Handheld SERS coupled with QuEChERs for the sensitive analysis of multiple pesticides in basmati rice

Pesticides are a safety issue globally and cause serious concerns for the environment, wildlife and human health. The handheld detection of four pesticide residues widely used in Basmati rice production using surface-enhanced Raman spectroscopy (SERS) is reported. Different SERS substrates were synthesised and their plasmonic and Raman scattering properties evaluated. Using this approach, detection limits for pesticide residues were achieved within the range of 5 ppb-75 ppb, in solvent. Various extraction techniques were assessed to recover pesticide residues from spiked Basmati rice. Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERs) acetate extraction was applied and characteristic spectral data for each pesticide was obtained from the spiked matrix and analysed using handheld-SERS. This approach allowed detection limits within the matrix conditions to be markedly improved, due to the rapid aggregation of nanogold caused by the extraction medium. Thus, detection limits for three out of four pesticides were detectable below the Maximum Residue Limits (MRLs) of 10 ppb in Basmati rice. Furthermore, the multiplexing performance of handheld-SERS was assessed in solvent and matrix conditions. This study highlights the great potential of handheld-SERS for the rapid on-site detection of pesticide residues in rice and other commodities.

Hydrothermal Synthesis of Ag Thin Films and Their SERS Application

In this article, a facile, one-step method for the formation of silver thin-film nanostructures on the surface of Al2O3 substrates using the hydrothermal method is proposed. The dependence of the SERS effect intensity of the formed films during the detection of methylene blue (MB) low concentrations on the synthesis conditions, additional temperature treatment, and laser radiation wavelength (532 and 780 nm) in comparison with similar dye films on commercial SERS substrates is shown. The detection limit of the analyte used for the indicated lasers is estimated. The effect of the synthesis temperature on the particle size, crystal structure, and microstructure features of the obtained thin films based on silver nanoparticles is demonstrated. Using spreading resistance microscopy, the interface between the substrate and Ag particles is studied, and the dependence of the size of the corresponding gap between them and the nature of microstructural defects on the parameters of hydrothermal treatment of reaction systems in the presence of Al2O3 substrates is shown. As a result of the study, the factors associated with the properties of the obtained SERS substrates and the parameters of recording the spectra, which affect the amplification factor of the spectral lines intensity of the analyte, are revealed.

Rapid formation methods of arrays of randomly distributed Au and Ag nanoparticles, their morphologies and optical characteristics

By the method of rapid radiation heating (at a speed of 20-25 K/s) of Au and Ag films with a thickness of 4-35 nm to temperatures of 573-693 K in air and in the process of vacuum deposition of silver on heated (up to 700 K at a heating rate of 10 K/s ) glass substrates formed Au and Ag NPs arrays with nanoparticle sizes from several tens to hundreds of nanometers, the position λSPR of which is in the range of 520-597 nm for Au NPs and 424-509 nm for Ag NPs. It is established that the average size of nanoparticles depends on the thickness of gold and silver films and the annealing temperature. The results testify that glass substrates with arrays of randomly distributed gold NPs can be used as effective SERS-substrates for the investigation of Raman spectra of nanosized (50-100 nm) chalcogenide films.

Fabrication of Au-Nanoparticle-Decorated Cu Mesh/Cu(OH)2 @HKUST-1 Nanorod Arrays and Their Applications in Surface-Enhanced Raman Scattering

Here we report a simple fabrication method for large-scale hybrid surface-enhanced Raman scattering (SERS) active substrates composed of Au-nanoparticle-decorated three-dimensional (3D) Cu(OH)2@HKUST-1 (Cu3(btc)2, H3btc = 1,3,5-benzenetricarboxylic acid) nanorod arrays on a woven Cu mesh (Cu mesh/Cu(OH)2@HKUST-1@Au). Cu(OH)2 nanorods were first obtained from a simple in situ chemical engraving Cu mesh and then utilized as self-sacrificing templates to achieve HKUST-1 nanocube-assembled nanorods; finally, Au nanoparticles (Au NPs) were sputtered onto the Cu(OH)2@HKUST-1 nanorods. Due to the large surface area, the three-dimensional Cu mesh/Cu(OH)2@HKUST-1 nanorods could load high-density Au NPs and capture target detection molecules, which is beneficial to the formation of a strong electromagnetic field coupling between Au NPs, and provides abundant “hot spots” for a sensitive and uniform SERS effect. Using the Cu mesh/Cu(OH)2@HKUST-1@Au nanorod arrays as the SERS substrate, 10−9 M Rhodamine 6G and 10−8 M 4-aminothiophenolcan were identified. To verify their practical application, the fabricated arrays were employed as SERS substrates for the detection of thiram, and 10−8 M thiram could be recognized. The hybrid SERS substrates show potential applications in the field of environmental pollutant detection and this is of great significance to the sustainable development of the environment.

Sensing the Anti-Epileptic Drug Perampanel with Paper-Based Spinning SERS Substrates

The applications of SERS in therapeutic drug monitoring, or other fields of analytical chemistry, require the availability of sensitive sensors and experimental approaches that can be implemented in affordable ways. In this contribution, we show the production of cost-effective SERS sensors obtained by depositing Lee-Meisel Ag colloids on filter paper either by natural sedimentation or centrifugation. We have characterized the morphological and plasmonic features of the sensors by optical microscopy, SEM, and UV-Vis spectroscopy. Such sensors can be used to quantify by SERS the anti-epileptic drug Perampanel (in the concentration range 1 × 10−4–5 × 10−6 M) by spinning them during the micro-Raman measurements on the top of a custom device obtained from spare part hard disk drives. This approach minimizes laser-induced heating effects and allows averaging over the spatial non-uniformity of the sensor.

Nanoscale engineering of ring-mounted nanostructure around AAO nanopores for highly sensitive and reliable SERS substrates

Surface-enhanced Raman scattering (SERS) is recognized as one of the most favored techniques for enhancing Raman signals. The morphology of the SERS substrate profoundly affects molecular Raman spectra. This study aimed to construct a ring-mounted nanostructured substrate via liquid–liquid two-phase self-assembly (LLSA) incorporated with anodic aluminum oxide (AAO) membrane transfer techniques. High-density nanoparticles (NPs) assembled on AAO membranes were ascribed to reduce the diameters of the nanopores, with Au–Ag alloy NPs to regulate the dielectric constant so as to reveal the local surface plasmon resonance tunability. SERS engineered in this way allowed for the fabrication of a ring-mounted nanostructured substrate where the distribution density of NPs and dielectric constant could be independently fine-tuned. High SERS activity of the substrate was revealed by detecting the enhanced factor of crystal violet and rhodamine 6G molecules, which was up to 1.56 × 106. Moreover, SERS of thiram target molecules confirmed the supersensitivity and repeatability of the substrate as a practical application. The results of this study manifested a low-cost but high-efficiency ring-mounted nanostructured SERS substrate that might be suitable in many fields, including biosensing, medical research, environmental monitoring, and optoelectronics.