Phthalate esters (PAEs) are a group of serious environmental pollutants, which lead to carcinogenicity or tumorigenicity in human body. In this study, a rapid, sensitive and green method by graphene oxide coated hollow fiber membrane extraction (GO-HFME) coupled with supercritical fluid chromatography (SFC) was proposed for the determination of 11 phthalate esters in bottled beverages. Graphene oxide (GO) was prepared and coated onto a porous hollow fiber membrane (HFM) to reinforce the efficiency of membrane extraction. The modified hollow fiber membrane was employed for the extraction of phthalate esters from bottled beverages prior to the determination by the supercritical fluid chromatography with UV detection. To achieve the maximum extraction efficiency, several parameters were investigated including GO concentration, extraction time, desorption solution and desorption time. SFC variables including stationary phase, modifier composition and percentage, column temperature, flow rate and backpressure were studied to improve the separation conditions. Under these optimized conditions, all the studied 11 phthalate esters were well separated and simultaneously determined in 7 min by SFC. The performance of the developed method was evaluated. Good linearity was observed (R ≥ 0.999) in the range of 0.02-10.0 μg/mL with limit of detection (LOD, S/N = 3) ranging from 1.5 to 3.0 ng/mL. Recoveries of all the PAEs for the spiked samples were between 92.1% and 99.3% with satisfactory relative standard deviations (RSD) less than 5.9%. The proposed method is time-saving, green, simple and robust, which will be an alternative way to the analysis of PAEs in real samples.

中文翻译：

---

氧化石墨烯包覆中空纤维膜萃取-超临界流体色谱法同时测定瓶装饮料中的11种邻苯二甲酸酯

邻苯二甲酸酯（PAEs）是一组严重的环境污染物，对人体具有致癌性或致瘤性。在本研究中，提出了一种通过氧化石墨烯涂层中空纤维膜萃取 (GO-HFME) 结合超临界流体色谱 (SFC) 的快速、灵敏和绿色的方法来测定瓶装饮料中的 11 种邻苯二甲酸酯。制备氧化石墨烯（GO）并涂覆在多孔中空纤维膜（HFM）上以增强膜提取的效率。改性中空纤维膜用于萃取瓶装饮料中的邻苯二甲酸酯，然后用紫外检测超临界流体色谱法测定。为了获得最大的提取效率，研究了几个参数，包括 GO 浓度、提取时间、解吸溶液和解吸时间。研究了 SFC 变量，包括固定相、改性剂组成和百分比、柱温、流速和背压，以改善分离条件。在这些优化条件下，所有研究的 11 种邻苯二甲酸酯都得到了很好的分离，并通过 SFC 在 7 分钟内同时测定。对所开发方法的性能进行了评估。在 0.02-10.0 μg/mL 范围内观察到良好的线性 (R ≥ 0.999)，检测限 (LOD，S/N = 3) 范围为 1.5 至 3.0 ng/mL。加标样品的所有 PAE 回收率介于 92.1% 和 99.3% 之间，相对标准偏差 (RSD) 小于 5.9%。该方法省时、绿色、简单且稳健，将成为分析实际样品中PAEs的一种替代方法。