Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
Anal Chim Acta. 2012 Oct 31;750:120-6. doi: 10.1016/j.aca.2012.04.014. Epub 2012 Apr 20.
In the present study, a rapid, highly efficient and environmentally friendly sample preparation method named ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (IL-USA-DLLME), followed by high performance liquid chromatography (HPLC) has been developed for the extraction and preconcentration of four benzophenone-type ultraviolet (UV) filters (viz. benzophenone (BP), 2-hydroxy-4-methoxybenzophenone (BP-3), ethylhexyl salicylate (EHS) and homosalate (HMS)) from three different water matrices. The procedure was based on a ternary solvent system containing tiny droplets of ionic liquid (IL) in the sample solution formed by dissolving an appropriate amount of the IL extraction solvent 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM][FAP]) in a small amount of water-miscible dispersive solvent (methanol). An ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution, which markedly increased the extraction efficiency and reduced the equilibrium time. Various parameters that affected the extraction efficiency (such as type and volume of extraction and dispersive solvents, ionic strength, pH and extraction time) were evaluated. Under optimal conditions, the proposed method provided good enrichment factors in the range of 354-464, and good repeatability of the extractions (RSDs below 6.3%, n=5). The limits of detection were in the range of 0.2-5.0 ng mL(-1), depending on the analytes. The linearities were between 1 and 500 ng mL(-1) for BP, 5 and 500 ng mL(-1) for BP-3 and HMS and 10 and 500 ng mL(-1) for EHS. Finally, the proposed method was successfully applied to the determination of UV filters in river, swimming pool and tap water samples and acceptable relative recoveries over the range of 71.0-118.0% were obtained.
在本研究中,建立了一种快速、高效、环境友好的样品前处理方法,即离子液体辅助超声分散液液微萃取(IL-USA-DLLME),结合高效液相色谱(HPLC),用于从三种不同水基质中提取和预浓缩四种二苯甲酮型紫外线(UV)过滤器(即二苯甲酮(BP)、2-羟基-4-甲氧基二苯甲酮(BP-3)、乙基己基水杨酸酯(EHS)和水杨酸异戊酯(HMS))。该方法基于包含在样品溶液中的微小离子液体(IL)液滴的三元溶剂体系,通过溶解适量的 IL 萃取溶剂 1-己基-3-甲基咪唑六氟磷酸盐([HMIM][FAP])在少量水混溶性分散溶剂(甲醇)中形成。应用超声辅助过程加速形成细的浑浊溶液,这显著提高了萃取效率并缩短了平衡时间。评估了影响萃取效率的各种参数(如萃取和分散溶剂的类型和体积、离子强度、pH 值和萃取时间)。在最佳条件下,该方法提供了 354-464 的良好富集因子,并且萃取具有良好的重复性(RSDs 低于 6.3%,n=5)。检测限范围为 0.2-5.0ng/mL,取决于分析物。BP 的线性范围在 1-500ng/mL 之间,BP-3 和 HMS 的线性范围在 5-500ng/mL 之间,EHS 的线性范围在 10-500ng/mL 之间。最后,该方法成功应用于河流水、游泳池水和自来水样品中 UV 过滤器的测定,获得了 71.0-118.0%范围内可接受的相对回收率。