Yao Zhoulin, Li Xiaoge, Miao Yelong, Lin Mei, Xu Mingfei, Wang Qiang, Zhang Hu
Institute of Quality and Standard for Agricultural Products, Zhejiang Academy of Agricultural Sciences, Hangzhou, 310021, China.
State Key Laboratory Breeding Base for Zhejiang Sustainable Pest and Disease Control, Zhejiang Academy of Agricultural Sciences, Hangzhou, 310021, China.
Anal Bioanal Chem. 2015 Nov;407(29):8849-59. doi: 10.1007/s00216-015-9046-y. Epub 2015 Sep 28.
A novel, sensitive, and efficient enantioselective method for the determination of triadimefon and its metabolite triadimenol in edible vegetable oil, was developed by gel permeation chromatography and ultraperformance convergence chromatography/tandem triple quadrupole mass spectrometry. After the vegetable oil samples were prepared using gel permeation chromatography, the eluent was collected, evaporated, and dried with nitrogen gas. The residue was redissolved by adding methanol up to a final volume of 1 mL. The analytes of six enantiomers were analyzed on Chiralpak IA-3 column (150 × 4.6 mm) using compressed liquid CO2-mixed 14 % co-solvents, comprising methanol/acetonitrile/isopropanol = 20/20/60 (v/v/v) in the mobile phase at 30 °C, and the total separation time was less than 4 min at a flow rate of 2 mL/min. Quantification was achieved using matrix-matched standard calibration curves. The overall mean recoveries for six enantiomers from vegetable oil were 90.1-97.3 %, with relative standard deviations of 0.8-5.4 % intra-day and 2.3-5.0 % inter-day at 0.5, 5, and 50 μg/kg levels. The limits of quantification were 0.5 μg/kg for all enantiomers based on five replicate extractions at the lowest fortified level in vegetable oil. Moreover, the absolute configuration of six enantiomers had been determined based on comparisons of the vibrational circular dichroism experimental spectra with the theoretical curve obtained by density functional theory calculations. Application of the proposed method to the 40 authentic vegetable oil samples from local markets suggests its potential use in enantioselective determination of triadimefon and triadimenol enantiomers. Graphical Abstract Chemical structures and UPC(2)-MS/MS separation chromatograms of triadimefon and triadimenol.
建立了一种新颖、灵敏且高效的对映体选择性方法,用于测定食用植物油中的三唑酮及其代谢物三唑醇,该方法采用凝胶渗透色谱法和超高效汇聚色谱/串联三重四极杆质谱法。植物油样品经凝胶渗透色谱法制备后,收集洗脱液,蒸发并用氮气吹干。残渣用甲醇重新溶解,最终体积为1 mL。在Chiralpak IA - 3柱(150×4.6 mm)上,使用压缩液体CO₂与14%共溶剂混合,其中流动相为甲醇/乙腈/异丙醇 = 20/20/60(v/v/v),在30℃下分析六种对映体的分析物,流速为2 mL/min时总分离时间小于4分钟。采用基质匹配标准校准曲线进行定量。植物油中六种对映体的总体平均回收率为90.1 - 97.3%,在0.5、5和50 μg/kg水平下,日内相对标准偏差为0.8 - 5.4%,日间相对标准偏差为2.3 - 5.0%。基于植物油中最低加标水平的五次重复萃取,所有对映体的定量限均为0.5 μg/kg。此外,通过将振动圆二色性实验光谱与密度泛函理论计算得到的理论曲线进行比较,确定了六种对映体的绝对构型。将该方法应用于当地市场的40个真实植物油样品,表明其在三唑酮和三唑醇对映体的对映体选择性测定中具有潜在应用价值。图形摘要 三唑酮和三唑醇的化学结构及UPC(2)-MS/MS分离色谱图