Zhiqiang Kong

Simultaneous determination of cyflumetofen and its main metabolite residues in samples of plant and animal origin using multi-walled carbon nanotubes in dispersive solid-phase extraction and ultrahigh performance liquid chromatography–tandem mass spectrometry

A rapid and effective method for the simultaneous determination of cyflumetofen and its main metabolite residues in samples of plant and animal origin (tomato, apple, eggplant, soybean, green tea, fish, and pork liver) was developed using ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Samples were extracted with acetonitrile and cleaned-up with multi-walled carbon nanotubes (MWCNTs). The determination of the presence of target compounds was achieved in less than 4.0min using an electrospray ionization source in the positive mode (ESI+) for cyflumetofen and 2-(trifluoromethyl) benzamide (B-3) and the negative mode (ESI-) for α,α,α-trifluoro-o-toluic acid (B-1). The entire method was validated by evaluating the repeatability, linearity, precision, trueness, and matrix effect. Average recoveries of the analytes were in the range of 79.3-117.6% with relative standard deviation values below 7.6%. Limits of quantification (LOQs) ranged from 0.7 to 9.8μgkg(-1), which were lower than the maximum residue limits (MRLs) for the cyflumetofen found in foods in Japan.

Simultaneous enantioselective determination of triazole fungicides in soil and water by chiral liquid chromatography/tandem mass spectrometry.

The manuscript concerns the development and validation of a novel and sensitive multi-residue method for simultaneous enantiomeric analysis of 8 triazole fungicides (tetraconazole, fenbuconazole, epoxiconazole, diniconazole, hexaconazole, triadimefon, paclobutrazol, and myclobutanil) in soil and water using chiral liquid chromatography coupled with tandem mass spectrometry. The separation and determination were performed using reversed-phase chromatography on a cellulose chiral stationary phase, a Chiralcel OD-RH (150 mm × 4.6 mm) column, under isocratic conditions using a mixture of ACN-2 mM ammonium acetate in water (55/45, v/v) as the mobile phase at 0.45 mL/min flow rate. The effects of three cellulose-based columns and three amylose-based columns on the separation were also investigated. The QuEChERS (acronym for quick, easy, cheap, effective, rugged and safe) method and solid-phase extraction (SPE) were used for the extraction and clean-up of the soil and water samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were undertaken. Under optimal conditions, the mean recoveries for all sixteen enantiomers from the soil samples were 76.4-108.1% with 2.6-12.0% intra-day relative standard deviations (RSD) and 4.2-14.1% inter-day RSD at 5, 25 and 50 μg/kg levels; the mean enantiomer recoveries from the water samples were 81.2-106.5% with 2.1-11.5% intra-day RSD and 3.4-13.6% inter-day RSD at 0.25, 0.5 and 2.5 μg/L levels. Coefficients of determination R2 ≥ 0.9989 were achieved for all studied analytes in the soil and water matrix calibration curves within the range of 1.0-125 μg/L. The limits of detection (LOD) (S/N=3) for all enantiomers in the soil and water were less than 1.0 μg/kg or μg/L, whereas the limit of quantification (LOQ) (S/N=10) did not exceed 3.0 μg/kg or μg/L. The results of the method validation confirm that this proposed method is convenient and reliable for the enantioselective determination of the enantiomers of triazole fungicides in soil and water.

Enantioselective analysis of triazole fungicide myclobutanil in cucumber and soil under different application modes by chiral liquid chromatography/tandem mass spectrometry.

A sensitive and enantioselective method was developed and validated for the determination of myclobutanil enantiomers by chiral liquid chromatography coupled with tandem mass spectrometry. The separation and determination were performed using reversed-phase chromatography on a Chiralcel OD-RH column, with ACN-water (70/30, v/v) as the mobile phase under isocratic conditions at 0.5 mL/min flow rate. The matrix effect, linearity, precision, accuracy, and stability were evaluated. The proposed method then was successfully applied to the study of enantioselective degradation of rac-myclobutanil in cucumber and soil under different application modes. The results showed that the preferential degradation of (+)-myclobutanil resulted in an enrichment of the (-)-myclobutanil residue in plant and soil. Moreover, in cucumber, the stereoselective intensity of myclobutanil under root douche treatment was stronger than that under foliar spraying treatment, whereas in soil, the intensity was exactly opposite. The probable reasons underlying these enantioselective effects were also discussed. This study highlighted the importance of examining the fate of both enantiomers in the greenhouse system for the correct use of chiral pesticides.

