Simultaneous determination of spiropidion and its five major metabolites in sweet orange fruit and various processing by-products using ultra-high performance liquid chromatography-tandem mass spectrometry.

The present work reported the application of an ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous analysis of spiropidion and its five major metabolites in sweet orange fruit and by-products throughout the whole industrial juicing process of the orange fruit. The reversed-dispersive solid phase extraction (r-DSPE) with multi-walled carbon nanotubes (MWCNTs) was employed for the extraction and purification. The established method was validated and satisfactory parameters (linearity, trueness, precision, sensitivity, matrix effect and stability) were obtained. And then, the field trial of spiropidion on sweet oranges has been conducted and the effect of commercial juicing processing on the residue of spiropidion and its metabolites was further investigated. The various processing factors (PFs) for washing, juicing, sterilization, concentrating and essential oil collecting were also determined. The final results indicated that washing processing reduced residues by 18.4%; the juicing step allowed a significant decrease of the spiropidion residue by 34.2-70.8%, with PFs value in the range of 0.290-0.658. However, high level of residual spiropidion (ranging from 4.016 to 4.205 mg/kg) was detected in orange essential oil, with PFs value of 17.157. All the above results demonstrated the efficiency of the established method in the routine control analysis of spiropidion residues in sweet orange fruits and their by-products, and will facilitate the further intensive research on its spatial distribution, transfer and degradation during the different processing procedures of the sweet orange fruits.

Simultaneous enantioselective determination of two succinate- dehydrogenase-inhibitor fungicides in plant-origin foods by ultra-high performance liquid chromatography-tandem mass spectrometry.

Fluindapyr and penthiopyrad are two new succinate-dehydrogenase-inhibitor fungicides both employed as racemic mixtures of enantiomers to control various fungal pathogens. In the present work, a robust and highly-sensitive method for simultaneous determination of fluindapyr and penthiopyrad enantiomers in plant-origin foods (cereals, fruits and vegetables) was developed using UPLC-MS/MS combined with a chiral stationary phase. Rapid baseline chiral separation of four stereoisomers of fluindapyr and penthiopyrad was obtained within 4.2 min on chiral MX(2)-RH column under reversed-phase conditions (with the eluent of acetonitrile/0.1% formic acid in water =70/30 (V:V) and column temperature maintained at 30 °C). The plant-origin samples were extracted quickly with acetonitrile and purified with multi-walled carbon nanotubes. Excellent linearity for the target analytes was observed in the concentration ranging from 1 to 250 µg/L with regression coefficient no less than 0.9967. The mean recoveries of fluindapyr and penthiopyrad enantiomers from six matrices were 77.1-107.2%, with all relative standard deviations values lower than 9.1%. The limit of quantification of four stereoisomers of two target chiral fungicides was 5 µg/kg. The analysis of real samples reveal that the developed method is suitable for the simultaneous chiral determination of fluindapyr and penthiopyrad residues in cereals, fruits and vegetables samples at enantiomeric level and can support their further investigation on enantioselective environmental behaviors and residue surveillance.

Determination of five pesticides in kumquat: Dissipation behaviors, residues and their health risk assessment under field conditions.

The present study was carried out to profile the dissipation patterns and residues of five pesticides (triazophos, profenofos, chlorpyrifos, etoxazole and bifenthrin) on kumquat using QuEChERS method coupled with HPLC-MS/MS. The corresponding dietary health risks were also estimated. In the method validation, satisfactory results of good linearity (r2 ≥ 0.9956), sensitivity (limits of quantification ≤0.01 mg/kg), recoveries (71.0-95.7%) with relative standard deviations (0.70-9.4%) were obtained. The half-lives of the five pesticides in kumquat were 13.6-38.5 d under field conditions according to first-order kinetics. Based on the final residue experiment, dietary exposure risks of profenofos, chlorpyrifos, etoxazole and bifenthrin were all acceptably low, with RQc and RQa values of 0.00199-0.122 and 0.00145-0.200, respectively. However, exposure intake of triazophos posed unacceptable acute and chronic health risks for Chinese residents, especially for children with RQa and RQc up to 4.25 and 2.19. Forbidden use suggestion of triazophos and recommended MRLs of profenofos and bifenthrin were put forward in kumquat for safe production and consumption. This work was significant in providing guidance on appropriate application and MRL establishment of pesticides in kumquat.

Simultaneous Enantioselective Determination of Two New Isopropanol-Triazole Fungicides in Plant-Origin Foods Using Multiwalled Carbon Nanotubes in Reversed-Dispersive Solid-Phase Extraction and Ultrahigh-Performance Liquid Chromatography-Tandem Mass Spectrometry.

A simple and sensitive enantiomeric analytical method was established for the determination of two new isopropanol-triazole fungicides mefentrifluconazole and ipfentrifluconazole in plant-origin foods using ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The best enantioseparation of the four target stereoisomers was achieved on a Chiral MX(2)-RH column within 7 min by reversed-phase liquid chromatography, which is a significant improvement in the resolution of different chiral compounds under one set of conditions. A simple and effective pretreatment procedure was developed for the extraction and purification of the two target chiral fungicides using reversed-dispersive solid-phase extraction (r-DSPE) with multiwalled carbon nanotubes (MWCNTs). The influence of the type and amount of MWCNTs on the purification efficiencies and recoveries was evaluated. The mean recoveries for all four stereoisomers were in the range of 76.9-91.2%, with relative standard deviation (RSD) values below 7.2%. The limit of quantification (LOQ) of all stereoisomers of mefentrifluconazole and ipfentrifluconazole was 5 µg/kg for all tested matrixes. The results of the method validation and real samples analysis confirm that the established method is efficient and reliable for the enantiomeric determination of mefentrifluconazole and ipfentrifluconazole in plant-origin food samples.

A Chinese Medicine Formula "Xian-Jia-Tang" for Treating Bladder Outlet Obstruction by Improving Urodynamics and Inhibiting Oxidative Stress through Potassium Channels.

The aim of this study is to investigate efficacy of a traditional Chinese medicine formula (named Xian-Jia-Tang, XJT) on bladder outlet obstruction (BOO) in rats and explore its mechanisms. Total 80 BOO model rats were established and randomly divided into 4 groups: physiological saline, XJT, Cesium Chloride (CC), and XJT and CC groups. Meanwhile, 12 rats were used as normal control. Bladder weight and urodynamics were measured. Oxidative stress level and mRNA expressions of potassium channels gene were detected in detrusor. The mRNA and protein levels of hypoxia inducible factor-α (HIF-α) in detrusor were detected by RT-PCR and Western blot. BOO model rats showed significantly higher bladder weight and abnormal urodynamics. XJT significantly improved the abnormal urodynamics and inhibited the oxidative stress and changes of mRNA levels of potassium channels genes in detrusor of BOO model rats. Moreover, KATP and SK2/3 mRNA were overexpressed in BOO model rats treated by XJT. Besides, the significantly increased levels of HIF-α mRNA and protein were also inhibited by XJT. However, these inhibition effects of XJT were weakened by CC. XJT could effectively improve the urodynamics and inhibit the oxidative stress caused by hypoxia through suppressing the role of potassium channels in BOO model rats.