Thiram, a prevalent dithiocarbamate insecticide in agriculture, is widely employed as a crop insecticide and preservative. Chronic exposure to thiram has been linked to various irreversible damages, including tibial cartilage dysplasia, erythrocytotoxicity, renal issues, and immune system compromise. Limited research exists on its effects on reproductive organs. This study investigated the reproductive toxicology in mouse testes exposure to varying concentrations (0, 30, 60, and 120 mg/kg) of thiram. Our study uncovered a series of adverse effects in mice subjected to thiram exposure, including emaciation, stunted growth, decreased water intake, and postponed testicular maturation. Biochemical analysis in thiram-exposed mice showed elevated levels of LDH and AST, while ALP, TG, ALT, and urea were decreased. Histologically, thiram disrupted the testis\' microarchitecture and compromised its barrier function by widening the gap between spermatogenic cells and promoting fibrosis. The expression of pro-apoptotic genes (Bax, APAF1, Cytc, and Caspase-3) was downregulated, whereas Bcl-2 expression increased in thiram-treated mice compared to controls. Conversely, the expression of Atg5 was upregulated, and mTOR and p62 expression decreased, with a trend towards lower LC3b levels. Thiram also disrupted the blood-testis barrier, significantly reducing the mRNA expression of zona occludens-1 (ZO-1) and occludin. In conclusion, chronic exposure to high thiram concentrations (120 mg/kg) caused testicular tissue damage, affecting the blood-testis barrier and modulating apoptosis and autophagy through the Bcl-2/Bax and mTOR/Atg5/p62 pathways. This study contributes to understanding the molecular basis of thiram-induced reproductive toxicity and underscores the need for further research and precautions for those chronically exposed to thiram and its environmental residuals.

In this work, a new surface plasmon resonance (SPR) sensor based on sulphur-doped titanium dioxide (S-TiO2) nanostructures and molecularly imprinted polymer (MIP) was presented for thiram (THI) determination in milk samples. Firstly, the S-TiO2 nanomaterial with a high product yield was prepared by using a facile sol-gel hydrolysis technique with a high product yield. After that, UV polymerization was carried out for the preparation of the THI-imprinted SPR chip based on S-TiO2 using a mixture including ethylene glycol dimethacrylate (EGDMA) as the cross-linker, N,N\'-azobisisobutyronitrile (AIBN) as the initiator, and methacryloylamidoglutamicacid (MAGA) as the monomer. The reliability of the sensor preparation procedure has been successfully proven by characterization studies of the prepared nanomaterials and SPR chip surfaces through spectroscopic, microscopic, and electrochemical methods. As a result, the prepared SPR sensor showed linearity in the range of 1.0 × 10-9-1.0 × 10-7 M with a detection limit (LOD) of 3.3 × 10-10 M in the real samples, and a sensor technique for THI determination with high sensitivity, repeatability, and selectivity can be included in the literature.

A gold nanogap substrate was used to measure the thiram and carbaryl residues in various fruit juices using surface-enhanced Raman scattering (SERS). The gold nanogap substrates can detect carbaryl and thiram with limits of detection of 0.13 ppb (0.13 μgkg-1) and 0.22 ppb (0.22 μgkg-1). Raw SERS data were first preprocessed to reduce noise and undesirable effects and, were later used for model creation, implementing classification, and regression analysis techniques. The partial least-squares regression models achieved the highest prediction correlation coefficient (R2) of 0.99 and the lowest root mean square of prediction value below 0.62 ppb for both pesticide-infected juice samples. Furthermore, to differentiate between juice samples contaminated by both pesticides and control (pesticide-free), logistic-regression classification models were produced and achieved the highest classification accuracies of 100% and 99% for contaminated juice containing thiram and 100% accurate results for contaminated juice containing carbaryl. This indicates that the gold nanogap surface has significant potential for achieving high sensitivity in detecting trace contaminants in food samples.

