We report on a synthetic approach to produce self-supported flexible surface-enhanced Raman scattering (SERS) active membranes consisting of polyamide (PA) nanofibers grafted with vertical Ag-nanosheets, via a combinatorial process of electrospinning PA-nanofiber membranes, assembling Au-nanoparticles on the PA-nanofibers as seeds for subsequent growth of Ag-nanosheets, and electrodepositing Ag-nanosheets on the electrospun PA-nanofibers. As a high density of Ag-nanosheets are vertically grown around each PA-nanofiber in the three-dimensional (3D) networked PA-nanofiber membranes, homogeneous nano-scaled gaps between the neighboring Ag-nanosheets are formed, leading to a high density of 3D SERS "hot spots" within the Ag-nanosheet-grafted PA-nanofiber membranes. The Ag-nanosheet-grafted PA-nanofiber membranes demonstrate high SERS activity with excellent Raman signal reproducibility for rhodamine 6G over the whole membrane. For a SERS-based trial analysis of polychlorinated biphenyls (PCBs, a kind of global environmental hazard), the 3D SERS substrate membranes are modified with mono-6-β-cychlodextrin to effectively capture PCB molecules. As a result, not only a low concentration down to 10(-6) M is reached, but also two congeners of PCBs in their mixed solution are identified, showing promising potential in SERS-based rapid detection of trace organic pollutants such as PCBs in the environment.

Large area arrays of length-tunable alumina nanotips on the joints of hexagonally patterned conical-pores in an anodic aluminum oxide (AAO) template are achieved via a repeated process of anodizing Al foil for pore growth downwards and phosphoric acid etching for pore-widening. By top-view sputtering Ag on the alumina nanotip arrays, hexagonally patterned arrays of Ag-nanorods (Ag-NRs) on the alumina nanotips and uniformly distributed Ag-nanoparticles (Ag-NPs) on the upper rim of the inner surface of the conical-pores are obtained and they exhibit strong surface-enhanced Raman scattering (SERS) activity due to the high density of sub-10 nm gaps between the nearest neighboring Ag-NRs and between the adjacent Ag-NPs. The resultant nanostructures are tailored to attain an optimal SERS enhancement factor of $3.2 Â 10 7 by tuning the Ag-sputtering duration. SERS measurements demonstrate that the as-fabricated large-scale Ag-nanostructures can serve as highly sensitive and reproducible SERS substrates. Finite element method calculation also confirms that the fabricated substrates possess excellent SERS activity. By modifying the Ag-NR arrays with mono-6-thio-b-cyclodextrin, the SERS detection limit of PCB-77 (a congener of polychlorinated biphenyls (PCBs)) reaches 10 À6 M, showing potential in SERS-based rapid detection of trace PCBs, a kind of global environmental hazardous material.

An improved label-free approach for highly sensitive and selective detection of 3,3',4,4'-tetrachlorobiphenyl (PCB-77), a type of polychlorinated biphenyl, via surface-enhanced Raman spectroscopy (SERS) using DNA aptamer-modified Ag-nanorod arrays as the effective substrate is reported. The devised system consists of Ag-nanorod (Ag-NR) arrays with the PCB-77 binding aptamers anchored covalently to the Ag surfaces through a thiol linker. The aptamers are made of single-stranded DNA (ssDNA) oligomers, with one end standing on the Ag surface, and upon conjugation with PCB-77, the ssDNA molecules can change their conformation to hairpin loops, so that the Raman intensity of guanines at the other end of the DNA strand increases accordingly. As such, the intensity ratio I(656 cm(-1))/I(733 cm(-1)) increases concomitantly with the increase of the concentration of PCB-77, making the quantitative evaluation of trace amounts of PCB-77 attainable. Moreover, it is found that the DNA aptamer-based Ag-NR arrays can be more responsive with a lower and optimal density of the DNA molecules modified on the substrate surface, and the best sensitivity for detection of PCB-77 can be achieved with the lower detection limit approaching 3.3 × 10(-8) M. This work therefore demonstrates that the design of aptamer-modified Ag-NRs can be used as a practically promising SERS substrate for label-free trace detection of persistent organic pollutants (POPs) in the environment.

