An overview on the green synthesis and removal methods of pyridaben.

Pyridaben is an acaricide widely used around the world to control phytophagous mites, white flies, aphids, and thrips. It is highly toxic to nontarget organisms such as predatory mites, bees, and fishes. Therefore, the occurrence and removal of pyridaben in food and the environment are worthy of concern. This mini-review focuses on pyridaben residue levels in crops, aquatic systems, and soils, as well as the green synthesis and removal of pyridaben. During the period of 2010-2022, pyridaben was reported in monitoring studies on fruits, vegetables, herbs, bee products, aquatic systems, and soils. Vegetable and agricultural soil samples exhibited the highest detection rates and residue levels. One-pot synthesis offers a green chemistry and sustainable alternative for the synthesis of pyridaben. Among traditional home treatments, peeling is the most effective way to remove pyridaben from crops. Magnetic solid-phase extraction technology has emerged as a powerful tool for the adsorption and separation of pyridaben. Photocatalytic methods using TiO2 as a catalyst were developed as advanced oxidation processes for the degradation of pyridaben in aqueous solutions. Current gaps in pyridaben removal were proposed to provide future development directions for minimizing the exposure risk of pyridaben residues to human and nontarget organisms.

Kinetics of the photolysis of pyridaben and its main photoproduct in aqueous environments under simulated solar irradiation.

The photolytic fate of pyridaben and its main photolysis product was investigated in different aqueous solutions. Results showed that the photolysis of pyridaben followed pseudo first-order kinetics or the hockey-stick model. In buffer solutions, the half-life of pyridaben was the shortest at pH 4, while the degradation rate within 24 h was the highest at pH 9. Humic acids (HA) at concentrations of 1-20 mg L-1 favored the photolysis of pyridaben while fulvic acids (FA) did not have a significant effect. Nitrate at low concentrations (0.01 mM) accelerated the photolysis and Fe(iii) at high concentrations (0.01 and 0.1 mM) significantly inhibited the photolysis. The photolysis rate of pyridaben in rainwater, tap water, and river water was significantly higher than that in distilled water. The half-lives in distilled water, rainwater, tap water, river water, and pond water were 2.36, 1.36, 1.61, 1.77, and 2.68 h, respectively. Ultra-high-performance liquid chromatography/high-resolution mass spectrometry identified M328 as a photolysis product. The degradation of M328 followed pseudo first-order kinetics in distilled water, buffer solutions and aqueous solutions fortified with HA. The half-lives of M328 were in the range of 7.07-13.95 h. These results are essential for further environmental risk assessment of pyridaben.

Combined Experimental and Computational Study on the Transformation of a Novel 1,3,4-Oxadiazole Thioether Nematicide in Aqueous Solutions.

It has been demonstrated that Exianliuyimi (EXLYM) exhibits good nematocidal activity. As a potential nematicide, EXLYM and its transformation products (TPs) may generate emerging pollutants with hazardous effects on the ecosystem. In this study, the fate of EXLYM in aqueous solutions was investigated using experimental and theoretical approaches. Laboratory-scale experiments showed that EXLYM is hydrolytically stable. Microbial processes are primarily responsible for the oxidation of sulfur in aqueous solutions. Under simulated sunlight, the t1/2 values of EXLYM in acidic, neutral, and alkaline buffer solutions were 5.02, 3.83, and 5.55 h, respectively. Six TPs were identified using a non-target screening strategy realized by ultra-high-performance liquid chromatography coupled with Q-Exactive Orbitrap high-resolution mass spectrometry and 18O-labeling experiments. Four of these were unambiguously confirmed using authentic standards. Reactive oxygen species scavenging experiments, 18O-labeling experiments, and quantum-theoretical calculations suggested that EXLYM could degrade mainly through four pathways: sulfur oxidation, nucleophilic aromatic photosubstitution, C-S bond cleavage, and oxidative ring-opening. The proposed degradation kinetics, TPs, and transformation pathways in aqueous solutions provide valuable information on the fate of EXLYM in aquatic ecosystems and lay the foundation for further toxicological tests.

Identification of genetic variants of the IL-22 gene in association with an altered risk of COPD susceptibility.

