Enantioseparation of napropamide by supercritical fluid chromatography: Effects of the chromatographic conditions and separation mechanism

Supercritical fluid chromatography (SFC) is already used for enantioseparation in the pharmaceutical industry, but it is rarely used for the separation of chiral pesticides. Comparing with high performence liquid chromatography, SFC uses much more environmnetal friendly and economic mobile phase, supercritical CO₂. In our work, the enantioseparation of an amide herbicide, napropamide, using three different polysaccharide‐type chiral stationary phases (CSPs) in SFC was investigated. By studying the effect of different CSPs, organic modifiers, temperature, back‐pressure regulator pressures, and flow rates for the enantioseparation of napropamide, we established a rapid and green method for enantioseparation that takes less than 2 minutes: The column was CEL2, the mobile phase was CO₂ with 20% 2‐propanol, and the flow rate was 2.0 mL/min. We found that CEL2 demonstrated the strongest resolution capability. Acetonitrile was favored over alcoholic solvents when the CSP was amylose and 2‐propanol was the best choice when using cellulose. When the concentration of the modifiers or the flow rate was decreased, resolutions and analysis times increased concurrently. The temperature and back‐pressure regulator pressure exhibited only minor influences on the resolution and analysis time of the napropamide enantioseparations with these chiral columns. The molecular docking analysis provided a deeper insight into the interactions between the enantiomers and the CSPs at the atomic level and partly explained the reason for the different elution orders using the different chiral columns.     

The Chiral Separation and Enantioselective Degradation of the Chiral Herbicide Napropamide

The chiral pesticide enantiomers often have different toxic effects and environmental behaviors, which suggests that the risk assessments should be on an enantiomeric level. In this work, the chiral separation of the napropamide enantiomers and the stereoselective degradation in tomato, cucumber, rape, cabbage, and soil were investigated. Napropamide enantiomers could be separated absolutely by high‐performance liquid chromatography (HPLC) using a Chiralpak IC column with a resolution factor of 11.75 under the optimized condition. Solid phase extraction (SPE) was used for cleanup of the enantiomers in the vegetable samples. The residue analysis method was validated. Good linearities (R² = 0.9997) and recoveries (71.43% ‐97.64%) were obtained. The limits of detection (LOD) were 0.05 mg/kg in soil and 0.20 mg/kg in vegetables. The results of degradation showed that napropamide dissipated rapidly in vegetables with half‐lives of only 1.13–2.21 days, but much more slowly in soil, with a half‐life of 11.95 d. Slight stereoselective degradation of the two enantiomers was only observed in cabbage, with enantiomeric fraction (EF) = 0.46, and there was no enantioselectivity in the other vegetables. The degradation of napropamide in the five matrixes was fast, and there was no enantioselectivity. Chirality 28:108–113, 2014. © 2014 Wiley Periodicals, Inc.     

一株敌草胺降解菌的分离鉴定及降解性能

为探讨酰胺类除草剂敌草胺的微生物降解机理和土壤中敌草胺降解的生物强化性能,从长期使用敌草胺的烟田土壤中分离到一株敌草胺降解细菌菌株,命名为LGY06.经形态特征、生理生化特性及16S rDNA序列分析将其鉴定为蜡状芽孢杆菌.在纯培养条件下,菌株LGY06对敌草胺的降解符合一级动力学特征,7 d内对50 mg·L^-1敌草胺降解率达到75.7%;LGY06降解敌草胺的最适温度和最适pH值分别为35 ℃和8.0.通过气相色谱-质谱鉴定了菌株LGY06降解敌草胺的降解产物并分析了其降解途径,α-萘酚和丙酰胺是主要的降解产物,LGY06对敌草胺的作用方式主要有脱烷基、氧化(或水解),为矿化过程.室内模拟条件下,LGY06能有效促进土壤中敌草胺残留的降解,与未接种灭菌土、非根际土和根际土相比,敌草胺在接种LGY06土壤中的降解半衰期分别缩短了79.5%、36.6%和41.1%.     

Sorption and Desorption of Napropamide in Sandy Soil Amended with Chicken Dung and Palm Oil Mill Effluent

Beach Ridges Interspersed with Swales (BRIS) is a sandy soil and in Malaysia it is found exclusively in the east coast of Peninsular Malaysia. It is a marginal soil because of its low nutrient and water-holding capacity. However, with proper management and organic matter amendments some areas with BRIS soil are cultivated. Napropamide is a selective herbicide widely used to control weeds in BRIS soil. No previous studies have been reported on the effects of organic matter amendments on napropamide sorption in BRIS soil. This study was conducted to determine sorption and desorption of napropamide in BRIS soil amended with chicken dung (CD) and palm oil mill effluent (POME) at 0, 20, 40, and 80 Mg ha^?1. Potential interaction of dissolved organic carbon (DOC) with napropamide and their competition for sorption sites were also determined. Sorption isotherm data were fitted to the log-transformed Freundlich's equation. Sorption of napropamide was higher in soils amended with CD and POME as compared to non-amended soil. At the same rates of application, sorption was higher in soil amended with CD than POME. The Freundlich's coefficient (K_f) values were 0.22, 3.96, and 41.6 for nonamended soil, soil amended with 80 Mg ha^?1 POME, and soil amended with 80 Mg ha^?1 CD, respectively. Desorption of napropamide showed positive hysteresis and the hysteresis were greater with higher rates of CD and POME. There was no association between napropamide and DOC extracted from BRIS soil amended with either CD or POME and also there were no competitions between napropamide and DOC extracted from either CD or POME for sorption sites of the soil samples.