An efficient and green approach was used to fabricate novel and low-cost surface-enhanced Raman scattering (SERS) spectroscopy sensors based on 4-aminothiophenol (4-ATP) functionalized ZnO-Ag hybrid nanoflowers for the detection of explosives. Such SERS sensors exhibited high sensitivity to rhodamine 6G (R6G) at a low concentration of 10(-12) M and an enhancement factor of over 4.12 × 10(6) was achieved. Moreover, the Raman-inactive trinitrotoluene (TNT) initiated the high Raman scattering of non-resonated 4-ATP through the formation of a π-donor-π-acceptor interaction between the π-acceptor, TNT, and the π-donor, the 4-ATP-Ag-ZnO complex, on the flower-like hybrids. Because this π-donor-π-acceptor interaction could effectively induce the "hot spots" for SERS, TNT concentrations as low as 5 × 10(-9) M could be detected. Furthermore, other derivatives of TNT were also explored, and this sensor exhibited better selectivity for TNT than other similarly structured explosives. The low-cost hybrid SERS substrates presented good sensitivity and reproducibility for the analytes employed, demonstrating promising application in forensic science and homeland security.
Hierarchical assembly of plasmonic nanostructures can induce high surface-enhanced Raman scattering (SERS) activity. However, it is a challenge to uniformly disperse the hierarchical nanostructures onto a planar substrate to achieve the SERS signal reproducibility. This report presents a facile route to fabricate a hexagonally patterned flower-like silver particle array as the SERS substrate. First, the hexagonally ordered silver hemisphere arrays with smooth surface are molded in the pores of an anodic aluminum oxide template. The Ag-nanosheets are then electrodeposited onto the surface of individual silver hemispheres. The numerous nano-edges and nano-gaps between adjacent nanosheets render a large number of hot spots, leading to high SERS activity over a larger area of chip. The silver flower-like array is employed as the SERS substrate, which is able to detect 0.1 nM rhodamine 6G and 1 µM 3,3’,4,4’-tetrachlorobiphenyl (PCB-77, a persistent organic pollutant).
Here we report a low-cost synthetic approach for the direct fabrication of large-area Au nanourchin arrays on indium tin oxide (ITO) via a facile galvanic-cell-reaction-driven deposition in an aqueous solution of chloroauric acid and poly(vinyl pyrrolidone) (PVP). The homogeneous Au nanourchins are composed of abundant sharp nanotips, which can served as nanoantennas and increase the local electromagnetic field enhancement dramatically. Finite element theoretical calculations confirm the strong electromagnetic field can be created around the sharp nanotips and located in the nanogaps between adjacent tips of the Au nanourchins. In addition, the interparticle nanogaps between the neighboring Au nanourchins may create additional hotspots, which can induce the higher electromagnetic field intensity. By using rhodamine 6G as a test molecule, the large-area Au nanourchin arrays on ITO exhibit active, uniform, and reproducible surface-enhanced Raman scattering (SERS) effect. To trial their practical application, the Au nanourchin arrays are utilized as SERS substrates to detect 3,3’,4,4’-tetrachlorobiphenyl (PCB-77) one congener of polychlorinated biphenyls (PCBs) as a notorious class of persistent organic pollutants. The characteristic Raman peaks can be still identified when the concentration of PCB-77 is down to 5 × 10−6 M.
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