The incidence of chronic obstructive pulmonary disease (COPD) is related to the interaction between environmental exposure and genetic factors. Far more than 15% of smokers eventually develop COPD. In addition to smoking, genetic susceptibility may be another factor in the development of COPD. IL-22 and its receptors are increased in human and experimental COPD and contribute to pathogenesis. Here, we conducted a case-control study to evaluate the association between IL-22 tag-single nucleotide polymorphisms (SNPs) and COPD risk. Four tag-SNPs (rs2227478, rs2227481, rs2227484 and rs2227485) were identified according to linkage disequilibrium (LD) analysis in 30 healthy controls. A total of 513 COPD cases and 504 controls were recruited to perform an association study between these four tag-SNPs and COPD risk. We found that the "C" allele of rs2227478T>C and the "T" allele of rs2227481C>T were obviously related to decreased COPD susceptibility. Genetic model analysis showed that rs2227478T>C and rs2227481C>T were significantly associated with a decreased risk of COPD under dominant models after adjusting for the above factors. In the recessive model, rs2227485T>C was obviously associated with decreased COPD risk. Our data showed that only rs2227485T>C was associated with a decreased COPD risk after Bonferroni correction. The eQTL analysis showed that rs2227485T>C was significantly associated with IL-22 expression. The pGL4-rs2227485-C gene reporter had a higher promoter activity than pGL4-rs2227485-T. In our study, rs2227485T>C, located in the promoter region of IL-22, was associated with a decreased risk of COPD and increased IL-22 promoter activity, suggesting that this variant might modulate COPD susceptibility.

Simple strategy for the construction of oxygen vacancies on α-MnO2 catalyst to improve toluene catalytic oxidation.

A strategy simple, safe and suitable for large scale production of α-MnO2 catalyst with high activity in VOCs oxidation is crucial for its application. The catalytic reactivity of α-MnO2 catalyst is largely related with its oxygen vacancy. Herein, we report effective construction of oxygen vacancies on α-MnO2 through simply adjusting precipitation temperature of a redox precipitation process. The key role of surface oxygen vacancies in toluene oxidation and the formation of different amount and distribution of the oxygen vacancies over the α-MnO2 catalysts were revealed by characterizations together with DFT calculations. The best catalyst (α-MnO2-60) exhibited significantly improved catalytic activity of α-MnO2 catalyst in toluene oxidation (T90 = 203 â„ƒ) and excellent water resistance. The richest surface oxygen vacancies of α-MnO2-60 contributed to its best catalytic activity, despite of its relatively lower specific surface area. This work may provide a new perspective for the rational design of high efficient VOCs catalysts.

Qualitative and Quantitative Analysis of the New Sulfone Bactericide 2-(4-Fluorophenyl)-5-(Methylsulfonyl)-1,3,4-Oxadiazole and Identification of Its Degradation Pathways in Paddy Water.

Rapid and simple methods for the determination of Jiahuangxianjunzuo (JHXJZ) in paddy water, brown rice, soil and rice straw was developed and validated. This method involved the use of ultrahigh-performance liquid chromatography equipped with photodiode array detector. The most important factor was chromatographic conditions, as identified through an orthogonal experimental design. This method showed good recoveries and precisions, thereby indicating its suitability for monitoring of JHXJZ residues in paddy water, brown rice, soil and rice straw. Furthermore, hydrolysis experiment was conducted in the laboratory under pH = 7 buffer solutions, and its degradation product was identified as 2-(4-fluorophenyl)-5-methoxy-1,3,4-oxadiazole by high-resolution mass spectrometry. JHXJZ has a major degradation pathway in the water which the OH- nucleophilic attack the C5 of 1,3,4-oxadiazole ring. Then it leaves mesyl to form intermediate 5-(4-fluorophenyl)-1,3,4-oxadiazol-2-ol and the intermediate combined with methanol formed the degradation product 2-(4-fluorophenyl)-5-methoxy-1,3,4-oxadiazole by the loss of one H2O.The degradation pathways of JHXJZ under the present indoor simulation conditions were proposed.

Determination of nitenpyram dissipation and residue in kiwifruit by LC-MS/MS.

To investigate the presence of nitenpyram in kiwifruit, a field experiment was conducted in six kiwifruit producing regions in China. A modified quick, easy, cheap, effective, rugged and safe method (QuEChERS) method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the determination of nitenpyram in kiwifruit. Quantitative detection was performed by LC-MS/MS in multiple reaction monitoring (MRM) mode under positive-ion electrospray ionisation. The proposed method is linear and accurate in the range of 0.005 to 4.5 µg/mL. The recovery of nitenpyram was satisfactory (71.96-96.67%) with reasonable RSDs (9.83 %) for 0.01-4.5 mg/kg spiked levels. The limit of quantification (LOQ) was 0.01 mg/kg for nitenpyram. Nitenpyram degraded rapidly in kiwifruit with a half-life <4 days. Residues of nitenpyram were <0.01 - 0.54 mg/kg in kiwifruit 7, 14 and 21 days after spraying at six sites.

Determination, risk assessment and processing factors for pyridaben in field-incurred kiwifruit samples.

