Ag-nanoparticles-decorated NiO-nanoflakes grafted Ni-nanorod arrays stuck out of porous AAO as effective SERS substrates.

NiO-nanoflakes (NiO-NFs) grafted Ni-nanorod (Ni-NR) arrays stuck out of the porous anodic aluminum oxide (AAO) template are achieved by a combinatorial process of AAO-confined electrodeposition of Ni-NRs, selectively etching part of the AAO template to expose the Ni-NRs, wet-etching the exposed Ni-NRs in ammonia to obtain Ni(OH)2-NFs grafted onto the cone-shaped Ni-NRs, and annealing to transform Ni(OH)2-NFs in situ into NiO-NFs. By top-view sputtering, Ag-nanoparticles (Ag-NPs) are decorated on each NiO-NFs grafted Ni-NR (denoted as NiO-NFs@Ni-NR). The resultant Ag-NPs-decorated NiO-NFs@Ni-NR (denoted as Ag-NPs@NiO-NFs@Ni-NR) arrays exhibit not only strong surface-enhanced Raman scattering (SERS) activity but also reproducible SERS-signals over the whole array. It is demonstrated that the strong SERS-activity is mainly ascribed to the high density of sub-10 nm gaps (hot spots) between the neighboring Ag-NPs, the semiconducting NiO-NFs induced chemical enhancement effect, and the lightning rod effect of the cone-shaped Ni-NRs. The three-level hierarchical nanostructure arrays stuck out of the AAO template can be utilized to probe polychlorinated biphenyls (PCBs, a kind of global environmental hazard) with a concentration as low as 5 × 10(-6) M, showing promising potential in SERS-based rapid detection of organic environmental pollutants.

Ostwald-ripening-induced growth of parallel face-exposed Ag nanoplates on micro-hemispheres for high SERS activity.

Ag nanoplates, as two-dimensional plasmonic nanostructures, have attracted intensive attention due to their strong shape-dependent optical properties and related applications. Here parallel face-exposed Ag nanoplates vertically grown on micro-hemisphere surfaces have been achieved by firstly electrodepositing the micro-hemispheres assembled by Ag nanoplates, whose planar surfaces are stuck together, on indium tin oxide substrates, and then Ostwald ripening the as-electrodeposited micro-hemispheres in water. The sizes of the nanoplates and the gaps between the neighboring nanoplates have been tailored by tuning the Ostwald-ripening duration, so that the SERS activity of the micro-hemispheres has been remarkably improved. The improved SERS activity can be well explained by our systematic finite-element simulation. Therefore, Ostwald ripening offers a route to the synthesis of Ag nanoplates, and the optimization of plasmon coupling and SERS activity of nanostructure-assembled systems.

Electrospun 1,4-DHAQ-doped cellulose nanofiber films for reusable fluorescence detection of trace Cu2+ and further for Cr3+.

1,4-Dihydroxyanthraquinone (1,4-DHAQ, a fluorophore) doped cellulose (CL) (denoted as 1,4-DHAQ@CL) microporous nanofiber film has been achieved via simple electrospinning and subsequent deacetylating, and used for highly sensitive and selective fluorescence detection of Cu(2+) in aqueous solution. As the resultant byproduct of Cu(2+)-contaminated 1,4-DHAQ@CL nanofiber film showed recovered fluorescence by extra addition of Cr(3+) nitrate solution, 1,4-DHAQ and Cu(2+) codoped CL (denoted as (1,4-DHAQ)-Cu(2+)@CL)) microporous nanofiber film has been further fabricated for the detection of Cr(3+) in aqueous solution. It was found that the fluorescence intensity of the 1,4-DHAQ@CL microporous nanofiber film linearly decreases with Cu(2+) concentration ranging from 2.5 × 10(-9) to 3.75 × 10(-8) M, while that of the codoped (1,4-DHAQ)-Cu(2+)@CL nanofiber film linearly increases with Cr(3+) concentration from 2.5 × 10(-9) to 2.5 × 10(-8) M, both with high selectivity over many other common heavy metal ions. The sensing mechanism for Cu(2+) is ascribed to the formation of phenolate between 1,4-DHAQ and Cu(2+), while that for Cr(3+) is attributed to the reversing reaction from Cu(2+)-based phenolate to Cu(2+) and Cr(3+)-based excited complex with recovered fluorescence. The sensitive and selective detection of Cu(2+) and Cr(3+) by using the 1,4-DHAQ@CL and the (1,4-DHAQ)-Cu(2+)@CL nanofiber films was further demonstrated in polluted lake waters, thus indicating their potential applications in environmental monitoring of Cu(2+) and Cr(3+) in polluted water. Additionally, both the 1,4-DHAQ@CL and (1,4-DHAQ)-Cu(2+)@CL microporous nanofiber films are reusable for the detection of Cu(2+) and Cr(3+), respectively, after simple treatment. The design concept in this work might also open a door to the design of effective fluorescence probes for other heavy metal ions.

