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Surface-enhanced Raman scattering (SERS) technology, known for its ultra-high sensitivity and molecular specificity, is widely used for material detection. In this study, a high-performance SERS substrate was successfully fabricated by depositing a 10 nm silver film on a silicon wafer under low-vacuum conditions, systematically optimizing the annealing temperature. At the optimal annealing temperature, the silver film underwent particle formation, creating a high-density “hotspot” distribution, which significantly enhanced the SERS sensitivity. With rhodamine 6G (R6G) as a beta-molecule, the SERS performance of the nanostructure was evaluated, with the optimized substrate demonstrating the detection LOD achieved 10 −8 M. A linear relationship was established between the intensity of the Characteristic Raman peak of thiram at 1384 cm −1 and the logarithm of its concentration, achieving a Correlation value is 0.986 and the LOD achieved 10 −9 M.

Here we reported a residue-free green nanotechnology which synergistically enhance the pesticides efficiency and successively eliminate its residue. We built up a composite antifungal system by a simple pre-treating and assembling procedure for investigating synergy. Investigations showed 0.25 g/L ZnO nanoparticles (NPs) with 0.01 g/L thiram could inhibit the fungal growth in a synergistic mode. More importantly, the 0.25 g/L ZnO NPs completely degraded 0.01 g/L thiram under simulated sunlight irradiation within 6 hours. It was demonstrated that the formation of ZnO- thiram antifungal system, electrostatic adsorption of ZnO NPs to fungi cells and the cellular internalization of ZnO- thiram composites played important roles in synergy. Oxidative stress test indicated ZnO-induced oxidative damage was enhanced by thiram that finally result in synergistic antifungal effect. By reducing the pesticides usage, this nanotechnology could control the plant disease economically, more significantly, the following photocatalytic degradation of pesticide greatly benefit the human social by avoiding negative influence of pesticide residue on public health and environment.

Pesticide coated seeds are commonly used in agriculture, and may be an important source of food for some birds in times of scarcity, as well as a route of pesticide ingestion. We tested the lethal and sub-lethal effects of treated seed ingestion by the red-legged partridge ( Alectoris rufa ), a game bird of high socio-economic value in Spain. One year-old partridges ( n  = 42 pairs) were fed for 10 days in spring (prior to breeding) with wheat treated with difenoconazole (fungicide), thiram (fungicide) or imidacloprid (insecticide), using two doses for each pesticide (the one recommended, and its double to represent potential cases of abuse of pesticides). We investigated the direct and indirect effects on the body condition, physiology, immunology, coloration and subsequent reproduction of exposed partridges. For the latter, eggs were collected, measured and incubated and the growth and survival of chicks were monitored. Thiram and imidacloprid at high exposure doses produced mortalities of 41.6 and 58.3 %, respectively. The first death was observed at day 3 for imidacloprid and at day 7 for thiram. Both doses of the three pesticides caused sublethal effects, such as altered biochemical parameters, oxidative stress and reduced carotenoid-based coloration. The high exposure doses of imidacloprid and thiram also produced a decrease in cellular immune response measured by the phytohemagglutinin test in males. Bearing in mind the limitation of the small number of surviving pairs in some treatments, we found that the three pesticides reduced the size of eggs and imidacloprid and difenoconazole also reduced the fertilization rate. In addition, both thiram and imidacloprid reduced chick survival. These experiments highlight that the toxicity of pesticide-treated seeds is a factor to consider in the decline of birds in agricultural environments.

In this study, SiO2@Au@4-MBA@Ag (4-mercaptobenzoic acid labeled gold-silver-alloy-embedded silica nanoparticles) nanomaterials were investigated for the detection of thiram, a pesticide. First, the presence of Au@4-MBA@Ag alloys on the surface of SiO2 was confirmed by the broad bands of ultraviolet-visible spectra in the range of 320–800 nm. The effect of the 4-MBA (4-mercaptobenzoic acid) concentration on the Ag shell deposition and its intrinsic SERS (surface-enhanced Raman scattering) signal was also studied. Ag shells were well coated on SiO2@Au@4-MBA in the range of 1–1000 µM. The SERS intensity of thiram-incubated SiO2@Au@4-MBA@Ag achieved the highest value by incubation with 500 µL thiram for 30 min, and SERS was measured at 200 µg/mL SiO2@Au@4-MBA@Ag. Finally, the SERS intensity of thiram at 560 cm−1 increased proportionally with the increase in thiram concentration in the range of 240–2400 ppb, with a limit of detection (LOD) of 72 ppb.

Soybean root rot has a serious effect on soybean yield. Pesticides such as thiram are used to prevent soybean root rot, but thiram remains in the soil, which seriously threatens food safety and human health. Microbial fertilizers can effectively control root rot, promote crop growth, and degrade pesticide residues. This study aimed to evaluate the synergistic effects of arbuscular mycorrhizal fungi and phosphorus-solubilizing bacteria in a controlled environment, specifically investigating their potential for prevention and control of soybean root rot and pesticide degradation. In this pot-based study, we investigated the effects of Rhizophagus intraradices , Acinetobacter calcoaceticus , and thiram on the incidence of root rot, soybean biomass, the number of bacterial colonies in rhizosphere soil, and thiram residues in soybean grains and rhizosphere soil. The results showed that inoculation with R. intraradices and A. calcoaceticus significantly increased arbuscular mycorrhizal fungi spore density (445%), arbuscular mycorrhizal fungi infection rate (103%), soybean biomass such as fresh weights (59%), nodule number (237%), and total bacterial colony number in the rhizosphere soil of soybean plants (133%) and presented the lowest incidence of root rot (20%) ( P  < 0.05), compared with the control group. A single inoculant significantly reduced the residual amount of thiram in soybean grains and rhizosphere soil, and a mixed inoculation ( R. intraradices and A. calcoaceticus ) produced the most significant reduction, relative to the group sprayed with only thiram, thiram residues were reduced by 73% and 69%, respectively ( P  < 0.05). These findings provide a foundation for the biological control of soybean root rot and the degradation of pesticides and contribute to the sustainable development of agricultural ecosystems.

