily reacted with carbon disulfide (CS2) under basic conditions to produce DTC ligands that have exhibited a high affinity for gold surfaces. GNPs were produced via citrate reduction method and the resulting 13 nm gold nanospheres were then recoated with an ether-terminated alkanethiol to provide stability in ethanol. Fluorescent enhancement was observed when excess GNPs were added to DTC coated dye-doped SiNPs to form nanoparticle aggregates. Optimization of this system gave a fluorescence brightness enhancement of over 200 fold. Samples that gave fluorescence enhancement were characterized through Transmission Emission Micrograph (TEM) to reveal a pattern of multiple aggregation of GNPs on the dye-doped SiNPs.
ABSTRACT
Graphene field-effect transistors (GFET) have emerged as powerful detection platforms enabled by the advent of chemical vapor deposition (CVD) production of the unique atomically thin 2D material on a large scale. DNA aptamers, short target-specific oligonucleotides, are excellent sensor moieties for GFETs due to their strong affinity to graphene, relatively short chain-length, selectivity, and a high degree of analyte variability. However, the interaction between DNA and graphene is not fully understood, leading to questions about the structure of surface-bound DNA, including the morphology of DNA nanostructures and the nature of the electronic response seen from analyte binding. This review critically evaluates recent insights into the nature of the DNA graphene interaction and its affect on sensor viability for DNA, small molecules, and proteins with respect to previously established sensing methods. We first discuss the sorption of DNA to graphene to introduce the interactions and forces acting in DNA based GFET devices and how these forces can potentially affect the performance of increasingly popular DNA aptamers and even future DNA nanostructures as sensor substrates. Next, we discuss the novel use of GFETs to detect DNA and the underlying electronic phenomena that are typically used as benchmarks for characterizing the analyte response of these devices. Finally, we address the use of DNA aptamers to increase the selectivity of GFET sensors for small molecules and proteins and compare them with other, state of the art, detection methods.
