Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Key Laboratory of Pesticide Chemistry and Application, Ministry of Agriculture, Beijing 100193, China.
J Chromatogr A. 2011 Sep 23;1218(38):6667-74. doi: 10.1016/j.chroma.2011.07.059. Epub 2011 Jul 24.
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.
建立了一种新颖、灵敏的手性液相色谱-串联质谱法，用于同时测定呋菌唑及其主要代谢物的对映体。分离和测定在反相色谱条件下，使用纤维素手性固定相，Chiralcel OD-RH（150mm×4.6mm）柱，在 0.5mL/min 的流速下进行等度洗脱。还研究了三种纤维素柱和三种直链淀粉柱对分离的影响。通过旋光检测器确定了洗脱对映体的洗脱顺序。采用 QuEChERS（快速、简便、廉价、有效、坚固和安全的缩写）方法和固相萃取（SPE）分别用于土壤和水样的提取和净化。评价了参数包括基质效应、线性、精密度、准确度和稳定性。在最佳条件下，所有对映体从土壤样品中的平均回收率为 82.5-104.1%，日内相对标准偏差（RSD）为 2.7-9.5%，5、25 和 50μg/kg 水平的日间 RSD 为 5.7-11.2%；从水样中的平均对映体回收率为 81.8-104.6%，日内 RSD 为 2.6-11.4%，0.25、0.5 和 2.5μg/L 水平的日间 RSD 为 5.3-10.4%。在土壤和水基质校准曲线的 1.0-125μg/L 范围内，每个对映体的相关系数 R2≥0.9991。所有对映体在土壤和水中的检测限（LOD）均小于 0.8μg/kg，定量限（LOQ）均不超过 2.5μg/kg。方法验证的结果证实，该方法方便、可靠，可用于同时测定土壤和水中呋菌唑及其主要代谢物的对映体。
