Analytical and Bioanalytical Chemistry ( IF 4.3 ) Pub Date : 2018-01-02 , DOI: 10.1007/s00216-017-0820-x Jiale Yang , Chen Fan , Dandan Kong , Gang Tang , Wenbing Zhang , Hongqiang Dong , You Liang , Deng Wang , Yongsong Cao
Five novel ionic liquids (ILs), 1,3-dibutylimidazolium bromide [BBMIm][Br], 1-pentyl-3-butylimidazolium bromide [BPMIm][Br], 1-hexyl-3-butylimidazolium bromide [BHMIm][Br], 1,1'-(butane-1,4-diyl)bis(3-butylimidazolium) bromide [C4(BMIm)2][Br2], and 1,1'-(butane-1,4-diyl)bis(3-methylimidazolium) bromide [C4(MIm)2][Br2], were prepared and used in situ to react with bis(trifluoromethane)sulfonamide lithium salt to extract the myclobutanil, tebuconazole, cyproconazole, and prothioconazole from water samples. The results showed that mono-cationic ILs had much better recovery than dicationic ILs, and mono-imidazolium IL bearing butyl groups at N-1 and N-3 sites had the best recovery. When the length of the alkyl substituent group was more than four carbons at N-3 site, the recovery decreased with increase of alkyl chain length of 1-butylimidazolium IL. The extraction efficiency order of triazoles from high to low was [BBMIm][Br], [BPMIm][Br], [BHMIm][Br], [BMIm][Br] (1-butyl-3-methylimidazolium bromide), [C4(BMIm)2]Br2, [C4(MIm)2]Br2. An in situ ionic liquid dispersive liquid–liquid microextraction combined with ultrasmall superparamagnetic Fe3O4 was established as a pretreatment method for enrichment of triazole fungicides in water samples by using the synthetic [BBMIm][Br] as the cationic IL and used to detect analytes followed by high-performance liquid chromatography. Under the optimized conditions, the proposed method showed a good linearity within a range of 5–250 μg L−1, with the determination coefficient (r2) varying from 0.998 to 0.999. High mean enrichment factors were achieved ranging from 187 to 323, and the recoveries of the target analytes from real water samples at spiking levels of 10.0, 20.0, and 50.0 μg L−1 were between 70.1% and 115.0%. The limits of detection for the analytes were 0.74–1.44 μg L−1, and the intra-day relative standard deviations varied from 5.23% to 8.65%. The proposed method can be further applied to analyze and monitor pesticides in other related samples.
中文翻译:
咪唑类离子液体作为萃取溶剂预处理水样中三唑类杀菌剂的合成及应用
五种新型离子液体(ILs),溴化1,3-二丁基咪唑鎓[Br],溴化1-戊基-3-丁基咪唑鎓[BP],溴化1-己基-3-丁基咪唑鎓[BHMIm] [Br] ,1,1'-(丁烷-1,4-二基)双(3-丁基咪唑鎓)溴化物[C 4(BMIm)2 ] [Br 2 ]和1,1'-(丁烷-1,4-二基)双(3-甲基咪唑鎓)溴化物[C 4(MIm)2 ] [Br 2制备,并原位用于与双(三氟甲烷)磺酰胺锂盐反应,以从水样中提取Myclobutanil,tebuconazole,cyproconazole和Prothioconazole。结果表明,单阳离子ILs的回收率要好于离子型IL,而在N-1和N-3位带有丁基的单咪唑类IL的回收率最好。当烷基取代基的长度在N-3位点处大于四个碳原子时,回收率随着1-丁基咪唑鎓IL的烷基链长度的增加而降低。三唑类化合物的萃取效率从高到低的顺序为[BBMIm] [Br],[BPMIm] [Br],[BHMIm] [Br],[BMIm] [Br](1-丁基-3-甲基咪唑鎓溴化物),[ C 4(BMIm)2 ] Br 2,[C 4(MIm)2] Br 2。建立了一种以原位离子液体分散液-液微萃取结合超小型超顺磁性Fe 3 O 4的预处理方法,以合成的[BBMIm] [Br]为阳离子IL,用于富集水样中的三唑类杀菌剂。分析物,然后进行高效液相色谱分析。在最佳条件下,该方法在5–250μgL -1范围内显示出良好的线性,测定系数为(r 2)从0.998到0.999不等。获得的平均富集系数较高,范围为187至323,加标浓度分别为10.0、20.0和50.0μgL -1的真实水样中目标分析物的回收率在70.1%至115.0%之间。分析物的检出限为0.74–1.44μgL -1,日内相对标准偏差在5.23%至8.65%之间。所提出的方法可以进一步应用于分析和监测其他相关样品中的农药。