The homogeneous attachment of metal-nanoparticles (metal-NPs) on pristine-graphene surface to construct pristine-graphene/metal-NPs hybrids is highly expected for application in many fi elds such as transparent electrodes and conductive composites. However, it remains a great challenge since the pristine-graphene is highly hydrophobic. Here, an environmentally friendly generic synthetic approach to large-scale pristine-graphene/ metal-NPs hybrids is presented, by a combinatorial process of exfoliating expanded graphite in N-methyl pyrrolidone via sonication and centrifugation to achieve the pristine-graphene, and attaching pre-synthesized metal-NPs on the pristine-graphene in ethanol via van der Waals interactions between the metal-NPs and the pristine-graphene. Nanoparticles of different metals (such as Ag, Au, and Pd) with various morphologies (such as sphere, cube, plate, multi-angle, and spherical-particle assembling) can be homogeneously attached on the defect-free pristine-graphene with controlled packing densities. Both the pristine-graphene and the metal-NPs preserve their original intrinsic structures. The as-synthesized pristine-graphene/Ag-NPs hybrids show very high surface-enhanced Raman scattering activity due to the combined effects of large surface area of the pristine-graphene to adsorb more target molecules and the electromagnetic enhancement of the Ag-NPs. This large-scale synthesis of the pristine-graphene/metal-NPs hybrids with tunable shape and packing density of metal-NPs opens up opportunities for fundamental research and potential applications ranging from devices to transparent electrodes and conductive composites.

Large-area Au-aggregate-assembled fractal patterns with tailored sizes and densities are achieved by sputtering Au nanoparticles on hexagonally patterned bowl-shaped-dimples on Al foil and subsequent annealing. After decorating with much smaller Ag nanoparticles, the resultant substrates exhibit an active and reproducible SERS effect.

A new type of surface-enhanced Raman scattering (SERS) substrate consisting of β-cyclodextrin (β-CD) coated SiO2@Au@Ag nanoparticles (SiO2@Au@Ag@CD NPs) has been achieved. Our protocol was a simplified approach as the fabrication and modification of the silver shell were realized in a single-step reaction by taking advantage of β-CD as both the reducing and stabilizing agents. The as-synthesized SiO2@Au@Ag@CD NPs were uniform in size and demonstrated high SERS activity and reproducibility. The substrates consisting of the SiO2@Au@Ag@CD NPs were employed for SERS detection of polychlorinated biphenyls (PCBs) including PCB-3, PCB-29 and PCB-77. The SERS detection sensitivity was significantly improved due to enrichment of more PCB molecules captured by β-CD on the substrate surface, as confirmed by the appearance of the new Raman bands which are attributed to the complexes between β-CD and PCBs according to the theoretical simulation. Therefore, this work presents a novel approach to the fabrication of effective SERS substrates that can be employed for rapid determination of trace amounts of PCBs in the environment with high detection sensitivity and recognition selectivity.

We present a surface-enhanced Raman scattering (SERS) substrate featured by large-scale homogeneously distributed Ag nanoparticles (Ag-NPs) with sub-10 nm gaps assembled on a two-layered honeycomb-like TiO(2) film. The two-layered honeycomb-like TiO(2) film was achieved by a two-step anodization of pure Ti foil, with its upper layer consisting of hexagonally arranged shallow nano-bowls of 160 nm in diameter, and the lower layer consisting of arrays of about fifty vertically aligned sub-20 nm diameter nanopores. The shallow nano-bowls in the upper layer divide the whole TiO(2) film into regularly arranged arrays of uniform hexagonal nano-cells, leading to a similar distribution pattern for the ion-sputtered Ag-NPs in each nano-cell. The lower layer with sub-20 nm diameter nanopores prevents the aggregation of the sputtered Ag-NPs, so that the Ag-NPs can get much closer with gaps in the sub-10 nm range. Therefore, large-scale high-density and quasi-ordered sub-10 nm gaps between the adjacent Ag-NPs were achieved, which ensures homogeneously distributed 'hot spots' over a large area for the SERS effect. Moreover, the honeycomb-like structure can also facilitate the capture of target analyte molecules. As expected, the SERS substrate exhibits an excellent SERS effect with high sensitivity and reproducibility. As an example, the SERS substrate was utilized to detect polychlorinated biphenyls (PCBs, a kind of persistent organic pollutants as global environmental hazard) such as 3,3',4,4'-pentachlorobiphenyl (PCB-77) with concentrations down to 10(-9) M. Therefore the large-scale Ag-NPs with sub-10 nm gaps assembled on the two-layered honeycomb-like TiO (2) film have potentials in SERS-based rapid trace detection of PCBs.

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