In recent years, incidents of pesticide pollution and abuse of feed additives have occurred frequently, which pose a great threat to human health. Raman spectroscopy has become an important method in the field of food safety due to its rapidity, simplicity and sensitivity. It is important to obtain complex structure to promote surface-enhanced Raman scattering (SERS) effect. In this study, gold helical nanoparticles with rich surface structure were synthesized using cysteine as induce agent. Notably, the complex helical structure and tip led to an excellent electromagnetic enhancement property. The helical structure showed ultra-sensitive detection of hazardous molecular, such as thiram and ractopamine. Interestingly, the D/L-Au structure had significant chiral optical activity and could be used as an unlabeled SERS platform for enantiomer identification. This study provided an effective strategy for the detection of pesticides and feed additives, which could be applied in other aspects of food safety in the future.

There is a growing interest in the use of flexible substrates for label-free and in situ Surface-enhanced Raman Spectroscopy (SERS) applications. In this study, a flexible SERS substrate was prepared using self-assembled Au/Ti3C2 nanocomposites deposited on a cellulose (CS) paper. The Au/Ti3C2 nanocomposites uniformly wrapped around the cellulose fibers to provide a three-dimensional plasma SERS platform. The limit of detection (LOD) of CS/Au/Ti3C2 was as low as 10-9 M for 4-mercaptobenzoic acid(4-MBA) and crystal violet (CV), demonstrating good SERS sensitivity. CS/Au/Ti3C2 was used for in situ SERS detection of thiram on apple surfaces by simple swabbing, and a limit of detection of 0.05 ppm of thiram was achieved. The results showed that CS/Au/Ti3C2 is a flexible SERS substrate that can be used for the detection of thiram on apple surfaces. These results demonstrate that CS/Au/Ti3C2 can be used for the non-destructive, rapid and sensitive detection of pesticides on fruit surfaces.

Over the last few decades, there is increasing worldwide concern over human health risks associated with extensive use of pesticides in agriculture. Developing excellent SERS substrate materials to achieve highly sensitive detection of pesticide residues in the food is very necessary owing to their serious threat to human health through food chains. Self-assembled metallic nanoparticles have been demonstrated to be excellent SERS substrate materials. Hence, alkanethiols-protected gold nanoparticles have been successfully prepared for forming larger-scale two-dimensional monolayer films. These films can be disassembled into a fluid state and re-assembled back to crystallized structure by controlling surface pressure. Further investigations reveal that their self-assembled structures are mainly dependent on the diameter of gold nanoparticles and ligand length. These results suggest that the size ratio of nanoparticle diameter/ligand length within the range of 4.45-2.35 facilitates the formation of highly ordered 2D arrays. Furthermore, these arrays present excellent Surface-Enhanced Raman Scattering performances in the detection of trace thiram, which can cause environmental toxicity to the soil, water, animals and result in severe damage to human health. Therefore, the current study provides an effective way for preparing monodispersed hydrophobic gold nanoparticles and forming highly ordered 2D close-packed SERS substrate materials via self-assembly to detect pesticide residues in food. We believe that, our research provides not only advanced SERS substrate materials for excellent detection performance of thiram in food, but also novel fundamental understandings of self-assembly, manipulation of nanoparticle interactions, and controllable synthesis.

Given the potential dangers of thiram to food safety, constructing a facile sensor is significantly critical. Herein, we presented a colorimetric sensor based on glutathione‑iron hybrid (GSH-Fe) nanozyme for specific and stable detection of thiram. The GSH-Fe nanozyme exhibits good peroxidase-mimicking activity with comparable Michaelis constant (Km = 0.551 mM) to the natural enzyme. Thiram pesticides can specifically limit the catalytic activity of GSH-Fe nanozyme via surface passivation, causing the change of colorimetric signal. It is worth mentioning that the platform was used to prepare a portable hydrogel kit for rapid qualitative monitoring of thiram. Coupling with an image-processing algorithm, the colorimetric image of the hydrogel reactor is converted into the data information for accurate quantification of thiram with a detection limit of 0.3 μg mL-1. The sensing system has good selectivity and high stability, with recovery rates in fruit juice samples ranging from 92.4% to 106.9%.

