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Guanidinium ionic liquid-based surfactants as low cytotoxic extractants: Analytical performance in an in-situ dispersive liquid–liquid microextraction method for determining personal care products
Journal of Chromatography A ( IF 3.8 ) Pub Date : 2017-05-01 , DOI: 10.1016/j.chroma.2017.04.061
Idaira Pacheco-Fernández , Verónica Pino , Juan H. Ayala , Ana M. Afonso

The IL-based surfactant octylguanidinium chloride (C8Gu-Cl) was designed and synthetized with the purpose of obtaining a less harmful surfactant: containing guanidinium as core cation and a relatively short alkyl chain. Its interfacial and aggregation behavior was evaluated through conductivity and fluorescence measurements, presenting a critical micelle concentration value of 42.5 and 44.6 mmol L−1, respectively. Cytotoxicity studies were carried out with C8Gu-Cl and other IL-based and conventional surfactants, specifically the analogue 1-octyl-3-methylimidazolium chloride (C8MIm-Cl), and other imidazolium- (C16MIm-Br) and pyridinium- (C16Py-Cl) based surfactants, together with the conventional cationic CTAB and the conventional anionic SDS. From these studies, C8Gu-Cl was the only one to achieve the classification of low cytotoxicity. An in situ dispersive liquid–liquid microextraction (DLLME) method based on transforming the water-soluble C8Gu-Cl IL-based surfactant into a water-insoluble IL microdroplet via a simple metathesis reaction was then selected as the extraction/preconcentration method for a group of 6 personal care products (PCPs) present in cosmetic samples. The method was carried out in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The method was properly optimized, requiring the use of only 30 μL of C8Gu-Cl for 10 mL of aqueous sample with a NaCl content of 8% (w/v) to adjust the ionic strength and pH value of 5. The metathesis reaction required the addition of the anion exchange reagent (bis[(trifluoromethyl)sulfonyl]imide − 1:1 molar ratio), followed by vortex and centrifugation, and dilution of the final microdroplet up to 60 μL with acetonitrile before the injection in the HPLC-DAD system. The optimum in situ DLLME-HPLC-DAD method takes ∼10 min for the extraction step and ∼22 min for the chromatographic separation, with analytical features of low detection limits: down to 0.4 μg L−1; high reproducibility: with RSD values lower than 10% (intra-day) and 16% (inter-day) for a spiked level of 15 μg L−1; and an average enrichment factor of 89. The requirement of low volumes (30 μL) of a low cytotoxic IL-based surfactant allows the method to be considered less harmful than other common analytical microextraction approaches.



中文翻译:

胍基离子液体基表面活性剂作为低细胞毒性提取剂:原位分散液-液微萃取法测定个人护理产品的分析性能

设计并合成了基于IL的表面活性剂辛基胍盐氯化物(C 8 Gu-Cl),目的是获得危害较小的表面活性剂:包含胍盐作为核心阳离子和较短的烷基链。通过电导率和荧光测量评估了其界面和聚集行为,其临界胶束浓度分别为42.5和44.6 mmol L -1。用C 8 Gu-Cl和其他基于IL的表面活性剂和常规表面活性剂,特别是类似的1-辛基-3-甲基咪唑鎓氯化物(C 8 MIm-Cl)和其他咪唑鎓-(C 16 MIm-Br)进行了细胞毒性研究。和吡啶鎓-(C 16基于Py-Cl)的表面活性剂,以及常规的阳离子CTAB和常规的阴离子SDS。从这些研究中,C 8 Gu-Cl是唯一实现低细胞毒性分类的化合物。一个原位基于变换所述水可溶性C-分散液液微萃取(DLLME)方法8通过一个简单的复分解反应的基于IL-谷-CL的表面活性剂为水不溶性IL微滴,然后选择为用于提取/富集方法化妆品样本中包含一组6种个人护理产品(PCP)。该方法与高效液相色谱(HPLC)和二极管阵列检测(DAD)相结合进行。该方法经过适当优化,仅需使用30μLC 8Gu-Cl用于10 mL NaCl含量为8%(w / v)的水性样品,以调节离子强度和pH值为5。复分解反应需要添加阴离子交换试剂(双[((三氟甲基)磺酰基]乙酰亚胺-1:1摩尔比),然后涡旋和离心分离,然后在HPLC-DAD系统中进样前用乙腈将最终的微滴稀释至60μL。最佳的原位DLLME-HPLC-DAD方法需要约10分钟的萃取步骤和约22分钟的色谱分离时间,且具有检测限低的分析功能:低至0.4μgL -1;高重现性:对于15μgL -1的加标水平,RSD值低于10%(日内)和16%(日间); 平均富集因子为89。低体积(30μL)的低细胞毒性基于IL的表面活性剂的要求,使该方法被认为比其他常见的分析微萃取方法危害更小。

更新日期:2017-05-01
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