Simultaneous enantioselective determination of fenbuconazole and its main metabolites in soil and water by chiral liquid chromatography/tandem mass spectrometry

A novel and sensitive method was developed for the simultaneous determination of fenbuconazole and its main metabolites enantioselectively using chiral liquid chromatography coupled with tandem mass spectrometry. The separation and determination were performed using reversed-phase chromatography on a cellulose chiral stationary phase, a Chiralcel OD-RH (150 mm×4.6 mm) column, under isocratic conditions at 0.5 mL/min flow rate. The effects of three cellulose-based columns and three amylose-based columns on the separation were also investigated. The elution orders of the eluting enantiomers were identified by an optical rotation detector. The QuEChERS (acronym for Quick, Easy, Cheap, Effective, Rugged and Safe) method and solid-phase extraction (SPE) were used for the extraction and clean-up of the soil and water samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were evaluated. Under optimal conditions, the mean recoveries for all enantiomers from the soil samples were 82.5-104.1% with 2.7-9.5% intra-day relative standard deviations (RSD) and 5.7-11.2% inter-day RSD at 5, 25 and 50 μg/kg levels; the mean enantiomer recoveries from the water samples were 81.8-104.6% with 2.6-11.4% intra-day RSD and 5.3-10.4% inter-day RSD at 0.25, 0.5 and 2.5 μg/L levels. Coefficients of determination R2≥0.9991 were achieved for each enantiomer in the soil and water matrix calibration curves within the range of 1.0-125 μg/L. The limits of detection (LOD) for all enantiomers in the soil and water were less than 0.8 μg/kg, whereas the limit of quantification (LOQ) did not exceed 2.5 μg/kg. The results of the method validation confirm that this proposed method is convenient and reliable for the enantioselective determination of the enantiomers of fenbuconazole and its main metabolites in soil and water.

Impact of imazethapyr on the microbial community structure in agricultural soils.

Large amounts of imazethapyr were applied for weed control in cultivation fields in China, but their effects on the soil microbial community remains unclear. In this study, two agricultural soils, a silty loam (HS) and a loamy soil (QL), were spiked with imazethapyr (CK, 0.1, 1 and 10 mg kg(-1)) and incubated for 1, 15, 30, 60, 90 and 120 d. In addition, untreated controls received only water. The soil microbial community structures were characterized by investigating the phospholipid fatty acids (PLFA) and microbial biomass C. Soil microbial biomass C and total concentration of PLFA were variable with incubation time, which were also reduced by the addition of imazethapyr. Imazethapyr addition also decreased the ratios of GN/GP and fungi/bacteria. A larger stress level, measured as the ratio of PLFA (cyc17:0+cyc19:0)/(16:1ω7c+18:1ω7c), was found in the high concentration (1 and 10 mg kg(-1)) herbicide treatment groups. The effects of imazethapyr at the field application on soil microbial biomass and microbial community were minor. Principal component analysis (PCA) of the PLFA clearly separated the treatments and incubation times. Both soils showed different total PLFA concentrations and ratios of GN/GP and fungi/bacteria, but similar changes in the PLFA pattern upon soil treatment. The soil microbial community structure was shifted by the addition of imazethapyr, which recovered after 60d. In addition, the dissipation of imazethapyr was slow in both soils. Our results demonstrated that the addition of imazethapyr shifted the microbial community structure, but that it recovered after a period of incubation.

Environmental behavior of the chiral triazole fungicide fenbuconazole and its chiral metabolites: enantioselective transformation and degradation in soils.

Fenbuconazole is a widely used systemic agricultural fungicide of the triazole class with one chiral center. In the present study, the enantioselective degradation of fenbuconazole and its chiral metabolites, RH-9129 and RH-9130, in two soils under aerobic and anaerobic conditions were investigated using a chiral OD-RH column on a reversed-phase liquid chromatography-tandem mass spectrometry system. Under aerobic or anaerobic conditions, the results showed the occurrence of enantioselectivity with (-)-fenbuconazole preferentially degraded in both soils. Further enantioselective analysis of converted products showed that the concentrations of four RH-9129 and RH-9130 stereoisomers were different from each other under both aerobic and anaerobic conditions. The four stereoisomer concentrations followed the order (-)-RH-9129 > (+)-RH-9129 > (-)-RH-9130 > (+)-RH-9130 in Langfang alkaline soil. However, in the case of Changsha acidic soil, different RH-9129 and RH-9130 stereoisomer patterns were produced in the order (-)-RH-9129 > (+)-RH-9129 > (+)-RH-9130 > (-)-RH-9130. The (-)-RH-9129 stereoisomer had the highest concentration formed by transformation of fenbuconazole in both soils. The degradation of RH-9129 and RH-9130 in the two soils is also stereoselective under both aerobic and anaerobic conditions, the results indicating that the (+)-RH-9130 enantiomer degraded faster than the (-)-RH-9130 enantiomer and the (+)-RH-9129 enantiomer degraded faster than the (-)-RH-9129 enantiomer. In addition, the (-)-RH-9129 isomer exhibited the slowest degradation rate in both soils. This study provides the first experimental evidence of stereoselective degradation and transformation of fenbuconazole as well as its chiral metabolites in the environment.