This study reports the reduction of AgNO 3 using green-synthesized carbon dots (CDs) derived from the leaf extract of Datura metel without the aid of any chemical-reducing agent. The CDs act as both reducing and stabilizing agent to synthesize CDs-functionalized silver nanoparticles (Ag/CDs) and are employed for surface-enhanced Raman spectroscopy (SERS)-based detection of thiram fungicide. The formation of Ag/CDs is confirmed with UV–Vis absorption spectroscopy and Raman spectroscopy. The synthesized Ag/CDs exhibit high stability and the fabricated SERS substrate exhibited a detection range of 10 –3 to 10 –8  M with a corresponding correlation coefficient of 0.98. The obtained minimum detection limit of thiram is 10 –8  M with an enhancement factor of 1.3 × 10 5 which is much lower than the maximum allowed residual limit of 7 ppm. This study emphasizes the green route to synthesize CDs-functionalized stable AgNPs for the SERS-based detection of thiram fungicide and explained the sensing mechanism.

A nanocomposite based on nanofibrillar cellulose (NFC) coated with gold–silver (core-shell) nanoparticles (Au@Ag NPs) was developed as a novel surface-enhanced Raman spectroscopy (SERS) substrate. SERS performance of NFC/Au@Ag NP nanocomposite was tested by 4-mercaptobenzoic acid. The cellulose nanofibril network was a suitable platform that allowed Au@Ag NPs to be evenly distributed and stabilized over the substrate, providing more SERS hotspots for the measurement. Two pesticides, thiram and paraquat, were successfully detected either individually or as a mixture in lettuce by SERS coupled with the nanocomposite. Strong Raman scattering signals for both thiram and paraquat were obtained within a Raman shift range of 400–2000 cm −1 and a Raman intensity ~ 8 times higher than those acquired by NFC/Au NP nanocomposite. Characteristic peaks were clearly observable in all SERS spectra even at a low concentration of 10 μg/L of pesticides. Limit of detection values of 71 and 46 μg/L were obtained for thiram and paraquat, respectively. Satisfactory SERS performance, reproducibility, and sensitivity of NFC/Au@Ag NP nanocomposite validate its applicability for real-world analysis to monitor pesticides and other contaminants in complex food matrices within a short acquisition time. Graphical abstract

We present a method for the surface-enhanced Raman scattering (SERS)-based detection of toxic contaminants in minimally processed liquid food products, through the use of a dendritic silver nanostructure, produced through electrokinetic assembly of nanoparticles from solution. The dendritic nanostructure is produced on the surface of a microelectrode chip, connected to an AC field with an imposed DC bias. We apply this chip for the detection of thiram, a toxic fruit pesticide, in apple juice, to a limit of detection of 115 ppb, with no sample preprocessing. We also apply the chip for the detection of melamine, a toxic contaminant/food additive, to a limit of detection of 1.5 ppm in milk and 105 ppb in infant formula. All the reported limits of detection are below the recommended safe limits in food products, rendering this technique useful as a screening method to identify liquid food with hazardous amounts of toxic contaminants.

A core–shell QDs@mSiO 2 @y-AuNCs nanoprobe was prepared, and a new ratiometric fluorescent sensor for thiram detection was developed. The mechanism of thiram sensing was investigated using FTIR, surface-enhanced Raman, XPS spectra, etc. The sensing of thiram was mainly ascribed to the formation of Au–S bonds between thiram and Au atoms on y-AuNCs surface, resulting in the dissociation of 11-MUA ligand from the y-AuNCs surface and the charge transfer between thiram and y-AuNCs. In the ratiometric fluorescence detection of thiram based on QDs@mSiO 2 @y-AuNCs, a linear range of 0.5–60 ng/mL was obtained with a LOD of 0.19 ng/mL. Compared with the fluorescence detection based on y-AuNCs, the ratiometric fluorescence detection of thiram demonstrated 3-fold enhanced sensitivity. The improvement was ascribed to two aspects: the fluorescence emission of y-AuNCs was enhanced after they were loaded onto the QDs@mSiO 2 nanoparticles; the ratiometric detection mode provided more precise sensing. The detection of thiram can be completed immediately after mixing the nanoprobe with thiram. Good recoveries of thiram in apple and pear samples were achieved. All the above results demonstrated the high potential of this method in practical applications. Graphical abstract

The widespread use of thiram has raised concerns for health and its toxic effects, but the underlying toxicity mechanism on platelets and bones is poorly defined. Here, we found a significant increase in the number of platelets in chickens with the thiram intake, due to the increased expression of thrombopoietin mRNA in the dysfunction liver. Furthermore, the decreased vascular distribution and cell death of chondrocytes in the tibial growth plates (TGPs) were observed, resulting in bone growth inhibition, which is associated with the abnormal activation of platelets leading to the extraordinary decrease of vascular endothelial growth factor A (VEGFA) and angiopoietin-1 protein were released and their corresponding receptors VEGFR2 and Tie-2 expressions were also reduced in the TGPs. Taken together, these findings revealed that thiram has an adverse effect on bones and platelets, which may have a high risk of thrombosis and osteoarthritis.