脲基衍生化β-环糊精液相色谱键合相拆分和测定苹果中已唑醇对映体

Enantioseparation and determination of hexaconazole enantiomers in apple on ureido-β-cyclodextrin-bonded stationary phase by HPLC

手性农药对映体常具有不同的杀虫活性、人体毒性和环境行为。手性农药的残留也给食品安全带来了新问题。利用自制的脲基衍生化β-环糊精键合SBA-15手性固定相(UCDSP),采用高效液相色谱法成功地拆分了手性农药己唑醇对映体,并考察了流动相组成、pH值、柱温等对手性分离的影响。结果表明,以甲醇-水(60:40,v/v)为流动相,流速0.5mL·min^(-1),柱温20℃,检测波长230nm时,己唑醇对映体的分离度2.26,分析时间在15min内。在优化的色谱条件下建立了快速测定苹果中己唑醇对映体含量的新方法。苹果中的已唑醇用乙腈提取,然后用氨基柱净化。己唑醇对映体在0.5~125μg·mL^(-1)浓度范围内呈良好的线性关系(γ≥0.9998),按3倍于噪声信号推算,苹果中己唑醇最小检出量均小于25μg·kg^(-1),两种对映体的加标回收率为88.0%~97.2%,相对标准偏差(RSD)分别小于0.98%和1.2%(n=5)。该环糊精柱制备方法简便,成本较低。对已唑醇有较高的手性选择性,不仅分析时间短,且回收率和重现性较高,在果蔬中手性农药对映体残留分析中存在良好的应用前景。

Chiral pesticides enantiomers often have different biological activity,toxicology and environmental behavior.The residues of enantiomers in food bring new problems to food safety.The hexaconazole enantiomers was sucessfully separated on a kind of homemade ureido-β-cyclodextrin-bonded stationary phase（UCDSP）by high-performance liquid chromatography.Some effect factors such as the composition of mobile phase,pH value,column temperature,etc.on the resolution of hexaconazole enantiomers were studied.The results showed the optimal chromatographic condition was as follows：methanol-water（60：40,v/v）as mobile phase at a flowrate of 0.5mL·min^-1,column temperature at 20 ℃ and detection wavelength at 230 nm.The resolution of hexaconazole enantiomers reached to 2.26 within 15min under the above condition.Based on the optimal condition,a new fast quantitive method about the residues of hexaconazole enantiomers in apple was developed.Hexaconazole enantiomers were extracted from apple sample with acetonitrile,and purified by solid-extracting column with amino group.Good linear relationships were observed in the range of 0.5~125μg·mL^-1 with corelation coefficience（γ≥0.999 8）.According to the sigal-to-noise 3,the detection limits of hexaconazole in apple were less than 25μg/Kg.The recoveries of two enantiomers by adding hexaconazole standard were in a range of 88.0%~97.2% for enantiomers with RSD≤0.98% and 1.2%（n=5）,respectively.The preparation of UCDSP column is simple and convenient at low cost.Moreover,the cyclodextrin-based phase has high selectivity,high recoveries and reproducibilities for hexaconazole enatiomers within a rather short analysis time.It show a bright presperous application in the residues determination of hexaconazole enantiomers in food.