Thiram is a dithiocarbamate derivative, which is used as a fungicide for seed dressing and spraying during the vegetation period of plants, and also as an active vulcanization accelerator in the production of rubber-based rubber products. In this study the content of reactive oxygen species (ROS) and the state of the glutathione system have been investigated in the oral fluid and gum tissues of adult male Wistar rats treated with thiram for 28 days during its administration with food at a dose of 1/50 LD50. Thiram induced formation of ROS in the oral cavity; this was accompanied by an imbalance in the ratio of reduced and oxidized forms of glutathione due to a decrease in glutathione and an increase in its oxidized form as compared to the control. Thiram administration caused an increase in the activity of glutathione-dependent enzymes (glutathione peroxidase, glutathione transferase, and glutathione reductase). However, the time-course of enzyme activation in the gum tissues and oral fluid varied in dependence on the time of exposure to thiram. In the oral fluid of thiram-treated rats changes in the antioxidant glutathione system appeared earlier. The standard diet did not allow the glutathione pool to be fully restored to physiological levels after cessation of thiram intake. The use of exogenous antioxidants resviratrol and an Echinacea purpurea extract led to the restoration of redox homeostasis in the oral cavity.

Thiram, a widely used organic pesticide in agriculture, exhibits both bactericidal and insecticidal effects. However, prolonged exposure to thiram has been linked to bone deformities and cartilage damage, contributing to the development of tibial dyschondroplasia (TD) in broilers and posing a significant threat to global agricultural production. TD, a prevalent nutritional metabolic disease, manifests as clinical symptoms like unstable standing, claudication, and sluggish movement in affected broilers. In recent years, there has been growing recognition of the regulatory role of long non-coding RNA (lncRNA) in tibial cartilage formation among broilers through diverse signaling pathways. This study employs in vitro experimental models, growth performance analysis, and clinical observation to assess broilers\' susceptibility to thiram pollution. Transcriptome sequencing analysis revealed a significant elevation in the expression of lncRNA MSTRG.74.1 in both the con group and the thiram-induced in vitro group. The results showed that lncRNA MSTRG.74.1 plays a pivotal role in influencing the proliferation and abnormal differentiation of chondrocytes. This regulation occurs through the negative modulation of apoptotic genes, including Bax, Cytc, Bcl2, Apaf1, and Caspase3, along with genes Atg5, Beclin1, LC3b, and protein p62. Moreover, the overexpression of lncRNA MSTRG.74.1 was found to regulate broiler chondrocyte development by upregulating BNIP3. In summary, this research sheds light on thiram-induced abnormal chondrocyte proliferation in TD broilers, emphasizing the significant regulatory role of the lncRNA MSTRG.74.1-BNIP3 axis, which will contribute to our understanding of the molecular mechanisms underlying TD development in broilers exposed to thiram.

Owing to good flexibility, prominent mechanical properties, three-dimensional (3D) nanofibrous structure and low background interference, sustainable bacterial nanocellulose (BNC) is a highly attractive matrix material for surface-enhanced Raman scattering (SERS) sensor. Herein, a highly sensitive, flexible and scalable silver nanorod-decorated BNC (AgNRs@BNC) SERS sensor is developed by a simple vacuum-assisted filtration. The AgNRs were firmly locked in the 3D nanofibrous network of cellulose nanofibers upon vacuum drying process, resulting in the formation of 3D SERS hotspots with a depth of more than 10 μm on the sensor. With 4-aminothiophenol (4-ATP) as a target molecule, a lowest distinguishable level of 10-12 M and a high enhancement factor of 1.1 × 109 were realized by the optimal AgNRs1.5@BNC SERS sensor. Moreover, the AgNRs@BNC SERS sensor exhibits high detectable level of 10-9 M for thiram molecules by integrating with a portable Raman spectrometer. Besides, toxic thiram residues on grape surface could be directly on-site identified by the combination of AgNRs@BNC SERS sensors and a portable Raman spectrometer through a feasible press-and-peel method. The flexible AgNRs@BNC SERS sensor cooperated with portable Raman system demonstrates great potential for on-site detection of pesticide residues on irregular food surfaces.