Enantioselective determination of triazole fungicide tebuconazole in vegetables, fruits, soil and water by chiral liquid chromatography/tandem mass spectrometry

A novel and sensitive method was developed for the determination of tebuconazole enantioselectively using reversed-phase LC-MS/MS. The separation and determination were performed using on an amylose-based chiral stationary phase, a Lux 3u Amylose-2 column (150 mm×2.0 mm), under isocratic conditions at 0.3 mL/min flow rate. A series of chiral stationary phases were investigated and the effect of mobile phase composition on the enantioseparation was discussed. Parameters including the matrix effect, linearity, precision, accuracy and stability were evaluated. Under optimal conditions, the overall mean recoveries for two enantiomers from the soil, tomato, cucumber, pear and apple samples were 79.3-101.1% with 2.8-11.5% intra-day relative standard deviations (RSDs) and 4.1-8.6% inter-day RSDs at 5, 25 and 50 μg/kg levels; the mean enantiomer recoveries from the water samples were 89.6-101.9% with 3.3-10.2% intra-day RSDs and 5.1-7.7% inter-day RSDs at 0.25, 0.5 and 2.5 μg/kg levels. The limits of detection (LODs) for all enantiomers in tomato, cucumber, pear, apple, soil and water were less than 0.6 μg/kg, whereas the limit of quantification (LOQ) did not exceed 2.0 μg/kg. The results indicate that this proposed method is convenient and reliable for the enantioselective determination of tebuconazole enantiomers in foods and environment samples.

Effect of home processing on the distribution and reduction of pesticide residues in apples

The effect of home processing (washing, peeling, coring and juicing) on residue levels of chlorpyrifos, β-cypermethrin, tebuconazole, acetamiprid and carbendazim in apple segments was investigated. The pesticide residues were determined by UPLC-MS/MS and GC with a flame photometric (FPD) and electron capture detection (ECD). The results indicated that the pesticide residue levels in the apple peel and core were higher compared with in the apple flesh. After peeled and cored apple was processed into apple juice and pomace, chlorpyrifos, β-cypermethrin and tebuconazole were concentrated in the apple pomace. However, residues of acetamiprid and carbendazim were exceptions. The apple pomace was free of acetamiprid, which was mainly present in the apple juice. After washing the mean loss of chlorpyrifos, β-cypermethrin, tebuconazole, acetamiprid and carbendazim from apples under recommended dosage and twofold higher dosage were 17–21%, 6.7–7.1%, 13–32%, 42–67% and 47–50%, respectively. The pesticide residues were significantly reduced in the edible part of the apple except for β-cypermethrin during peeling and coring process. The removal effect of apple juicing was found to be the most pronounced on β-cypermethrin residue, which was reduced in the range of 81–84%, and the reductions of chlorpyrifos, tebuconazole, acetamiprid and carbendazim upon apple juicing were in the range of 15–36%.

Rapid residue analysis of pyriproxyfen, avermectins and diflubenzuron in mushrooms by ultra-performance liquid chromatography coupled with tandem mass spectrometry

A quick, easy, cheap, effective, rugged, and safe (QuEChERS) analytical procedure for the simultaneous determination of pyriproxyfen, diflubenzuron and avermectin residues in mushrooms and their substrates was developed using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). Pyriproxyfen, diflubenzuron and avermectin were extracted with acetonitrile and the purification procedure was carried out using primary-secondary amine (PSA). The determination of target compounds was achieved in less than 3.0 min using an electrospray ionization source in positive mode (ESI+). Chromatographic separation was achieved using gradient elution with a mobile phase consisting of acetonitrile and water containing 0.2% formic acid. Average recoveries were in the range of 78.1–112.5% with the relative standard deviation values below 11.8% for all analytes. The limits of detection ranged from 0.016 to 1.5 μg kg−1, and limits of quantification ranged from 0.052 to 5 μg kg−1. The results of the method validation confirmed that this proposed method is convenient and reliable for the determination of pyriproxyfen, diflubenzuron and avermectin residues in mushrooms and their substrates.

A Simple Method for the Isolation and Purification of 2,4-Dihydroxy-7-Methoxy-2H-1,4-Benzoxazin-3(4H)-One (DIMBOA) from Maize (Zea mays L.) Seedlings

Abstract 2,4-Dihydroxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one (DIMBOA), the dominant benzoxazinoid hydroxamic acid in maize (Zea Mays L.), serves as important factors of resistance against insects and microbial diseases, allelochemicals used in competition with other plants. In this paper, a novel and simple method for the isolation and purification of DIMBOA from maize seedlings was developed. Frozen shoots from 7-d-old maize seedlings (1 000×g) were firstly defrosted and then were directly homogenized and extracted with ethyl acetate. The macerate was allowed to stand at room temperature (25±2)°C for 1 h to allow enzymatic release of DIMBOA from DIMBOA-glucoside. Then the ethyl acetate phase was filtered, dried and evaporated to dryness. The resulting light-tan, semicrystalline residue was stored at −20°C for 24 h. Upon recrystallization from acetone-hexane, a relative higher yield (0.58 g) of pure DIMBOA crystals was obtained compared with the yield afforded by Woodward methodology (0.26 g).