Surface-Enhanced Raman Scattering Spectral Imaging for the Attomolar Range Detection of Crystal Violet in Contaminated Water

A series of nanocomposites based on polyamide (NL16, PA) filter membranes containing metal nanoparticles (NPs) have been prepared by filtration under reduced pressure of the metal colloids. The ensuing materials were then investigated as substrates for surface-enhanced Raman scattering (SERS) imaging studies envisaging the spectroscopic detection of vestigial organic pollutants dissolved in contaminated water. The organic dye crystal violet (CV) was used here as a model pollutant because it is a hazardous compound present in certain effluent waters. Moreover this compound is well-known for its strong SERS activity, which is clearly advantageous in the context of material development for SERS. Indeed, several preparative strategies were employed to prepare PA-based composites, and the impact on SERS detection was investigated. These include the use of chemical and morphological distinct plasmonic NPs (Ag, Au), a variable metal load and changing the order of addition of the analytical specimens. These studies demonstrate that the parameters employed in the fabrication of the SERS substrates have a strong impact on the Raman signal enhancement. The use of Raman imaging during the fabrication process allows establishing improvements that translate to better performances of the substrates in the analyte detection. The results have been interpreted by considering an integrated set of operational parameters that include the affinity of CV molecules to the substrate, amount and dispersion of NPs in the PA membranes, and the detection method.  Noteworthy the use of SERS analysis assisted with Raman imaging allowed achieving a detection limit for CV as low as 100 aM in ultrapure water and 10 fM in real samples

Raman Signal Enhancement Dependence on the Gel Strength of Ag/Hydrogels Used as SERS Substrates

A series of hydrogel samples composed of Ag nanoparticles dispersed in carrageenan gels have been prepared and used in SERS studies. These studies demonstrate the dependence of the enhancement of the SERS signal on the strength of the Ag/polysaccharide hydrogel. 2,2′-Dithiodipyridine was used as the analyte probe. Several strategies were employed in order to vary the gel strength. These include the increase of the polysaccharide content in the gel, the addition of KCl as cross-linker, and the variation of the type of carrageenan (κ, ι, λ) network. An increase in the gel strength originates an increase in the SERS enhancement observed. The results have been interpreted considering hot spots increase due to the formation of Ag particles nanojunctions as the biopolymer matrix tends to rearrange into stronger gels. This is the first report showing that there is a direct correlation between the gel strength of a hydrogel composite used as substrate and its analytical SERS sensitivity

High-throughput tool to discriminate effects of NMs (Cu-NPs, Cu-nanowires, CuNO₃, and Cu salt aged): transcriptomics in <i>Enchytraeus crypticus</i>

<p>The current testing of nanomaterials (NMs) via standard toxicity tests does not cover many of the NMs specificities. One of the recommendations lays on understanding the mechanisms of action, as these can help predicting long-term effects and safe-by-design production. In the present study, we used the high-throughput gene expression tool, developed for <i>Enchytraeus crypticus</i> (4 × 44k Agilent microarray), to study the effects of exposure to several copper (Cu) forms. The Cu treatments included two NMs (spherical and wires) and two copper-salt treatments (CuNO₃ spiked and Cu salt field historical contamination). To relate gene expression with higher effect level, testing was done with reproduction effect concentrations (EC₂₀, EC₅₀), using 3 and 7 days as exposure periods. Results showed that time plays a major role in the transcriptomic response, most of it occurring after 3 days. Analysis of gene expression profiles showed that Cu-salt-aged and Cu-nanowires (Nwires) differed from CuNO₃ and Cu-nanoparticles (NPs). Functional analysis revealed specific mechanisms: Cu-NPs uniquely affected senescence and cuticle pattern formation, which can result from the contact of the NPs with the worms’ tegument. Cu-Nwires affected reproduction via male gamete generation and hermaphrodite genitalia development. CuNO₃ affected neurotransmission and locomotory behavior, both of which can be related with avoidance response. Cu salt-aged uniquely affected phagocytosis and reproductive system development (via different mechanisms than Cu-Nwires). For the first time for Cu (nano)materials, the adverse outcome pathways (AOPs) drafted here provide an overview for common and unique effects per material and linkage with apical effects.</p

Fluorescent Bioactive Corrole Grafted-Chitosan Films

Transparent corrole grafted-chitosan films were prepared by chemical modification of chitosan with a corrole macrocycle, namely, 5,10,15-tris­(pentafluorophenyl)­corrole (TPFC), followed by solvent casting. The obtained films were characterized in terms of absorption spectra (UV–vis), FLIM (fluorescence lifetime imaging microscopy), structure (FTIR, XPS), thermal stability (TGA), thermomechanical properties (DMA), and antibacterial activity. The results showed that the chemical grafting of chitosan with corrole units did not affect its film-forming ability and that the grafting yield increased with the reaction time. The obtained transparent films presented fluorescence which increases with the amount of grafted corrole units. Additionally, all films showed bacteriostatic effect against S. aureus, as well as good thermomechanical properties and thermal stability. Considering these features, promising applications may be envisaged for these corrole-chitosan films, such as biosensors, bioimaging agents, and bioactive optical devices