We report label-free small molecule sensing on nanoporous gold disks functionalized with stabilized Guanine-quadruplex (G4) moieties using surface-enhanced Raman spectroscopy (SERS). By utilizing the unique G4 topological structure, target molecules can be selectively captured onto nanoporous gold (NPG) disk surfaces via π-π stacking and electrostatic attractions. Together with high-density plasmonic "hot spots" of NPG disks, the captured molecules produce a remarkable SERS signal. Our strategy represents the first example of the detection of foreign molecules conjugated to nondouble helical DNA nanostructures using SERS while providing a new technique for studying the formation and evolution of G4 moieties. The molecular specificity of G4 is known to be controlled by its unit sequence. Without losing generality, we have selected d(GGT)GG sequence for the sensing of malachite green (MG), a known carcinogen frequently abused illegally in aquaculture. The newly developed technique achieved a lowest detectable concentration at an impressive 50 pM, two orders of magnitude lower than the European Union (EU) regulatory requirement, with high specificity against potential interferents. To demonstrate the translational potential of this technology, we achieved a lowest detectable concentration of 5.0 nM, meeting the EU regulatory requirement, using a portable probe based detection system.
A rapid and cost-effective colorimetric sensor has been developed for the detection of bacteria (Bacillus subtilis was selected as an example). The sensor was designed to rely on lysozyme-capped AuNPs with the advantages of effective amplification and high specificity. In the sensing system, lysozyme was able to bind strongly to Bacillus subtilis, which effectively induced a color change of the solution from light purple to purplish red. The lowest concentration of Bacillus subtilis detectable by the naked eye was 4.5 × 10(3) colony-forming units (CFU) mL(-1). Similar results were discernable from UV-Vis absorption measurements. A good specificity was observed through a statistical analysis method using the SPSS software (version 17.0). This simple colorimetric sensor may therefore be a rapid and specific method for a bacterial detection assay in complex samples.
A promising and highly sensitive electrochemiluminescence (ECL) sensor for the detection of Cu(2+) based on Cu(+)-catalyzed click reaction is described in this paper. Firstly, 1-azidoundecan-11-thiol was assembled on the Au electrode surface via a simple thiol-Au reaction, then the propargyl-functionalized Ru(bpy)(3)(2+)-doped SiO(2) nanoparticles (Ru-SNPs) ECL probe was covalently coupled on the electrode surfaces via click chemistry. Cu(+), the catalyst for click chemistry, is derived from the electrolytic reduction of Cu(2+)via the Bulk Electrolysis with coulometry (BE) technique and without any reductants. It is found that the ECL intensity detected from the electrode surface has a linear relationship with the logarithm of Cu(2+) concentration in the range of 1.0 × 10(-15) to 1.0 × 10(-11) M with a detection limit of 1.0 × 10(-16) M. Also, the method is highly specific even in the presence of high concentrations of other metal cations. It has been applied to detect trace Cu(2+) in complex samples (hepatoma cell) without sample treatment.
A highly selective and sensitive electrochemical sensor for ascorbic acid (AA) assay has been prepared through Cu(I) catalyzed azide-alkyne cycloaddition reaction (CuAAC). The catalyst, Cu(I) species, is acquired from the reduction of Cu(II) by AA in situ. In the presence of Cu(I) catalyst, the azide modified Au electrode surface is shown to react quantitatively with terminal propargyl-functionalized ferrocene forming 1,2,3-triazoles. The electrochemical response of propargyl-functionalized ferrocene modified Au electrode surface can be monitored using differential pulse voltammetry (DPV) technique. Under optimal conditions, it is found that the current intensity has a linear relationship with the logarithm of AA concentration in the range of 5.0 × 10(-12) to 1.0 × 10(-9) M. Furthermore, the proposed electrochemical sensor shows a good stability (RSD 4.2%), high selectivity and low detection limit for AA detection. In addition, it also demonstrates that the proposed sensor can be applied to detect AA in real urine samples with satisfactory results.
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