Detection and Identification of Pesticides in Fruits Coupling to an Au-Au Nanorod Array SERS Substrate and RF-1D-CNN Model Analysis.

In this research, a method was developed for fabricating Au-Au nanorod array substrates through the deposition of large-area Au nanostructures on an Au nanorod array using a galvanic cell reaction. The incorporation of a granular structure enhanced both the number and intensity of surface-enhanced Raman scattering (SERS) hot spots on the substrate, thereby elevating the SERS performance beyond that of substrates composed solely of an Au nanorod. Calculations using the finite difference time domain method confirmed the generation of a strong electromagnetic field around the nanoparticles. Motivated by the electromotive force, Au ions in the chloroauric acid solution were reduced to form nanostructures on the nanorod array. The size and distribution density of these granular nanostructures could be modulated by varying the reaction time and the concentration of chloroauric acid. The resulting Au-Au nanorod array substrate exhibited an active, uniform, and reproducible SERS effect. With 1,2-bis(4-pyridyl)ethylene as the probe molecule, the detection sensitivity of the Au-Au nanorod array substrate was enhanced to 10-11 M, improving by five orders of magnitude over the substrate consisting only of an Au nanorod array. For a practical application, this substrate was utilized for the detection of pesticides, including thiram, thiabendazole, carbendazim, and phosmet, within the concentration range of 10-4 to 5 × 10-7 M. An analytical model combining a random forest and a one-dimensional convolutional neural network, referring to the important variable-one-dimensional convolutional neural network model, was developed for the precise identification of thiram. This approach demonstrated significant potential for biochemical sensing and rapid on-site identification.

The novel sandwich composite structure: a new detection strategy for the ultra-sensitive detection of cyclotrimethylenetrinitramine (RDX).

This study presents a novel sandwich composite structure that was designed for the ultra-sensitive detection of cyclotrimethylenetrinitramine (RDX). Au nanorod arrays (Au NRAs) were prepared and bound to 10-7M 6-MNA as adsorption sites for RDX, while Au nanorods (Au NRs) were modified using 10-5M 6-MNA as SERS probes. During detection, RDX molecules connect the SERS probe to the surface of the Au NRAs, forming a novel type of Au NRAs-RDX-Au NRs 'sandwich' composite structure. The electromagnetic coupling effect between Au NRs and Au NRAs is enhanced due to the molecular level of the connection spacing, resulting in new 'hot spots'. Meanwhile, Au NRAs and Au NRs have an auto-enhancement effect on 6-MNA. In addition, the presence of charge transfer in the formed 6-MNA-RDX complex induced chemical enhancement. The limits of detection of RDX evaluated by Raman spectroscopy using 6-MNA were as low as 10-12mg ml-1(4.5 × 10-15M) with good linear correlation between 10-12and 10-8mg ml-1(correlation coefficientR2 = 0.9985). This novel sandwich composite structure accurately detected RDX contamination in drinking water and on plant surfaces in an environment with detection limits as low as 10-12mg ml-1and 10-8mg ml-1.

A 'sandwich' structure for highly sensitive detection of TNT based on surface-enhanced Raman scattering.

Ultra-sensitive detection of 2,4,6-trinitrotoluene (TNT) plays an important role in society security and human health. The Raman probe molecule p-aminothiophenol (PATP) can interact with TNT in three ways to form a TNT-PATP complex. In this paper, a 'sandwich' structure was developed to detect TNT with high sensitivity. Au nano-pillar arrays (AuNPAs) substrates modified by low-concentration PATP through Au-S bonds were acted as capture probe for TNT. Meanwhile, Ag nano-particles (AgNPs) modified by PATP at higher concentration were employed as tags for surface-enhanced Raman scattering (SERS). The formation of the TNT-PATP complex is not only the means by which AuNPAs substrates recognize and capture TNT, but also links the SERS tags to TNT, forming an AuNPAs-TNT-AgNPs 'sandwich' structure. The Raman signal of PATP was greatly enhanced mainly because novel 'hot spots' formed between the AuNPAs and AgNPs of the 'sandwich' structure. The Raman signal of PATP was further amplified by the chemical enhancement effect induced by the TNT-PATP complex formation. Based on this mechanism, the limit of detection (LOD) of TNT was determined from the Raman signal of PATP. The LOD reached 10-9 mg/mL (4.4 × 10-12 M), much lower than that suggested by the US Environmental Protection Agency (88 nM). Moreover, TNT was selectively detected over several TNT analogues 2,4-dinitrotoluene (DNT), p-nitrotoluene (NT) and hexogen (RDX). Finally, the 'sandwich' structure was successfully applied to TNT detection in environmental water and sand.

Fabrication of Ag@Au (core@shell) nanorods as a SERS substrate by the oblique angle deposition process and sputtering technology.

Gold (Au) and silver (Ag) are the main materials exhibiting strong Surface-Enhanced Raman Scattering (SERS) effects. The Ag nano-rods (AgNRs) and Au nano-rods (AuNRs) SERS substrates prepared using the technology of the oblique angle deposition (OAD) process have received considerable attention in recent years because of their rapid preparation process and good repeatability. However, AgNR substrates are unstable due to the low chemical stability of Ag. To overcome these limitations, an Ag@Au core-shell nano-rod (NR) array SERS substrate was fabricated using the OAD process and sputtering technology. Moreover, simulation analysis was performed using finite-difference time-domain calculations to evaluate the enhancement mechanism of the Ag@Au NR array substrate. Based on the simulation results and actual process conditions, the Ag@Au core-shell NR array substrate with the Au shell thickness of 20 nm was studied. To characterize the substrate's SERS performance, 1,2-bis(4-pyridyl)ethylene (BPE) was used as the Raman probe. The limit of detection of BPE could reach 10-12 M. The Ag@Au NR array substrate demonstrated uniformity with an acceptable relative standard deviation. Despite the strong oxidation of the hydrogen peroxide (H2O2) solution, the Ag@Au NR array substrate maintains good chemical stability and SERS performance. And long-term stability of the Ag@Au NR substrate was observed over 8 months of storage time. Our results show the successful preparation of a highly sensitive, repeatable and stable substrate. Furthermore, this substrate proves great potential in the field of biochemical sensing.