Field trials in six agricultural sites were carried out to investigate the dissipation and residue levels of pyridaben in kiwifruit. Each sample was extracted with acetonitrile, purified with octadecylsilane and analyzed with high-performance liquid chromatography-tandem mass spectrometry. The method had good linearity (R2 > 0.99), accuracy (recoveries of 78.53-98.00%) and precision (relative standard deviation of 0.86-6.11%). The dissipation of pyrdaben in kiwifruit followed first-order kinetics with a half-life < 8 d, and terminal residues in kiwifruit were lower than 0.5 mg/kg after 14 d of application. Risk assessment indicated that both chronic and acute dietary intake risk values were far below 100%, suggesting that pyridaben residues in kiwifruit were relatively safe to humans. Moreover, the effects of traditional household processes on kiwifruit were investigated. The processing factors (PFs) indicated that peeling and peeling-juicing processes could remove pyridaben residues from kiwifruit, and the former was more effective than the latter (PF at 0.15 vs. 0.51). Nevertheless, drying kiwifruit with an oven increased the amount of pyridaben (PF at 1.05). These results could provide guidance for the safe and reasonable use of pyridaben in agriculture and may be helpful for the Chinese government to determine maximum residue limit of pyridaben in kiwifruit.

Sodium tanshinone IIA sulfonate protects against acute exacerbation of cigarette smoke-induced chronic obstructive pulmonary disease in mice.

Exacerbation of chronic obstructive pulmonary disease (COPD) is characterized by acute airway inflammation and mucus hypersecretion, which is by far the most costly aspect of its management. Thus, it is essential to develop therapeutics with low side effects for CODP exacerbation. Sodium tanshinone IIA sulfonate (STS) is a water-soluble derivative of tanshinone IIA isolated as the major active component of Chinese herbal medicine Danshen. Although it possesses anti-inflammatory, anti-oxidative and anti-apoptotic properties, it remains unknown whether STS protects against COPD exacerbation. In this study, we challenged cigarette smoke (CS)-exposed mice with lipopolysaccharide (LPS), and then treated these mice with STS. We found that STS significantly ameliorated pulmonary inflammatory responses, mucus hypersecretion and lung function decline in CS-exposed mice challenged with LPS. STS treatment also significantly attenuated increased IL-6 and IL-8 releases from cigarette smoke extract (CSE)-treated human bronchial epithelial cells (16HBE) challenged with LPS. Mechanistically, STS reduced activation of ERK1/2 and NF-κB in lungs of CS-exposed mice and CSE-treated 16HBE cells challenged with LPS. Taken together, STS protects against acute exacerbation of CS-induced lung injury, which provides a promising and potential therapeutic avenue to halt acute exacerbation of COPD.

Hydrogen sulfide inhibits cigarette smoke-induced inflammation and injury in alveolar epithelial cells by suppressing PHD2/HIF-1α/MAPK signaling pathway.

Chronic obstructive pulmonary fibrosis (COPD) is a chronic and fatal lung disease with few treatment options. Sodium hydrosulfide (NaHS), a donor of hydrogen sulfide (H2S), was found to alleviate cigarette smoke (CS)-induced emphysema in mice, however, the underlying mechanisms have not yet been clarified. In this study, we investigated its effects on COPD in a CS-induced mouse model in vivo and in cigarette smoke extract (CSE)-stimulated alveolar epithelial A549 cells in vitro. The results showed that NaHS not only relieved emphysema, but also improved pulmonary function in CS-exposed mice. NaHS significantly increased the expressions of tight junction proteins (i.e., ZO-1, Occludin and claudin-1), and reduced apoptosis and secretion of pro-inflammatory cytokines (i.e., TNF-α, IL-6 and IL-1ß) in CS-exposed mouse lungs and CSE-incubated A549 cells, indicating H2S inhibits CS-induced inflammation, injury and apoptosis in alveolar epithelial cells. NaHS also upregulated prolyl hydroxylase (PHD)2, and suppressed hypoxia-inducible factor (HIF)-1α expression in vivo and in vitro, suggesting H2S inhibits CS-induced activation of PHD2/HIF-1α axis. Moreover, NaHS inhibited CS-induced phosphorylation of ERK, JNK and p38 MAPK in vivo and in vitro, and treatment with their inhibitors reversed CSE-induced ZO-1 expression and inflammation in A549 cells. These results suggest that NaHS may prevent emphysema via the suppression of PHD2/HIF-1α/MAPK signaling pathway, and subsequently inhibition of inflammation, epithelial cell injury and apoptosis, and may be a novel strategy for the treatment of COPD.