A novel assessment considering spatial and temporal variations of water quality to identify pollution sources in urban rivers.

It's vital to explore critical indicators when identifying potential pollution sources of urban rivers. However, the variations of urban river water qualities following temporal and spatial disturbances were highly local-dependent, further complicating the understanding of pollution emission laws. In order to understand the successional trajectory of water qualities of urban rivers and the underlying mechanisms controlling these dynamics at local scale, we collected daily monitoring data for 17 physical and chemical parameters from seven on-line monitoring stations in Nanfeihe River, Anhui, China, during the year 2018. The water quality at tributaries were similar, while that at main river was much different. A seasonal ''turning-back" pattern was observed in the water quality, which changed significantly from spring to summer but finally changed back in winter. This result was possibly regulated by seasonally-changed dissolved oxygen and water temperature. Linear mixed models showed that the site 2, with the highest loads of pollution, contributed the highest (ß = 0.316, P < 0.001) to the main river City Water Quality Index (CWQI) index, but site 5, the geographically nearest site to main river monitoring station, did not show significant effect. In contrast, site 5 but not site 2 contributed the highest (ß = 0.379, P < 0.001) to the main river water quality. Therefore, CWQI index was a better index than water quality to identify potential pollution sources with heavy loads of pollutants, despite temporal and spatial disturbances at local scales. These results highlight the role of aeration in water quality controlling of urban rivers, and emphasized the necessity to select proper index to accurately trace the latent pollution sources.

Flexible membranes of Ag-nanosheet-grafted polyamide-nanofibers as effective 3D SERS substrates.

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-ß-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.

Green synthesis of large-scale highly ordered core@shell nanoporous Au@Ag nanorod arrays as sensitive and reproducible 3D SERS substrates.

We present a simple green synthetic approach to large-scale and highly ordered arrays of vertical nanoporous Au nanorods, with an ultrathin Ag-layer in situ electrodeposited on each nanoporous Au nanorod (denoted as core@shell nanoporous Au@Ag nanorod). As both the nanopores within each nanorod and the gaps between the neighboring nanorods create three-dimensional (3D) "hot spots" homogeneously distributed throughout the whole substrate, the core@shell nanoporous Au@Ag nanorod arrays were proved to be sensitive and reproducible surface-enhanced Raman scattering (SERS) substrates. Not only universal probe molecules (rhodamine 6G, R6G) but also nonadsorbing molecules (polychlorinated biphenyls, PCBs) have been detected by using the substrates. After mono-6-thio-ß-cyclodextrin (HS-ß-CD) was modified to efficiently capture more PCBs molecules, the detection limit of PCBs was further reduced to 5.35 × 10(-7) M. As a trial of practical application, R6G and PCBs with different molar ratios in their mixed solutions were identified, and two congeners of PCBs in their mixture could also be distinguished, showing great potentials in real-time simultaneous detection of multiple pollutants.