Department of Pharmacy, Anhui University of Chinese Medicine, Hefei, 230038, Anhui, China.
Department of Biological Physics, University of Science and Technology of China, Hefei, 230026, Anhui, China.
Anal Bioanal Chem. 2018 Aug;410(21):5277-5285. doi: 10.1007/s00216-018-1184-6. Epub 2018 Jun 25.
Recent years have seen a large number of incidents involving the contamination of liquor with phthalate plasticizers (PAEs). There is therefore an urgent need to develop novel analytical strategies for the rapid and sensitive detection of PAEs. The PAE butyl benzyl phthalate (BBP) is very harmful to the human body, so we developed a surface-enhanced Raman spectroscopy (SERS) platform for the rapid detection of BBP in liquor based on liquid-liquid extraction and the simultaneous self-assembly of arrays of Au nanoparticles (Au NPs) at an organic/aqueous interface. The self-assembly of Au NPs occurs under the influence of the surface tension at the interface between the immiscible solvents. In the first step of the strategy, cyclohexane (CYH) is mixed with BBP-containing liquor to extract the BBP. Then the self-assembly of Au NPs at an organic/aqueous interface is induced using the CYH supernatant as the organic phase, a colloid of Au NPs as the aqueous phase, and ethanol as the inducer. During this process, the BBP molecules extracted from the liquor participate directly in the Au NP self-assembly process, which causes the analytes to be loaded into SERS-active nanogaps in the Au NP arrays, thus permitting the sensitive detection of BBP. BBP levels as low as 1.3 mg/kg in the liquor were detected using this method. Fifteen batches of the assembled SERS platform produced a relative standard deviation of 10.58% in the SERS intensity of the peak at 1178 cm generated in the presence of 0.08 ppm crystal violet, indicating that this strategy possesses good reproducibility. Furthermore, interfacial assembly allowed the dual-analyte detection of BBP in the organic phase and an edible pigment (sunset yellow) in the aqueous phase to be achieved with high sensitivity and credible reproducibility using the SERS platform. Interfacial self-assembled SERS-active arrays therefore show great potential for the rapid and sensitive in situ detection of BBP in liquor samples. Graphical abstract ᅟ.
近年来,大量涉及邻苯二甲酸酯类增塑剂(PAEs)污染白酒的事件时有发生。因此,急需开发新的分析策略,以实现对 PAEs 的快速、灵敏检测。邻苯二甲酸丁基苄基酯(BBP)对人体危害极大,因此,我们基于液-液萃取和金纳米粒子(Au NPs)在有机/水界面的同时自组装,开发了一种用于快速检测白酒中 BBP 的表面增强拉曼光谱(SERS)平台。Au NPs 的自组装是在不混溶溶剂界面处的表面张力的影响下发生的。在该策略的第一步中,将环己烷(CYH)与含 BBP 的白酒混合,以萃取 BBP。然后,将 CYH 上清液作为有机相,胶体 Au NPs 作为水相,乙醇作为诱导剂,在有机/水界面诱导 Au NPs 的自组装。在此过程中,从白酒中提取的 BBP 分子直接参与 Au NP 的自组装过程,导致分析物被加载到 Au NP 阵列中的 SERS 活性纳米间隙中,从而实现对 BBP 的灵敏检测。使用该方法可检测到白酒中低至 1.3mg/kg 的 BBP。15 批组装的 SERS 平台在 0.08ppm 结晶紫存在下生成的 1178cm-1 处的 SERS 强度峰的相对标准偏差为 10.58%,表明该策略具有良好的重现性。此外,界面组装允许使用 SERS 平台以高灵敏度和可靠的重现性实现有机相中的 BBP 和水相中的食用色素(日落黄)的双分析物检测。因此,界面自组装 SERS 活性阵列在快速、灵敏的原位检测白酒样品中的 BBP 方面具有很大的潜力。